US3779702A

US3779702A - Bright pink, lavender and blue mineral dyeing single bath process for cellulosics

Info

Publication number: US3779702A
Application number: US00250560A
Authority: US
Inventors: C Conner
Original assignee: US Department of Agriculture USDA
Current assignee: US Department of Agriculture USDA
Priority date: 1972-05-05
Filing date: 1972-05-05
Publication date: 1973-12-18
Anticipated expiration: 1990-12-18

Abstract

A certain cobalt organic salt was found to produce a water soluble aqueous complex with zirconyl ammonium carbonate, from which an insoluble pink deposit of cobalt and zirconia is deposited on cellulosics by heat. The deposit is bright pink and is completely resistant to hot water washings. The incorporation of varying amounts of copper metaborate into the aqueous cobalt complex produces compatible, uniform, soluble single bath complexes of copper, cobalt, and zirconia which produce lavender to bright blue insoluble deposits on cellulosics by heating (curing). By increasing the ratio of zirconia (ZrO2) to cobalt (Co) by about 7 or 8 to 1, in the bath, lavender to bluish-pink deposits are produced by heat curing without copper. Using low ratios of approximately 1:1 of cobalt and zirconia, produces bright pink mineral pigments on heating (curing), while gradually increasing the copper ratio to cobalt, from 1:1 to 1.5 to 1, produces lavender to bright blue insoluble deposits on heating (curing). The copper containing mineral dyeings on cellulosic are fungicidal and algaecidal. Bright color shades, resistant to light and microorganisms, are desirable for the protection and sales appeal of textiles and other cellulosics.

Description

United States Patent [191 Conner Dec. 18, 11973 [75] Inventor: Charles J. Conner, Metairie, La.

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

[22] Filed: May 5, 1972 [21] Appl. No.: 250,560

[52] US. Cl 8/52, 8/17, 117/143 R, 424/140 [51] Int. Cl D06p 3/60 [58] Field of Search 8/52, 17; 117/143 R; 424/140 [56] References Cited UNITED STATES PATENTS 3,291,635 12/1966 Conner et a1. ll7/l38.5 3,431,059 3/1969 Conner et al. 8/52 OTHER PUBLlCATlONS Textile Research Journal, Vol. 34, No. 4, 1964, pp. 347-357 Textile Research Journal, Vol. 37, No. 2, 1967, pp. 94-102.

Primary .Examiner-Donald Levy Assistant ExaminerBruce H. Hess Attorney-R. Hoffman et al.

[5 7] ABSTRACT A certain cobalt organic salt was found to produce a water soluble aqueous complex with zirconyl ammonium carbonate, from which an insoluble pink deposit of cobalt and zirconia is deposited on cellulosics by heat. The deposit is bright pink and is completely resistant to hot water washings. The incorporation of varying amounts of copper metaborate into the aqueous cobalt complex produces compatible, uniform, soluble single bath complexes of copper, cobalt, and zirconia which produce lavender to bright blue insoluble deposits on cellulosics by heating (curing). By increasing the ratio of zirconia (ZrO to cobalt (Co) by about 7 or 8 to 1, in the bath, lavender to bluish-pink deposits are produced by heat curing without copper. Using low ratios of approximately 1:1 of cobalt and zirconia, produces bright pink mineral pigments on heating (curing), while gradually increasing the copper ratio to cobalt, from 1:1 to 1.5 to 1, produces lavender to bright blue insoluble deposits on heating (curing). The copper containing mineral dyeings on cellulosic are fungicidal and algaecidal. Bright color shades, resistant to light and microorganisms, are desirable for the protection and sales appeal of textiles and other cellulosics.

12 Claims, No Drawings BRIGHT PINK, LAVENDER AND BLUE MINERAL DYEING SINGLE BATH PROCESS FOR CELLULOSICS 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.

Numerous organic dyes have been known to produce bright shades of pink, lavender, and blue but these materials are not durable to sunlight'exposure on awnings, umbrellas, sails, etc. Most organic colors are of poor light fastness when used on weatherable fabrics. The textile industry has long desired attractive bright mineral dye shades that could be applied from single bath systems, and which would be resistant to sunlight as a result of their mineral (inorganic) composition. It had been visualized that aqueous complexes of certain metal salts with alkaline zirconyl ammonium carbonate could deposit colored insoluble deposits ofzirconia and the complexed metal salt oxide or other basic compounds (carbonate, basic acetate, borate, etc.).

