US3183149A - Process for making cellulosic textiles rot resistant with zirconium salts and phenols - Google Patents

Description

United States Patent PROCESS FOR MAKING CELLULOSIC TEXTILES ROT RESISTANT WITH ZIRCONIUM SALTS AND PHENOLS Elwood J. Gonzales, Kenner, and Clark M. Welch and John D. Guthrie, New Orleans, La., assignors to the United States of America as represented by the Secretary ofAgriculture No Drawing. Filed Sept. 20, 1962, Ser. No. 225,166

22 Claims. (Cl. 16738.7)

(Granted under Title 35, US. Code (1952), see. 266) A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This invention relates to the bonding of phenolic compounds to cellulosic textiles with zirconium salts. An object of the invention is to produce cellulosic textiles with increased rot resistance. A second object is to provide enhanced breaking strength. Other objects will become evident from a description of the invention.

It is well known that phenols are highly effective in inhibiting the attack of microorganisms on a given substrate. Heretofore, no satisfactory method has been devised for durably bonding the phenol to a solid substrate without at the same time destroying the bacteriocidal activity of the phenol. The present invention utilizes zirconium salts as the bonding agent. These have the property of undergoing olation in aqueous media to give polymers of the type 0 0 (IIO) Z r r Z r(OH) //\L Moreover, the zirconium salts and their olated polymers have the property of forming coordination complexes with phenols and with hydroxy compounds in general (B. I. Intorre and A. E. Martell, J. Am. Chem. Soc. 82, 358 (1960)). It is therefore likely that the zirconium salts serve in the present invention to form polymers which coordinate both with the phenol and with hydroxyl groups of the cellulose, thus forming a bridge between the two. It is found that this mode of bonding does not destroy the ability of the phenol to inhibit attack by microorganisms, and unexpectedly, the tensile strength of the textiles so treated is found to be increased. The coating obtained has no appreciable effect on the suppleness of the textile material. Many of the finishes also impart water repellency to the textile. The treatments are highly durable to washing with hot water and to extraction with hot organic solvents.

The process described herein differs from all previously described textile finishing methods that utilize metal salts, hydroxides or oxides as bonding agents, in that heretofore only those organic materials which were chelating agents could be bonded to cellulosic textiles. The present invention applies to phenols in general, including those that are incapable of forming chelate rings. Monohydric phenols as well as polyhydric phenols may be applied. Among the phenols most efficiently bound to cellulosic textiles are those whose complexes with zirconium salts have a high stability constant, and also those whose complexes with zirconium salts are insoluble in water. Phenols having very large and bulky substituents were less efficiently bonded to cellulose. The present invention also is novel in that it permits the bonding of the phenol to the cellulose in amounts up to 10% of the latter by weight, in some cases. Not all phenols are equally effecice tive in imparting rot resistance to cellulose. Halogenated phenols such as pentachlorophenol, pentabromophenol or 2,2-methylenebis(4-chlorophenol) are especially active in inhibiting microbiological attack. Mercurated phenols such as p-hydroxyphenylmercuric chloride also are effective. The phenol may be used directly or as its alkali metal salt.

Although any salt of tetravalent zirconium soluble in water at a pH of 2 or higher may be used, the zirconium salt is preferably one derived from zirconium hydroxide, or zirconyl hydroxide, and a volatile acid having an acid dissociation constant equal to or less than 5 10- and a boiling point equal to or less than 160 C. With zirconium salts or zirconyl salts of strong acids, the acid liberated during the olation process will degrade and tender the cellulosic textile material. The olation proceeds more nearly to completion, the more readily the acid is removed by volatilization. Examples of suitable salts are zirconium acetate, zirconyl acetate and sodium zirconium acetate.

In carrying out the process of this invention, the phenol and the zirconium salt may be applied either together or separately to the cellulosic textile material, followed by drying the textile at 70-170 C. If the phenol and the zirconium salt are applied together, the textile material is soaked in a homogeneous solution or an emulsion of the phenol and the zirconium salt in an inert solvent. Solvents suitable for preparing homogeneous solutions include water and water-miscible organic solvents such as low-molecular-weight alcohols, ketones, cyclic ethers and amides, as well as mixtures of water with such organic solvents. Vehicles suitable for emulsions may be made from mixtures of water with water-immiscible inert solvents such as aromatic or aliphatic hydrocarbons.

