US3917446A

US3917446A - Single bath fungicidal chrome-zirconyl acetate mineral dyeing process for cellulosics

Info

Publication number: US3917446A
Application number: US453910A
Authority: US
Inventors: Charles J Conner
Original assignee: US Department of Agriculture USDA
Current assignee: US Department of Agriculture USDA
Priority date: 1974-03-22
Filing date: 1974-03-22
Publication date: 1975-11-04
Anticipated expiration: 1992-11-04

Abstract

The present unique process is based on an acid complex of chromium hydroxydiacetate and zirconyl acetate and a dodecylbenzylfurfuryldimethyl ammonium chloride quaternary, with or without an aliphatic polyether wetting agent. The clear blackish-green bath is stable for days, and decomposes on cellulosics, with heat, to produce a chrome gray-green mineral dyeing along with a quaternary-zirconium fungicide. The process makes it possible to produce a chrome fungicidal mineral dyeing from a single bath zirconyl acetate system, where no alkali is required, and only one bath is required to deposit both dye and fungicide.

Description

United States Patent 1 Conner Nov. 4, 1975 [75] lnventorz Charles J. Conner, Metairie, La.

[73] Assignee: The United States of America as represented by the Secretary of Agriculture, Washington, DC.

[22] Filed: Mar. 22, 1974 [21] Appl. No.: 453,910

[52] US. Cl. 8/52; 8/99; 8/115.6; 117/1385; 252/8.8

[51] Int. Cl. C09B 63/00; D06P 3/64 [58] Field of Search .1 8/52, 99, 115.6

[56] References Cited UNITED STATES PATENTS 1,648,433 11/1927 White 8/17 3,169,043 2/1965 Baumgartner 8/4 3,423,162 1/1969 Papayannis et a1. 8/94.25

FOREIGN PATENTS OR APPLICATlONS 778,415 7/1957 United Kingdom OTHER PUBLICATIONS Conner et al., Textile Research Journal, 1967, 37, pp. 94-102.

Conner et al., Textile Research Journal, 1964, 34, pp. 347-357.

Zorn et al., Das Leder, 1965, 16, pp. 73-78.

Primary Examiner-Joseph L. Schofer Assistant ExaminerA. L. Clingman Attorney, Agent, or Firm-M. Howard Silverstein; Max D. Hensley [57] ABSTRACT The present unique process is based on an acid complex of chromium hydroxydiacetate and zirconyl acetate and a dodecylbenzylfurfuryldimethyl ammonium chloride quaternary, with or without an aliphatic polyether wetting agent. The clear blackish-green bath is stable for days, and decomposes on cellulosics, with heat, to produce a chrome gray-green mineral dyeing along with a quaternary-zirconium fungicide. The process makes it possible to produce a chrome fungicidal mineral dyeing from a single bath zirconyl acetate system, where no alkali is required, and only one bath is required to deposit both dye and fungicide.

6*Claims, N0 Drawings 1 SINGLE BATH FUNGIC IDAL CHROME-ZIRCONYL ACETATE MINERAL DYEING PROCESS FOR CELLULOSICS The prior art discloses many mineral dyeing processes based on' two or more bathsto produce green chromium oxide deposits (dye pigments) in cellulosics. These processes are resultant from the decomposition of a chromium acid salt, with alkalis. Several other single bath dye processes are known, but these are based on alkaline chromium salt complexes. These alkaline systems require a Zirconyl ammonium carbonate complex of a trivalent or hexavalent chromium salt in a strongly alkaline system, and these systems are imcompatible with acid p systems, such as the present inventlon.

It has been known from prior art that trivalent chromium salts react with alkali hydroxides and carbonates to produce a precipitate of hydrated chromium oxide, having a gray-green color, and referred to in the trade as pearl gray. The cellulosic is wetted with a solution of the trivalent chrmoium salt in water, oven dried, and then wetted in a second alkali bath to precipate the hy drated chromium oxide (mirieral' dye). The prior art A third object of the invention is to demonstrate the feasibility of locking both the'chromium ion and the quaternary (through the furfuryl radical) to cellulosics. with basic Zirconyl acetate. to produce a unique chrome fungicidal mineral dyeing by a simple pad. dry. and cure technique.

The prior art teaches that conventional chromic chloride will degrade and tender cellulosics when heat dried on them. Chromium hydroxydiacetate, with zirconyl acetate. and dedecylbenzylfurfuryldimethyl ammonium chloride, is slightly acid from acetic acid. but does not degrade or tender the cellulosic, even with temperatures as high as 155C.