Cobalt citrate produces alkaline soluble complexes with ammonium hydroxide and ammonium carbonate, as well as zirconyl ammonium carbonate. Hydrated zirconia is a sunlight screener and algaecide and locks other metal ions onto cellulosics. Consequently, the solubilization of cobalt citrate in z'irconyl ammonium carbonate produces an alkaline complex of both cobalt and zirconia from which the cobalt-zirconia deposit, by heating, is a bright pink mineral pigment deposit, resistant to leaching and water washing, and being mineral in nature, free of organics after washing, resistant to light and algae, and resistant to both algae and fungi when formulated with copper.

The dye shades of pink, lavender, and blue are very bright and attractive, and desirable for mineral dyeing textiles and paper (cellulosics).

The main object of the invention is to provide a single bath aqueous system which can be used to dye cellulosics a bright shade of pink, lavender, or blue with mineral pigments having light screening, algaecidal, and fungicidal properties.

A second object of the invention is to provide bright shades of mineral dyeings, comparable to organic dyeings, but being of mineral composition for resistance to light, microorganisms, and weathering.

A third object of the invention is to shorten conventional mineral dyeing procedures to a simple pad, dry, and cure process where the fungicidal component contributes to the color shade produced and the zirconia furnishes algaecidal properties.

A fourth object of the invention is to provide a new and unique method to lock cobalt pink deposits onto cellulosics by a single bath application.

A fifth object of the invention is to provide a unique single bath system for applying cobalt, copper and other metal salts with zirconia to cellulosics by merely wetting and heating.

The prior art teaches that pink, lavender, and blue cellulosic dyeings, of bright shade, are best accomplished with organic dyes, applied by various and numerous processing steps. It also teaches that these same bright colors fade rapidly in direct sunlight and are not suitable for outdoor use. The prior art also teaches that cobalt and copper mineral dyeings must be applied to cellulosics by double decomposition, followed by washings and further dryings, with fungicide added by separate processing. The present invention shows that cobalt and combinations of cobalt, copper, and zirconia, can be applied to cellulosics from a single bath system by merely pad, dry, cure and wash processing, where the mineral deposit constitutes the mineral color (dye), fungicide, algaecide and light screener. The same bath system can be modified with copper to give any desired shade of pink. lavender or bright blue, by making more or less additions of copper metaborate to the cobaltzirconyl ammonium carbonate single bath system.

The bath system, so produced, is stable for paddings and produces the dyeing when wetted onto the cellulosic and drying on same, followed by heating to a conventional oven temperature of 150C-l55C for a few minutes (2 to 3). Hot water washing does not affect the dyeing, which is stable, uniform, and bright.

Thus, a pad bath formulation consisting of about 2 to 5 parts of cobalt citrate, about 10 to 48 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, and about 40 to parts water will effect the pink coloration of cellulosic fabrics. In use, a cellulosic fabric is padded with said formulation, the padded fabric dried at 120 C., for about 2 to 3 minutes, the dried fabric then cured at 130 C., for about 2 to 3 minutes, the cured fabric washed, and the cured, washed fabric finally dired at 130 C., for about 2 to 3 minutes.

A pad bath formulation consisting of about 2 to 5 parts of cobalt citrate and about to 96 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide will effect the lavender coloration of cellulosic fabrics. In use, a cellulosic fabric is padded with said formulation, the padded fabric dried at C., for about 2 to 3 minutes, the dried fabric then cured at C., for about 2 3 minutes, the cured fabric washed, and the cured, washed fabric finally dried at 130 C., for about 2 to 3 minutes.

A pad bath formulation consisting of about 3 to 5 parts of cobalt citrate, about 0.5 to 1.0 part copper metaborate, about 90 to 95 parts carbonate solution containing about 10 weight percent zirconium of a zirconly ammonium/dioxide, and about 0.5 to 1.5 parts ammonium carbonate will effect the lavender-blue coloration of cellulosic fabrics and will, in addition, confer fungicidal properties to said cellulosic fabrics. In use, a cellulosic fabric is padded with said formulation, the padded fabric dried at 130 C., for about 2 to 3 minutes, the dried fabric then cured at 150 C. to 1550 C., for about 3 to 4 minutes, the cured fabric washed, and the cured, washed fabric finally dired at 130 C. to C., for about 3 to 4 minutes.