If the zirconium salt and the phenol or the alkali metal salt of the phenol are applied in separate setps, any order of addition may be used, but it is preferable to apply the zirconium salt first. The textile material is soaked in an aqueous solution containing 1-25% by weight of the zirconium salt, concentrations of 515% being preferable for many purposes. The cellulosic textile material is subsequently dried either by heat or by being allowed to stand at room temperature, after which it is soaked in a solution of the phenol or an alkali metal salt of the phenol dissolved either in water or in any inert organic solvent, such as an aromatic or aliphatic hydrocarbon, alcohol, ester, ketone or ether. The concentration of the phenol or its alkali metal salt to be used will depend on the amount needed in the textile finish, but for most purposes may fall in the range of 05-15%. The textile material is subsequently dried at a temperature of 70170 C.

The materials to which the processes of this invention may be applied include any solid cellulosic material in the form of fiber, yarn, or fabric. Cotton, rayon, ramie, jute, and flax are suitable materials.

The following examples illustrate some of the procedures which may be used and some of the rot-resistant products which can be obtained. The invention is not limited to those substances and conditions mentioned in the examples since the scope of the invention may include many compounds and variations in procedure not cited. Rot resistance tests were carried out by ASTM Method D684-45T (AATCC Method 30-4957). Breaking and tearing strengths were measured in the warp direction, the breaks being made on 1" strips. Water repellency was measured by AATCC test method 22-1952.

Example 1 Cotton print cloth x 80) weighing 16.75 grams was soaked in 12.5% aqueous zirconium acetate. The fabric was then padded once through a laboratory wringer and cured 5 minutes at C. in a forced draft oven. Im-

mediately after curing, the print cloth was soaked in a solution of grams pentachlorophenol dissolved in 50 m1. absolute ethanol, again padded once through the wringer, and cured minutes at 135 C. in the oven. The swatch was extracted minutes at the boil with ethanol, rinsed once with this solvent, oven-dried and air-equilibrated overnight. The fabric showed a 9.4% increase in Weight and contained 0.70% chlorine. Its breaking strength was 10% greater than for untreated fabric. Its rot resistance, as compared with controls treated as above but omitting one of the reagents and also omitting the extraction step was as follows:

Example 2 The procedure of Example 1 was repeated using 95% ethanol as the solvent for the pentachlorophenol, and omitting the ethanol extraction of the treated fabric. The weight gain was 14.5%, the chlorine content was 3.48%, and the ash content was 6.04%. The fabric had a breaking strength of 63.3 lbs. (thread count86) and an E1- mendorf tear strength of 750 g. Moderate water repel lency was indicated by a spray rating of 50. The untreated fabric was the same as used in Example 1, having a breaking strength of 54.3 lbs. (thread count82) and a tearing strength of 1034 g.

The treated fabric retained a breaking strength of 53.1 lbs. after 10 weeks burial and 18.5 lbs. after 12 weeks burial. Data for control fabrics are given in Example 1.

Example 3 The procedure of Example 2 was repeated except that the concentration of pentachlorophenol was tripled and the treated fabric was extracted with boiling 95% ethanol for 15 minutes. The fabric showed a weight increase of 13.9%, a chlorine content of 0.39% and an ash content of 7.78%. The breaking strength of 67.7 lbs. decreased to 14 and 5.2 pounds after the fabric was in the rot bed 7 and 8 weeks, respectively. Data for control fabrics are given in Example 1.