Utility of the invention is obviously in the field of textile mineral dyeings and weatherable goods. such as for tents. sails. tarpaulins, umbrellas, awnings. rope. shoe the invention and certain aspects of its usefulness.

also teaches that this wet treatedfabric (or cellulosic) The present invention consists of preparing a solution of chromium hydroxydiac etate inwater, adding zirconyl acetate, and dodecylbenzylfurfuryldimethyl ammonium chloride (quaternary),v to produce a clear blackish-green bath solution. To increase wettability of cellulosics, anda deeper. color shade, a small amount of aliphatic polyester (wetting agent) is incorporated into the bath. The. bath is stable for days inan open container. In use, the cellulosic is wetted with the bath, squeezed free of excess liquid, and then oven dried at temperature between 120 and 130C for 2 or 3 minutes, followed by oven cur ing at 150C to 155C for 2 or 3 minutes. The cured dyed cellulosic is dyed a green-gray. The zirconyl acetate is converted to basic zirconyl acetate during heat curing, producingan insoluble complex deposit with the chromium hydroxy diacetate and the furfuryl quaternary. The dyed cellulosic is washed for 1 to 2 minutes in hot tap water, squeezed free of excess water, and oven dried at 130C to 135C for 2 to 3 minutes. The cellulosic is permanently mineral dyed a green-gray color and contains the quaternary-basic zirconyl acetate fungicide.

The main object of the invention is to provide a single-bath chrome mineral dye bath with fungicide, having an acid (acetic) p, and being capable of depositing a chrome mineral dyeing and fungicide through heat decomposition onto cellulosics, using a simple pad, dry, cure technique, followed by water washing and drying. The grayish-green color shade, so produced, conforms with a true pearl gray, and is desired in the trade.

to produce fungicidal chrome mineral dyeings, where the fungicide is colorless and does not affect the color shade.

These are not to be interpreted as limiting the invention in any manner whatever. The treatments were also ap* plied to paper. porous ceramics. wood, and other fabrics having a cellulose composition.

EXAMPLE 1 Five (5.0) grams of 50% syrupy chromium hydroxydiacetate were mixed with 25 grams of distilled water. and stirred until a clear uniform blackish-green solution was produced(A).

In another 250 ml beaker, five (5.0) grams of 50% syrupy chromium hydroxydiacetate, 10.0 grams of 50% zirconyl acetate solution. and 15.0 grams of distilled water were mixed and stirred to a clear blackish-green solution( B).

Two pieces of scoured 9 02. cotton duck. 5 X 4 inches. were cut. One piece was wetted in (A) and the other in (B). The wetted duck samples were blotted free of excess liquid. oven dried at 120C/2 minutes. and oven cured at 1 50C/2 minutes. The cured samples were washed with hot tap water for 2 minutes. The duck sample treated with (A), without zirconyl acetate. lost all of the green color (deposit from curing) in washing. The duck sample treated with (B), with zirconyl acetatearetained a gray-green mineral dye deposit after washing, showing that zirconyl acetate locks the chromium ion to cellulosic fabric.

EXAMPLE 2 Zirconyl acetate produces an insoluble fungicide deposit with quaternary compounds containing unsaturated alkyl radicals, such as furfuryl, making it possible to deposit a colorless fungicide into cellulosics, when the quaternary has a microbiological activity. The following furfuryV quatemary was used to demonstrate this:

I Dodecylbenzyl furfuryl dimethyl ammonium ]chloride (quaternary) fur-fury quater- 4 nary" 0"" w This quaternary contains an unsaturated furfuryl alkyl radical, which is subject to reaction and lock-on to the cellulosic with zirconyl acetate, when heat curing deposits the quaternary with basic zirconyl acetate. The reactions could proceed as follows:

basic zirconyl acetate virconyl acetate and the basic acetate quaternary deposit would have the following lock-on structure:

In order to demonstrate this. grams of the furfuryl quaternary, grams of 13% ZrO- zirconyl acetate. and 30 grams of water were mixed to grams of clear solution. A section of scoured 9 oz. cellulosic cotton duck was wetted with the solution. blotted free of excess, and oven dried at C/2 minutes, followed by oven curing at C for 2 minutes. The fabric had a yellowish-white color, and was hot tap water washed for 2 minutes. followed by oven drying at 120C/2 minutes. The washed and dried fabric retained a nitrogen content, as evidenced by decomposition of the residue and estimation as ammonia.

paper. until thoroughly extracted. The solid residue was dried and digested with concentrated sulphuric acid. followed by treatment with sodium hydroxide. Ammonia was liberated. showing the presence of nitrogen (quaternary) in the washed basic zirconyl acetate residue.