A pad bath formulation consisting of about 3 to 8 parts of cobalt citrate, about 2 to 2.5 parts copper metaborate, about 90 to 95 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, and about 0.5 to 1.5 parts of ammonium carbonate will effect the purple-blue coloration of cellulosic fabrics and will, in addition, confer fungicidal properties to said cellulosic fabrics. In use, a cellulosic fabric is padded with said formulation, the padded fabric dried at 130 C., for about 2 to 3 minutes, the dried fabric then cured at C. to C., for about 3 to 4 minutes, the cured fabric washed, and the cured, washed fabric finally dried at 130 C. to 140 C., for about 3 to 4 minutes.

A pad bath formulation consisting of about 3 to parts of cobalt citrate, about 3 to 5 parts copper metaborate, about 90 to 94 parts of a zirconyl ammonium carbonate solution containing about weight percent zirconium dioxide, and about 1.0 part ammonium carbonate will effect the blue coloration of cellulosic fabrics and will, in addition, confer fungicidal properties to said cellulosic fabrics. In use, a cellulosic fabric is padded with said formulation, the padded fabric dried at 130 C., for about 2 to 3 minutes, the dried fabric then cured at 150C. to 155 C., for about 3 to 4 minutes, the cured fabric washed, and the cured, washed fabric finally dried at 130 C. to 140 C., for about 3 to 4 minutes.

A pad bath formulation consisting of about 2 to 4 parts of cobalt citrate, about 0.5 to 1.0 part copper metaborate, about 10 to 48 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, about 40 to 75 parts water, and about 5 parts ammonium hydroxide will effect the pink coloration of cellulosic fabrics and will, in addition, confer fungicidal properties to said cellulosic fabrics. In use, a cellulosic fabric is padded with said formulation, the padded fabric dried at about 120, for about 2 to 3 minutes, the dried fabric then cured at about 130 C., for about 2 to 3 minutes, the cured fabric washed, and the cured, washed fabric finally dired at about 120 C., for about 2 to 3 minutes.

Utility of the invention is obviously in the field of textile dyeing and dyeing of other cellulosics (paper and wood). It is recommended for non-weatherable goods and also outdoor weatherable goods of a cellulosic nature, such as awnings, tents, umbrellas, sails, shoe lining, boat covers, apparel, canvas shoes, writing paper, wall paper, tarpaulins, rope, jackets, socks, upholstery, paper bags, hats, etc.

The following examples are presented to illustrate the invention and certain aspects of its usefulness. These are not to be interpreted as limiting the invention in any manner whatever. The treatments were applied to leather, wood, and paper and are not restricted to cellulosics alone. Porous ceramics dipped into the baths and oven dried and cured, were also mineraldyed the respective color shades.

EXAMPLE 1 One gram (1.0) of cobalt citrate, having the formula of CO (C H O )"6H O was weighed into a 250 ml beaker and mixed with 34.0 grams of distilled water. The salt was practically insoluble on stirring. To this mix was added 10.0 grams of zirconyl ammonium carbonate, and stirring continued for 5 minutes. A large percentage, approximately 98% (0.98 gm) of the salt dissolves on stirring to produce an aqueous cobaltzirconia complex.

EXAMPLE 2 The clear aqueous complex from Example 1 was poured into a dish and used to wet a piece of scoured 9 Oz army duck, 4 X 4 inches. The wetted duck was blotted free of excess liquid and oven dried at 130C for 2 minutes, followed by an oven cure of 140C (2 minutes). The sample was dyed pink. The pink sample was hot tap water (55C) washed for 5 minutes, followed by oven drying at 130C/2 min. The sample shows no loss of color and remains dyed a bright shade of pink.

EXAMPLE 3 Examples 1 and 2 were repeated with 5.0 grams of ammonium hydroxide (29.4% NH added to the bath to produce percent solubility of the cobalt citrate. The results were the same as with Examples 1 and 2 and bright pink mineral dyeings resulted.

EXAMPLE 4 Example 3 was repeated with the cure temperature of the wetted duck being carried out at C instead of 140C. A slightly deeper and brigher pink" dyeing resulted.

EXAMPLE 5 Two grams (2.0) of coblat citrate was mixed with 38.0 grams of water, 10 grams of zirconyl ammonium carbonate (10% ZrO and 5 grams of ammonium hydroxide (29.4% NH to give 55 grams of bath. The bath was clear and brownish pink, showing complete solubility. Example 2 was repeated with this bath. A deep pink" mineral dyeing was produced, which was not effected by hot tap water washing.