Example 4 A 13.80 g. sample of 80 x 80 print cloth was soaked in 12.5% aqueous zirconium acetate, padded once through a laboratory wringer and cured 5 minutes in a forced-air oven at 135 C. The cured fabric was then immediately treated with a 6.8% solution of sodium pentachlorophenate, padded once as above and cured 10 minutes at 135 C. in the oven. Washing 5 minutes each in cold and hot running tap water, oven-drying, and allowing the fabric to equilibrate overnight, produced a light tan cloth having 19.8% weight increase, 3.32% chlorine, 7.53% total ash, and a 50 spray rating. Breaking and Elmendorf tear strengths were 63.2 lbs. (thread count 86) and 693 g., respectively. After 7 weeks soil burial, the breaking strength was reduced to 21.5 lbs. after 10 weeks the strength fell to 12.2 lbs. This treatment may be compared with the zirconium acetate control given in Example 1 and also with a sodium hydroxide-zirconium acetate control prepared as follows: print cloth was treated with 12.5% zirconium acetate and cured as above. The cloth was subsequently steeped in a 3.2% aqueous sodium hydroxide, wrung as before. cured 10 minutes at 135 C. in the oven, water-washed as above, oven-dried and air cquilibratcd. The following properties were 4 noted: 11.3% add-on, 8.40% ash, a breaking strength of 63.6 lbs., and an Elmendorf tearing strength of 740 g. After only 10 days in the rot bed, the breaking strength decreased to 2.3 lbs. The test and controls show that the sodium pentachlorophenate was bonded to fabric and imparted rot resistance to it.

Example 5 Print colth x 80) was steeped in 12.5% aqueous zirconium acetate, padded once through the wringer, and cured as before. The cured fabric was then soaked in a 6.1% solution of pentachlorophenol containing excess sodium hydroxide (3 g. of the phenol was added to 15 ml. 10% aqueous sodium hydroxide and the precipitated sodium salt dissolved with stirring in 30 ml. distilled water), wrung once as above, cured 10 minutes at 135 C., water-washed, oven-dried, and equilibrated overnight. A very light tan fabric, possessing a good hand, 0 spray rating and 11.7% weight gain was obtained. Soil burial disintegrated the material in 3 weeks. Breaking and tear strength were originally 66.3 lbs. (thread count-87) and 750 g., respectively. Analyses indicated 0.28% chlorine and 7.46% total ash content. This treatment may be compared to the controls cited in Example 4 and Example 1.

Example 6 Print cloth (80 x 80) was treated with 12.5% aqueous zirconium acetate, put through a wringer to give a 117% wet pickup, and cured 5 minutes in the oven at 135 C. In a second step the fabric was soaked in a 10.3% aqueous solution of sodium pentachlorophenate and put through a wringer to give a wet pickup of 148%. It was cured at 135 C. for 10 minutes. After the second curing step, 200 ml. of 0.1 N HCl was used to soak the swatch for 5 minutes. The fabric was washed 5 minutes each in cold and hot running tap water and was ovendried. Properties obtained were a weight gain of 19.5%, 50 spray rating, slight phenolic odor, fair to good hand, light tan color, 5.08% ash content, 5.52% chlorine content, Elmendorf tear strength of 760 g. and a thread count of 87. The original warp breaking strength decreased from 63.3 to 61.3 lbs. on 4 weeks soil burial; after 9 weeks burial it was 24.5 lbs. The controls noted in Example 4 had much less rot resistance.

Example 7 A 14.05 g. sample of 80 x 80 print cloth was soaked in a solution consisting of 25 ml. n-propyl alcohol, 25 ml. of 25% aqueous zirconium acetate (0.033 mole ZrO and 5 g. (.019 mole) pentachlorophenol. The solution was applied in two dips, two nips through a wringer to a wet pickup. Curing conditions were 10 minutes in a forced-air oven at C. Water-washing, ovendrying, extracting with boiling methanol, and equilibrating overnight gave a fabric having a weight gain of 11.9%, 1.19% chlorine, and 5.92% total ash. The treatment imparted a good hand and light tan color to the print cloth. The Elmendorf tear strength was 727 g. Soil burial lowered the breaking strength from 64.7 lbs. (thread count-85) to 45.1 lbs. in 4 weeks and holes were noted in burial strips at 6 weeks. A comparison of observed properties may be made with the untreated fabric as well as the zirconium acetate and pentachlorophenol-treated controls given in Example 1.

Example 8 An emulsion was prepared by adding 5 g. of pentachlorophenol in 30 ml. xylene to a solution of 25 ml. tap water, 25 ml. 25% aqueous zirconium acetate and 7.5 grams of 35% aqueous N-cetyl-N-ethylmorpholinium ethosulfate, the latter serving as the emulsifying and wetting agent. The mixlnre was agitated in a blender for one minute. The emulsion was padded onto 80 x 80 cotton print cloth in two dips and two nips through a wringer, resulting in a 103% wet pickup. Curing was t 9.3 lbs.