EXAMPLE 3 The following bath formulation demonstrates the compatibility of the chromium hydroxydiacetate with the zirconylacetate and furfuryl quaternary:

Approx.-l5q- 5.00 grams chromium hydroxydiacetate (50% syrup) Appro.\.--102l5.00 grams zirconyl acetate (50% solution) Approx.--10'/ 10.00 grams distilled water Approx. SQ- 2.00 grams "Furfuryl quaternary" Approx.-l0l).' -3l00 grams Dye-Fungicide Bath (Blackish-green color) EXAMPLE 4 The fungicidal dyeing of greige cotton duck was made feasible by the incorporation of a wetting agent into the dye bath, and also reducing the bath concentration (which would reduce chemical costs):

Approx. 8.0% 2.50 grams chromium hydroxydiacetate (5071 syrup) Approx. 25.09? 8.00 grams zirconyl acetate (50% solution) Approx. 56.0% l 8.00 grams distilled water Approx. 5.0% 1.50 grams Furfuryl quaternary Approx. 6.0% 2.00 grams wetting agent (Discopen 205) (aliphatic polyester mfg. by Dixie Size 6'; Chemical Co. of Columbus. Ga.) Approx. l00.0/l --32.()() grams Wettable Dye-Fungicide Bath Some of the bath was evaporated to dryness on the hot plate, producing a solid glassy residue. This was pulverized, washed with warm distilled water on a filter (Blackish-Green) The clear blackish-green bath was stable for 96 hours in an open beaker, and possibly indefinitely in closed containers.

A section of 6 X 4 inches scoured duck was wetted with the bath, squeezed free of excess liquid, dried at 120C/3 minutes, followed by oven curing at 155C/2 minutes. The duck was dyed a deep shade of greenishgray. It was hot tap water washed (55C for 2 minutes. followed by oven drying at 120C-l 30C for 2 minutes. The dyed, washed, and dried duck was uniformly dyed a greenish-gray color shade of good depth of color, and comparable to conventional pearl grays on the market.

EXAMPLE 5 Samples of scoured duck, 6 X 4 inches, dyed with the bath and procedures of Examples 1, 3 and 4 were selected. The dyed, washed, and dried ducks were wetted in a paraffinammonium stearate water wax emulsion containing 7% paraffin and 2 to 3% of ammonium stearate emulsifier. The wetted samples were blotted free of excess liquid, oven dried at 130C for 3 minutes, and oven cured at 150C for 2 minutes. The wax finisheddyed samples were greenish-gray in color, and water repellent. Spray ratings were recorded of 90 to 100, showing a wax water repellent to attribute hydrophobic characteristics without adversely affecting the color. The paraffin-ammonium stearate emulsion is a commercial product, manufactured by Blue Grass Resins Inc. of Louisville, Ky. under the name Blu Wax".

EXAMPLE 6 Untreated 9 oz. scoured duck, and 9 oz. scoured duck, dyed by the bath and procedures in Example 4. were subjected to Scott Breaking Strength determinations. The untreated duck had a breaking strength of 132 lbs., while the dyed duck had a breaking strength of 130 lbs., showing that the fungicidal dye treatment does not degrade fabric strength significantly.

EXAMPLE 7 The dodecylbenzyl dimethyl furfuryl ammonium chloride quaternary was tested for Phenol Coefficient. and was found to have a Phenol Coefficient of 125. This is indicative of a high microbiological activity. Since Example 2 demonstrates that this compound can be locked onto cellulosic materials with zirconyl acetate, by heat conversion to a basic zirconyl acetate derivative, it follows that this deposit would have microbiological activity.

EXAMPLE 8 A soil burial test was conducted with plain untreated scoured 9 oz. duck and scoured 9 oz. duck which had been fungicidally dyed with the bath and by the procedures in Example 4. The untreated scoured duck control rotted completely in 1 week, while the fungicidally dyed duck sample resisted 3 weeks in soil burial, showing the treatment to afford microbiological protection to the 9 oz. duck.

EXAMPLE 9 The stability of the dye bath in Example 4 was evalu ated by allowing the bath to stand in a beaker at room temperature (25C) for several days. The bath remained stable and clear for 5 days. A sample of scoured duck was wetted with the 5-day old bath, blotted free of excess liquid, dried at 130C/2 minutes and oven cured at 150C/3 minutes. The duck was uniformly dyed a greenish-gray, resisted a hot tap water wash for l minute, and after drying at 130C for 3 minutes, was found 6 to be dyed a deep greenish-gray, comparable to dyeings obtained with a freshly prepared bath (per Example 4).