EXAMPLE 6 Two grams (2.0) of cobalt citrate was mixed with 48.0 grams of zirconyl ammonium carbonate 10% Zr0 and stirred for 10 minutes until all of the salt dissolves. A clear deep pink bath solution resulted. The bath contains 9.6% Zr0 and 0.48% Co since cobalt citrate contains approximately 12% cobalt as metal. This single bath complex (high zirconium) is capable of producing lavender" mineral dyeings.

EXAMPLE 7 The clear bath from Example 6 was used to wet a 4 X 8 inch sample of scoured 9 oz army duck. The thoroughly wetted duck was blotted free of excess liquid and oven dried at 130C/2 minutes, followed by oven curing at C/3 minutes. The cured fabric appears violet prior to wash. The cured sample was washed 5 minutes in hot running tap water, becoming bluish-pink It was then oven-dried at 130C for 4 minutes, producing a pure bright lavender" mineral dyed fabric.

EXAMPLE 8 EXAMPLE 9 The clear bath from Example 8 was used to wet a 9 X 8 inch sample of 9 oz scoured army duck which was blotted free of excess liquid and oven dried at 130C/2 minutes, followed by an oven cure of 155C/3 minutes. The freshly cured fabric was purple" in color. It was then hot tap water washed for 5 minutes and then oven dried at 130C/4 minutes. A bright lavender (bluish) mineral dyeing resultedQ EXAMPLE The bath prepared in Example 8 was modified to include 1.0 grams of copper metaborate with 2.0 to 4.0 grams cobalt citrate and 45 to 47.0 grams of zirconyl ammonium carbonate (10% ZrO Drying, curing, and washing procedures were followed as in Example 9 with scoured duck. A lavender-purple mineral dyeing resulted.

EXAMPLE 1 1 EXAMPLE 12 The clear bath from Example 11 was applied to a 9 inch X 8 inch section of scoured army duck, which was blotted, and oven dried at 130C/2 minutes, followed by oven cure at 155C/3 minutes. A blue dyed fabric resulted. The cured sample was hot tap water washed for 5 minutes, followed by oven drying at 130C/4 minutes. A bright blue mineral dyed fabric resulted.

EXAMPLE 13 Example 8 bath was again prepared and applied to a 4 X 8 inch sample of scoured 9 oz army duck. The fabric was oven dried at 120C/2 minutes and oven cured at 140C/2 minutes, followed by 5 minutes hot tap wash and oven dry at 120C/2 minutes. The color shade was bluish-pink and contains copper fungicide.

EXAMPLE 14 Examples 1, 3, 4, 5, 6, 8, 10, 11 were repeated and applied to filter paper and porous wooden splints. In each instance, a pink-lavender-blue mineral dyeing was produced in cure at 150C.

EXAMPLE 15 Examples 2, 7, 9, 10, and 12 were repeated with oven drying at 120C, followed by cures at 130C/3 minutes, instead of drying at 130C and curing at 155C. The color shades were lighter and brighter, being more of a pestel pink-lavender-blue in each instance. The higher cure temperature of 155C produces deeper and darker color shades.

EXAMPLE 16 Fabrics treated by Examples 2, 5, 7, 9, and 12 were exposed to outdoor sunlight and weather for one week (to be reused as exposure time is lengthened). The dyeings were exposed to severe weather conditions of frequent rain followed by sunlight and high temperatures without significant color changes or evidence of fading. No growths of mildew or algae were detected.

EXAMPLE 17 Fabrics (duck) treated in Example 9, 10, and 12 were exposed to soil burial with plain scoured (untreated) duck. After 2 weeks, the untreated duck showed no retained strength (disintegrated), while the Example 9, 10, and 12 treated samples were intact and not degraded.

I claim:

I. A single bath mineral dyeing process for producing a pink cellulosic fabric, which process comprises:

a. padding a cellulosic fabric with a solution consisting of about 2 to 5 parts of cobalt citrate, about 10 to 48 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, and about 40 to parts water,

b. drying the fabric from (a) at 120C for about 2 to 3 minutes,

c. curing the fabric from (b) at 130C for about 2 to 3 minutes,

d. washing the fabric from (c), and

e. drying the fabric from (d) at 130C for about 2 to 3 minutes.

2. A pad bath formulation for producing a pink cellulosic fabric, said bath consisting of about 2 to 5 parts of cobalt citrate, about 10 to 48 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, and about 40 to 75 parts water.