Example 9 To 3 g. (0.006 mole) pentabromophenol was added 15 ml. 10% aqueous sodium hydroxide (0.038 mole). White flakes of sodium pentabromophenate which precipitated were redissolved with stirring by addition of 30 ml. distilled water. The 6.1% solution of the sodium salt was applied to 80 x 80 cotton print cloth by soaking, padding once through a laboratory wringer and drying 5 minutes in the oven at 135 C. The cloth was subsequently steeped in 12.5% aqueous zirconium acetate and cured minutes in a 135 C. oven. Washing successively in cold and hot running tap water for 5 minute periods, oven-drying, and equilibrating overnight gave a fabric having the following properties: light tan color, good hand, 50 spray rating, 90 flame resistance (by the strip angle test method), 19.9% weight gain, 5.66% bromine, 6.77% ash content, an Elmendorf tear strength of 710 g. and a breaking strength of 65 lb. (thread count -89). The breaking strength remained at 66.5 lbs. after 14 weeks soil burial.

Example 10 Print cloth was treated by steeping in a 12.5 aqueous zirconium acetate solution, cured 5 minutes at 135 C. in an oven after passing the soaked fabric once through wringer rolls to give a 113% wet pickup. A second bath consisting of a solution of 2.02 grams (0.0075 mole) 2,2'-methylenebis(4-chlorophenol) in 50 ml. of 95% ethanol, and containing 0.3 ml. of the cationic wetting agent of Example 8, was used to soak the fabric which was subsequently wrung as above (103% wet pickup) and cured 10 minutes at 135 C.' Washing 5 minutes each in cold and hot running tap water, oven-drying and air equilibrating gave a fabric having a 16.1% weight gain, a yellow color, somewhat rough hand, and slight water repellency. It had a breaking strength of 67.8 lbs., an Elmendorf tearing strength of 700 g., and contained 6.75% ash as well as 1.07% chlorine. Soil burial tests gave the following results for breaking strength (in pounds): 69.8 after 6 weeks, 61.1 after 11 weeks, 57.0 after 12 weeks, 30.5 after 20 weeks. A control in which the zirconium acetate treatment was omitted showed a weight gain of 0.8%, a pale yellow color, good hand and no water repellency. Values of 63.1 lbs. (thread count-- 85) and 810 g. were observed for the breaking and Elmendorf tear strengths, respectively. The fabric contained 0.48% chlorine. The control was observed to rot in just 3 weeks of burial. This shows that the zirconium Cotton print cloth was soaked in 12.5% aqueous zirconium acetate, padded once through a wringer to a 108% wet pickup, and cured in the oven 5 minutes at 135 C. A second treatment was then made with a solution composed of 2.02 g. (0.0075 mole) 2,2'-methylenebis(4- chlorophenol), 33 ml. 0.91% aqueous sodium hydroxide (0.0075 mole), 17 ml. distilled water, and 0.3 ml. of the cationic surfactant of Example 8. Padding was performed as in the first step, giving a 126% wet pickup. Curing was done 10 minutes at 135 C., followed by washing 5 minutes successively in cold and hot running tap water, oven-drying, and air-equilibrating overnight. The following properties were noted: 16.1% weight gain, a slight degree of water repellency, 6.49% ash, 1.49% chlorine, an Elmendorf tear strength of 760 g., and a breaking 6 strength of 67.2 lbs. (thread count-88). The breaking strength decreased to 63.9 (3 weeks), 50.9 (6 weeks), 15.9 (11 weeks) after soil burial.

Example 12 Example 11 was repeated using only half as great a concentration of zirconium acetate. The weight gain was 10%. The fabric was lemon-yellow and had a good hand. Analytical data showed the treated cloth contained 4.04% ash and 1.51% chlorine. The Elmendorf tear strength was 750 g. and the breaking strength was 69.9 lbs. (87 thread count). This breaking strength decreased to 66.4, 66.0, 23.8, and 20.2 lbs. after 2, 3, 6, and 11 weeks exposure, respectively, to bacteria-inoculated soil.