EXAMPLE 10 The dodecylbenzyl furfuryl dimethyl ammonium chloride quaternary not only functionsas a fungicide. but also produces a deeper chrome mineral dye color shade, thus making it an essential process component for the dyeing as well as the fungicidal effects. This is demonstrated by preparing two separate, baths, one without the quaternary, and one with the quaternary, and dyeing separate scoured duck samples with each of the baths:

Bath A (Without Quatemary) 5.0 grams Chromium Hydroxydiacetate (50% Syrup- Diamond Alkali Co.) 15.0 grams 50% Zirconyl Acetate Solution (Harshaw Chemical Co.) 10.0 grams Distilled Water 30.0 grams Dye Bath A A second bath (B) was prepared similar to bath (A). but including the dodecylbenzyl furfuryl dimethyl ammonium chloride quaternary:

Bath B1 (With Quaternary) 5.0 grams Chromium Hydroxydiacetate (50% Syrup- Diamond Alkali Co.) 15.0 grams 50% Zirconyl Acetate Solution (Harshaw Chemical Co.) 10.0 grams Distilled Water 2.0 grams Quaternary 32.0 grams Dye Bath B A piece of scoured duck (5 X 4 inches) was wetted in Bath A, blotted, and oven dried and cured according to Example 3 procedures. A piece of scoured duck was wetted in Bath B, blotted, and oven dried and cured according to Example 3 procedures. The cured duck samples were hot tap water washed for two minutes, followed by oven drying at C/2 minutes.

The duck sample dyed with Bath A, without quaternary, was dyed a light shade of greenish'gray. while the duck sample dyed with Bath B was dyed a deep greenish-gray color shade, showing the quaternary to be essential to deposit of maximum dye pigment, as well as to furnish a fungicidal effect with the mineral dyeing. Both the chromium ion and the quaternary are well locked to the cotton duck, together. to produce a fungicidal chrome mineral dyeing on the cellulosic.

I claim:

1. A single bath chrome mineral dyeing process for cellulosics (fabrics) comprising:

a. Wetting a cellulosic material in an aqueous solution containing about 1 to 2.5 weight percent chromium (as chromium hydroxydiacetate), 16 to 25 weight percent zirconyl acetate, and about 72.5 to 83 weight percent water,

b. drying, and subsequently curing the wetted fabric from (a).

2. A fungicidal single bath chrome mineral dyeing process for cellulosics (fabrics) comprising:

a. Wetting a cellulosic material in an aqueous solution containing about 1 to 2.5 weight percent chromium (as chromium hydroxydiacetate), 16 to 25 weight percent zirconyl acetate, 4 to,6 weight per- 7 cent dodecylbenzylfurfuryldimethyl ammonium chloride (quaternary), and the remainder water to make 100 weight percent.

b. drying. and subsequently curing the wetted fabric from (a).

3. A fungicidal single bath chrome mineral dyeing process for cellulosics (fabrics) comprising:

a Wetting a cellulosic material in an aqueous solution containing about I to 2.5 weight percent chromium (as chromium hydroxydiacetate). l6'to 25 weight percent zirconyl acetate. 4 to 6 weight percent dodecylbenzylfurfuryldimethyl ammonium chloride. and about 5 to 6 weight percent of an aliphatic polyether. with the difference as water to make 100 weight percent.

b. drying and subsequently euring the wetted fabric from (a).

4. A fungicidal single bath chrome mineral dyeing process for cellulosics (fabrics) comprisingr a. Wetting a cellulosic material in an aqueous solution containing about 1 to 2.5 weight percent chromium (as chromium hydroxydiacetate). 16 to weight percent zirconyl acetate. 4 to 6 weight percent dodecylbenzylfurfuryldimethyl ammonium chloride, and the remainder as water to make 100 weight percent.

b. drying. and subsequently curing the wetted fabric from (a). and

c. wetting the dyed cellulosic from (b) with a paraffin-ammonium stearate water-wax emulsion. containing 77! paraffin (weight percent). and

d. drying and subsequently curing the wetted fabric from (c).