3. A single bath mineral dyeing process for producing a lavender cellulosic fabric, which process comprises:

a. padding a cellulosic fabric with a solution consisting of about 2 to 5 parts of cobalt citrate and about to 96 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide,

b. drying the fabric from (a) at C for about 2 to 3 minutes,

0. curing the fabric from (b) at C for about 2 to 3 minutes,

d. washing the fabric from (c), and

e. drying the fabric from (d) at 130C. for about 2 to 3 minutes.

4. A pad bathformulation for producing a lavender cellulosic fabric, said bath consisting of about 2 to 5 parts of cobalt citrate and about 90 to 96 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide.

5. A single bath mineral dyeing process for producing a lavender-blue cellulosic fabric with fungicidal properties, which process comprises:

a. padding a cellulosic fabric with a solution consisting of about 3 to 5 parts of cobalt citrate, about 0.5 to 1.0 part copper metaborate, about 90 to 95 parts of zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, and about 0.5 to 1.5 parts ammonium carbonate,

b. drying the fabric from (a) at 130C for about 2 to 3 minutes,

c. curing the fabric from (b) at C-l55C for about 3 to 4 minutes,

d. washing the fabric from (c), and

e. drying the fabric from (d) at 130C-140C for about 3 to 4 minutes.

6. A pad bath formulation for producing a lavenderblue cellulosic fabric with fungicidal properties, said bath consisting of about 3 to 5 parts of cobalt citrate, about 0.5 to 1.0 part copper metaborate, about 90 to 95 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, and about 0.5 to 1.5 parts ammonium carbonate.

7. A single bath mineral dyeing process for producing a purple-blue cellulosic fabric with fungicidal properties, which process comprises:

a. padding a cellulosic fabric with a solution consisting of about 3 to 8 parts of cobalt citrate, about 2 to 2.5 parts copper metaborate, about 90 to 95 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, and about 0.5 to 1.5 parts of ammonium carbonate,

b. drying the fabric from (a) at 130C for about 2 to 3 minutes,

0. curing the fabric from (b) at about l50l 55C for about 3 to 4 minutes,

d. washing the fabric from (c), and

e. drying the fabric from (d) at about l30140C for about 3 to 4 minutes.

8. A pad bath formulation for producing a purpleblue cellulosic fabric with fungicidal properties, said bath consisting of about 3 to 8 parts of cobalt citrate, about 2 to 2.5 parts copper metaborate, about 90 to 95 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, and about 0.5 to 1.5 parts of ammonium carbonate.

9. A single bath mineral dyeing process for producing a blue cellulosic fabric with fungicidal properties, which process comprises:

a. padding a cellulosic fabric with a solution consisting of about 3 to parts of cobalt citrate, about 3 to 5 parts copper metaborate, about 90 to 94 parts of a zirconyl ammonium carbonate solution containing about weight percent zirconium dioxide, and about 1.0 part ammonium carbonate,

b. drying the fabric from (a) at about 130C for about 2 to 3 minutes,

c. curing the fabric from (b) at about l50l55C.

for about 3 to 4 minutes,

d. washing the fabric from (c), and

e. drying the fabric from (d) at about l30-l40C for about 3 to 4 minutes.

10. A pad bath formulation for producing a blue cellulosic fabric with fungicidal properties, said bath consisting of about 3 to 5 parts of cobalt citrate, about 3 to 5 parts copper metaborate, about to 94 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, and about 1.0 part ammonium carbonate.

1]. A single bath mineral dyeing process for producing a pink cellulosic fabric with fungicidal properties, which process comprises:

a. padding a cellulosic fabric with a solution consisting of about 2 to 4 parts of cobalt citrate, about 0.5 to 1.0 part copper metaborate, about 10 to 48 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, about 40 to 75 parts water, and about 5 parts ammonium hydroxide,

b. drying the fabric from (a) at about C for about 2 to 3 minutes,

c. curing the fabric from (b) at about l30C for about 2 to 3 minutes,

d. washing the fabric from (c), and

e. drying the fabric from (d) at about 120C for about 2 to 3 minutes.

12. A pad bath formulation for producing a pink cellulosic fabric with fungicidal properties, said bath consisting of about 2 to 4 part of cobalt citrate, about 0.5 to 1.0 parts copper metaborate, about 10 to 48 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, about 40 to 75 parts water, and about 5 parts ammonium hydroxide.