Example 13 Cotton print cloth was treated by steeping in 12.5% aqueous zirconium acetate, padding once through laboratory squeeze rolls to a 112% wet pickup and curing 5 minutes in the oven at 135 C. A second bath was prepared by diluting 2.02 g. (0.0075 mole) of 2,2'-methylenebis(4-ohlorophenol) and 12 m1. 5% aqueous sodium hydroxide (0.015 mole) with 38 ml. of water. A 0.3 ml. quantity of the cationic wetting agent of Example 8 was then added to the resulting solution. Padding as above to a wet pickup, curing 10 minutes at C., washing 5 minutes each in cold and hot running tap water, oven-drying and air-equilibrating overnight produced a fabric having 13.6% weight gain, a yellow color, and slight water repellency. The ash and chlorine contents were 6.88% and 1.15%, respectively. The Elmendorf tear strength was 750 g. The original breaking strength of 60.7 lbs. (86 thread count) was unchanged after 6 weeks soil burial. It decreased to 51.3 lbs. at 11 weeks and 33.1 lbs. at 14 weeks.

Example 14 Cotton print cloth (80 x 80) was treated by soaking one minute in a 12.5% aqueous zirconium acetate solution, padding once through a laboratory wringer, and curing 5 minutes in a forced draft oven at 135 C. Immediately after curing, the fabric was again soaked one minute in a solution of 1.65 g. (0.005 mole) of p-hydroxyphenylmercuric chloride dissolved in 60 ml. tetrahydrofuran, padded as above, and cured 10 minutes at 135 C. Extracting the swatch with tetrahydrofuran for 15 minutes at the boil, washing 5 minutes successively in cold and hot runing .tap water, and air-drying overnight gave a very pale gray fabric having a 13.5% weight gain, and a good hand. The ash content was 6.97% and the chlorine content was 0.046%. The Elmendorf tear strength was 760 g. and the breaking strength was 63.9 lbs. (86 thread count). The treated fabric after 4 weeks in the rot bed was in good condition. However, the warp breaking strength at 6 weeks was 8.5 lbs. A control experiment run in exactly the same manner but omitting the p-hydroxyphenylmercuric chloride showed a 13.6% weight gain, a good hand, and a 50 spray rating. The ash content was 7.17%, the Elmendorf tear strengthwas 1000 g., and the breaking strength was 60.6 lbs. (86 thread count). This decreased to 11.1 lbs. in just 2 weeks exposure to soil-borne microorganisms, showing that the presence of p-hydroxyphenylmercuric chloride was essential for rot resistance.

Example 15 Print cloth was first treated, padded, and cured with zirconium acetate as in Example 14. In a second step the cured fabric was soaked 5 minutes in a solution containing 60 ml. distilled water, 0.4 g. (0.010 mole) sodium hydroxide, and 1.65 g. (0.005 mole) p-hydroxyphenylminutes at the boil, washing minutes successively in cold and hot running tap water, and air drying was given the fabric. The weight gain was 12.2%. The resulting fabric, which was white in color and had a good band, contained 7.07% ash and 0.041% chlorine. The Elmendorf tear strength was 1120 g. Its breaking strength of 66.7 lbs. (86 thread count) decreased to 46.3 lbs. after 6 weeks in the soil bed. The treated cloth remained intact for 9 weeks but rotted at 10 weeks.

Example 1 6 To 30 ml. of 25% aqueous zirconium acetate was added 50 ml. of dimethylformamide and 1.65 grams (0.005 mole) p-hydroxyphenylmercuric chloride. The solid was dissolved with vigorous stirring. Cotton print cloth (80 x 80) was soaked in the nearly colorless solution for one minute, then passed once through a laboratory wringe-r and cured 10 minutes at 135 C. in an oven. The cured fabric was given a minute afterboil in dimethylformamide prior to-wastu'ng and drying as in Example 15. The weight gain was 10.4%. The fabric was very slightly discolored and had a fair hand. The ash content was 5.18% and the chlorine content was 0.042%. The Elmendorf tear strength was 880 g. and the breaking strength was 67.5 lbs. (87 thread count). A control in which only the mercuric compound was omitted in the procedure showed a weight gain of 10.2%. Total ash found was 5.85%. The Elrnendorf tear strength was 810 g. and the breaking strength was 61.2 lbs. (87 thread count). The fabric containing the mercury compound resisted rotting by microorganisms for 3 weeks but began to decompose at 5 weeks. The control rotted in only one week.