5. A fungicidal signle bath chrome mineral dyeing process for cellulosics (fabrics) comprising:

a. Wetting a cellulosic material in an aqueous solution containing about I to 2.5 weight percent chromium (as chromium hydroxydiacetate), 16 to 25 weight percent zirconyl acetate. 4 to 6. weight percent dodecylbenzylfurfuryldimethyl ammonium chloride. and about 5 to 6 weight percent of an aliphatic'polyether (wetting agent). with the difference as water to make weight percent.

b. drying and subsequently curing the wetted fabric from (a). and c. wetting the dyed fabric from (b) with a paraffinammonium stearate water-wax emulsion, containing 7% paraffin (weight percent). and

d. drying and subsequently curing the wetted fabric from (c). 7

6. A single bath chrome mineral dyeing process fo cellulosics (fabrics) comprising:

a. Wetting a cellulosic material in an aqueous solution containing about 1 to 2.5 weight percent chromium (as chromium hydroxydiacetate), 16 to 25 weight percent zireonyl acetate, and the difference (about 72.5 to 83 weight percent) water to make 100 weight percent.

b. drying and subsequently curing the wetted fabric from (a). and

c. wetting the dyed cellulosic from (b) with a paraffin-ammonium stearate water-wax emulsion, containing 7% paraffin (weight percent). and

d. drying and subsequently curing the wetted fabric

Claims

1. A single bath chrome mineral dyeing process for cellulosics (fabrics) comprising: a. Wetting a cellulosic material in an aqueous solution containing about 1 to 2.5 weight percent chromium (as chromium hydroxydiacetate), 16 to 25 weight percent zirconyl acetate, and about 72.5 to 83 weight percent water, b. drying, and subsequently curing the wetted fabric from (a).

2. A fungicidal single bath chrome mineral dyeing process for cellulosics (fabrics) comprising: a. Wetting a cellulosic material in an aqueous solution containing about 1 to 2.5 weight percent chromium (as chromium hydroxydiacetate), 16 to 25 weight percent zirconyl acetate, 4 to 6 weight percent dodecylbenzylfurfuryldimethyl ammonium chloride (quaternary), and the remainder water to make 100 weight percent, b. drying, and subsequently curing the wetted fabric from (a).

3. A fungicidal single bath chrome mineral dyeing process for cellulosics (fabrics) comprising: a. Wetting a cellulosic material in an aqueous solution containing about 1 to 2.5 weight percent chromium (as chromium hydroxydiacetate), 16 to 25 weight percent zirconyl acetate, 4 to 6 weight percent dodecylbenzylfurfuryldimethyl ammonium chloride, and about 5 to 6 weight percent of an aliphatic polyether, with the difference as water to make 100 weight percent, b. drying and subsequently curing the wetted fabric from (a).

4. A fungicidal single bath chrome mineral dyeing process for cellulosics (fabrics) comprising: a. Wetting a cellulosic material in an aqueous solution containing abOut 1 to 2.5 weight percent chromium (as chromium hydroxydiacetate), 16 to 25 weight percent zirconyl acetate, 4 to 6 weight percent dodecylbenzylfurfuryldimethyl ammonium chloride, and the remainder as water to make 100 weight percent, b. drying, and subsequently curing the wetted fabric from (a), and c. wetting the dyed cellulosic from (b) with a paraffin-ammonium stearate water-wax emulsion, containing 7% paraffin (weight percent), and d. drying and subsequently curing the wetted fabric from (c).

5. A fungicidal signle bath chrome mineral dyeing process for cellulosics (fabrics) comprising: a. Wetting a cellulosic material in an aqueous solution containing about 1 to 2.5 weight percent chromium (as chromium hydroxydiacetate), 16 to 25 weight percent zirconyl acetate, 4 to 6 weight percent dodecylbenzylfurfuryldimethyl ammonium chloride, and about 5 to 6 weight percent of an aliphatic polyether (wetting agent), with the difference as water to make 100 weight percent, b. drying and subsequently curing the wetted fabric from (a), and c. wetting the dyed fabric from (b) with a paraffinammonium stearate water-wax emulsion, containing 7% paraffin (weight percent), and d. drying and subsequently curing the wetted fabric from (c).

6. A SINGLE BATH CHROME MINERAL DYEING PROCESS FOR CELLULOSICS (FABRICS) COMPRISING: A. WETTING A CELLULOSIC MATERIAL IN AN AQUEOUS SOLUTION CONTAINING ABOUT 1 TO 2.5 WEIGHT PERCENT CHROMIUM (AS CHROMIUM HYDROXYDIACETATE), 16 TO 25 WEIGHT PERCENT ZIRCONYL ACETATE, AND THE DIFFERENCE (ABOUT 72.5 TO 83 WEIGHT PERCENT) - WATER TO MAKE 100 WEIGHT PERCENT, B. DRYING AND SUBSEQUENTLY CURING THE WETTED FABRIC FROM (A) AND C. WETTING THE DYED CELLULOSIC FROM (B) WITH A PARAFFINAMMONIUM STEARATE WATER-WAX EMULSION, CONTAINING 7% PARAFFIN (WEIGHT PERCENT), AND D. DRYING AND SUBSEQUENTLY CURING THE WETTED FABRIC FROM (C).