Claims

2. A pad bath formulation for producing a pink cellulosic fabric, said bath consisting of about 2 to 5 parts of cobalt citrate, about 10 to 48 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, and about 40 to 75 parts water.
3. A single bath mineral dyeing process for producing a lavender cellulosic fabric, which process comprises: a. padding a cellulosic fabric with a solution consisting of about 2 to 5 parts of cobalt citrate and about 90 to 96 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, b. drying the fabric from (a) at 120*C for about 2 to 3 minutes, c. curing the fabric from (b) at 130*C for about 2 to 3 minutes, d. washing the fabric from (c), and e. drying the fabric from (d) at 130*C. for about 2 to 3 minutes.
4. A pad bathformulation for producing a lavender cellulosic fabric, said bath consisting of about 2 to 5 parts of cobalt citrate and about 90 to 96 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide.
5. A single bath mineral dyeing process for producing a lavender-blue cellulosic fabric with fungicidal properties, which process comprises: a. padding a cellulosic fabric with a solution consisting of about 3 to 5 parts of cobalt citrate, about 0.5 to 1.0 part copper metaborate, about 90 to 95 parts of zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, and about 0.5 to 1.5 parts ammonium carbonate, b. drying the fabric from (a) at 130*C for about 2 to 3 minutes, c. curing the fabric from (b) at 150*C-155*C for about 3 to 4 minutes, d. washing the fabric from (c), and e. drying the fabric from (d) at 130*C-140*C for about 3 to 4 minutes.
6. A pad bath formulation for producing a lavender-blue cellulosic fabric with fungicidal properties, said bath consisting of about 3 to 5 parts of cobalt citrate, about 0.5 to 1.0 part copper metaborate, about 90 to 95 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, and about 0.5 to 1.5 parts ammonium carbonate.
7. A single bath mineral dyeing process for producing a purple-blue cellulosic fabric with fungicidal properties, which process comprises: a. padding a cellulosic fabric with a solution consisting of about 3 to 8 parts of cobalt citrate, about 2 to 2.5 parts copper metaborate, about 90 to 95 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, and about 0.5 to 1.5 parts of ammonium carbonate, b. drying the fabric from (a) at 130*C for about 2 to 3 minutes, c. curing the fabric from (b) at about 150*-155*C for about 3 to 4 minutes, d. washing the fabric from (c), and e. drying the fabric from (d) at about 130*-140*C for about 3 to 4 minutes.
8. A pad bath formulation for producing a purple-blue cellulosic fabric with fungicidal properties, said bath consisting of about 3 to 8 parts of cobalt citrate, about 2 to 2.5 parts copper metaborate, about 90 to 95 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, and about 0.5 to 1.5 parts of ammonium carbonate.
9. A single bath mineral dyeing process for producing a blue cellulosic fabric with fungicidal properties, which process comprises: a. padding a cellulosic fabric with a solution consisting of about 3 to 5 parts of cobalt citrate, about 3 to 5 parts copper metaborate, about 90 to 94 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, and about 1.0 part ammonium carbonate, b. drying the fabric from (a) at about 130*C for about 2 to 3 minutes, c. curing the fabric from (b) at about 150*-155*C. for about 3 to 4 minutes, d. washing the fabric from (c), and e. drying the fabric from (d) at about 130-140*C for about 3 to 4 minutes.
10. A pad bath formulation for producing a blue cellulosic fabric with fungicidal properties, said bath consisting of about 3 to 5 parts of cobalt citrate, about 3 to 5 parts copper metaborate, about 90 to 94 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, and about 1.0 part ammonium carbonate.
11. A single bath mineral dyeing process for producing a pink cellulosic fabric with fungicidal properties, which process comprises: a. padding a cellulosic fabric with a solution consisting of about 2 to 4 parts of cobalt citrate, about 0.5 to 1.0 part copper metaborate, about 10 to 48 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, about 40 to 75 parts water, and about 5 parts ammonium hydroxide, b. drying the fabric from (a) at about 120*C for about 2 to 3 minutes, c. curing the fabric from (b) at about 130*C for about 2 to 3 minutes, d. washing the fabric from (c), and e. drying the fabric from (d) at about 120*C for about 2 to 3 minutes.
12. A pad bath formulation for producing a pink cellulosic fabric with fungicidal properties, said bath consisting of about 2 to 4 part of cobalt citrate, about 0.5 to 1.0 parts copper metaborate, about 10 to 48 parts of a zirconyl ammonium carbonate solution containing about 10 weight percent zirconium dioxide, about 40 to 75 parts water, and about 5 parts ammonium hydroxide.