Example 17 The procedure was similar to that described in Example 16 with the exception that tetrahydrofuran was used as the afterboil solvent. The weight gain obtained was 10.8%. A fairly white color and a fair hand were noted. The ash and chlorine contents were 5.49 and 0.008%, respectively. The Elmendorf tear strength was 790 g. and the breaking strength was 64.7 lbs. (84 thread count). The breaking strength decreased to 25.6 lbs. after 5 weeks soil burial. Extensive rotting was noted at 6 weeks. A control similarly run but with the omission of the mercury compound had a 10.6% weight gain and contained 5.84% ash. The Elmendorf tear strength was 820 g. and the breaking strength was 63.5 lbs. (thread count86). The control rotted in one week.

We claim:

1. A process for imparting increased rot-resistance,

breaking strength, and water repellency to a cellulosic textile material which comprises treating the cellulosic textile material with reagents consisting of from 0.5- 15% by weight of a phenol, from 1-25% by weight of a zirconium salt of a volatile acid the dissociation constant of which is not greater than 5 10 and the boiling point of which is not higher than 160 C., the balance of the cellulosic textile treating reagent being a liquid which is chemically inert with respect to cellulose and chemically inert with respect to the said reagents and drying the treated cellulosic textile material at a temperature of from 70-170 C.

2. A process for imparting increased rot-resistance, breaking strength, and water repellency to a cellulosic textile material which comprises treating the cellulosic textile material with reagents consisting of from 05-15% by weight of a phenol selected from the group consisting of pentachlorophenol, pentabromophenol, 2,2'-methylenebis(4-chlorophenol), p-hydroxyphenylmercuric chloride, from l-% by weight of a zirconium salt of a volatile acid the dissociation constant of which is not greater than 5 10- and the boiling point of which is not higher than 160 C., the balance of the cellulosic textile treating reagent being a liquid which is chemically inert with respect to cellulose and chemically inert with respect to the said reagents and drying the treated cellulosic textile material at a temperature of from -170 C.

3. The process of claim 2 in which the phenol is pentachlorophenol.

4. The process of claim 2 in which the phenol is pentabromophenol.

5. The process of claim 2 in which the phenol is 2,2- methylenebis (4-chlorophenol) 6. The process of claim 2 in which the phenol is phydroxyphenylmercuric chloride.

7. A process for imparting increased rot-resistance, breaking strength, and water repellency to a cellulosic textile material which comprises treating the cellulosic textile material with reagents consisting of from 0.5- 15% by weight of the alkali metal salt of a phenol, from 1-25% by weight of a zirconium salt of a volatile acid the dissociation constant of which is not greater than 5x10" and the boiling point of which is not higher than C., the balance of the cellulosic textile treating reagent being a liquid which is chemically inert with respect to cellulose and chemically inert with respect to the said reagents and drying the treated cellulosic textile material at a temperature of from 70-170 C.

8. A process for imparting increased rot-resistance, breaking strength, and water repellency to a cellulosic textile material which comprises treating the cellulosic textile material with reagents consisting of from 0.5- 15 by weight of the alkali metal salt of a phenol selected from the group consisting of pentachlorophenol, pentabromophenol, 2,2 methylenebis-(4-chlorophenol) p -hylroxyphenylmercuric chloride, from 125% by weight of a zirconium salt of a volatile acid the dissociation constant of which is not greater than 5 X 10- and the boiling point of which is not higher than 160 C., the balance of the cellulosic textile treating reagent being a liquid which is chemically inert with respect to cellulose and chemically inert with respect to the said reagents and drying the treated cellulosic textile material at a temperature of from 70-170 C.

9. The process of claim 8 in which the phenol is pentachlorophenol.

10. The process of claim 8 in which the phenol is pentabromophenol.

11. The process of claim 8 in which the phenol is 2,2- methylenebis (4-chlorophenol) 12. The process of claim 8 in which the phenol is phydroxyphenylmercuric chloride.

13. A process for imparting increased rot-resistance, breaking strength, and water repellency to a cellulosic textile material which comprises treating the cellulosic textile material with an aqueous medium containing about from 05-15% by weight of a phenol and about from 1-25% by weight of a zirconium salt of a volatile acid the dissociation constant of which is not greater than 5 X 10" and the boiling point of which is not higher than 160 C., and drying the treated cellulosic textile material at a temperature of about from 70-170 C.

14. The process of claim 13 wherein the phenol is selected from the group consisting of pentachlorophenol, pentabromophenol, 2,2-methylenebis(4 chlorophenol), and p-hydroxyphenylmercuric chloride.

15. The process of claim 13 wherein the zirconium salt is zirconium acetate.

16. A process for imparting increased rot-resistance, breaking strength, and water repellency to a cellulosic textile material which comprises treating the cellulosic textile material with an aqueous medium containing about from 05-15% by weight of a phenol selected from the group consisting of pentachlorophenol, pentabromophenol, 2,2-methylenebis(4-chlorophenol), and p-hydroxyphenylmercuric chloride and about from 125% by weight of zirconium acetate, and drying the treated cellulosic textile material at a temeprature of about from 70-170 C.

17. A process for imparting increased rot-resistance,

breaking strength, and water repellency to a cellulosic textile material which comprises treating the cellulosic textile material with an aqueous medium containing about from 05-15% by weight of an alkali metal salt of a phenol and about from 1-25% by weight of a zirconium salt of a volatile acid the dissociation constant of which is not greater than 5x10- and the boiling point of which is not higher than 160 C., and drying the treated cellulosic textile material at a temperature of about from 70-170 C.

18. The process of claim 17 wherein the phenol is selected from the group consisting of pentachlorophenol, pentabromophenol, 2,2'-methylenebis(4 chlorophenol) and p-hydroxyphenylmercuric chloride.

19. The process of claim 17 wherein the zirconium salt is zirconium acetate.

20. A process for imparting increased rot-resistance, breaking strength, and water repellency to a cellulosic textile material which comprises treating the cellulosic textile material with an aqueous medium containing about from 05-15% by weight of an alkali metal salt of a phenol selected from the group consisting of pentachlorophenol, pentabromophenol, 2,2'-methylenebis(4- chlorophenol), and p-hydroxyphenylmeircuric chloride and about from 1-25% by weight of zirconium acetate, and drying the temperature of about from 70-170 C.

21. The process of claim 20 wherein the alkali metal salt of the phenol is sodium pentachlorophenate.

22. The process of claim 20 wherein the alkali metal salt of the phenol is sodium 'pentabromophenate.

References Cited by the Examiner UNITED STATES PATENTS 2,713,008 7/55 Schulenburg 117----138.5 2,762,158 9/56 Dutfey 167--38.6 2,913,369 11/59 Haslam 167-30 2,939,164 6/60 Rosenthal 167--30 OTHER REFERENCES Intorre et al.: J.A.C.S., vol. 82, p. 358 (1960).

JULIAN S. LEVI'IT, Primary Examiner.

treated cellulosic textile material at a

Claims (1)

1. A PROCESS FOR IMPARTING INCREASED ROT-RESISTANCE, BREAKING STRENTH, AND WATER REPELLENCY TO A CELLULOSIC TEXTILE MATERIAL WHICH COMPRISES TREATING THE CELLULOSIC TEXTILE MATERIAL WITH REAGENTS CONSISTING OF FROM 0.515% BY WEIGHT OF A PHENOL, FROM 1-25% BY WEIGHT OF A ZIRCONIUM SALT OF A VOLATILE ACID THE DISSOCIATION CONSTANT OF WHICH IS NOT GREATER THAN 5X10-3 AND THE BOILING POINT OF WHICH IS NOT HIGHER KTHAN 160*C., THE BALANCE OF THE CELLULOSIC TEXTILE TREATING REAGENT BEING A LIQUID WHICH IS CHEMICALLY INERT WITH RESPECT TO CELLULOSE AND CHEMICALLY INERT WITH RESPECT TO THE SAID REAGENTS AND DRYING THE TREATED CELLULOSIC TEXTILE MATERIAL AT A TEMPERATURE OF FROM 70-170*C.