US3768965A

US3768965A - Activated single bath pearl gray chrome green mineral dyeing and composition therefor

Info

Publication number: US3768965A
Application number: US00176736A
Authority: US
Inventors: C Conner
Original assignee: US Department of Agriculture USDA
Current assignee: US Department of Agriculture USDA
Priority date: 1971-08-31
Filing date: 1971-08-31
Publication date: 1973-10-30
Anticipated expiration: 1990-10-30

Abstract

Conventional ''''pearl gray'''' chrome green mineral dyes require a double decomposition process for depositing green chromium oxide in cellulosics. By forming a unique alkaline complex of a chromic chloride with ammonium oxalate and zirconyl ammonium carbonate, a single dye bath is produced, enabling the dyes to apply the ''''pearl gray'''' chrome green mineral dyeing by a simple pad, dry, cure, and wash procedure. The dyeings are uniform and the cellulosic is not tendered or physically degraded. Not only does this invention reduce processing steps, but it eliminates the conventional problem of tendering resulting from drying the chromic chloride on cellulosics prior to processing through a second bath of soda ash and soap. The invention makes it possible to prepare a modified chromic chloride stock solution that can be used for either the conventional ''''pearl gray'''' processing or the single bath process described above.

Description

United States Patent 1 Conner 51 Oct. 30, 1973 [75] Inventor:

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

[22] Filed: Aug. 31, 1971 [21] Appl. No.: 176,736

Charles J. Conner, Metairie, La.

[52] U.S. Cl 8/17, 8/52, 106/304,

[51] Int. Cl C09b 61/00 [58] Field ofSearch "r 8/17, 52

[56] References Cited UNITED STATES .PATENTS 2,091,539 l/l935 White 8/76 X 2,035,527 7/1932 3,431,059 3/1969 2,202,328 5/1940 2,229,923 1/1941 Primary Examiner-Harold Ansher Assistant Examiner-Patricia C. Ives Atto'meyR. Hoffman et a1.

57 ABSTRACT Conventional pearl gray chrome green mineral dyes require a double-decomposition process for depositing green chromium oxide in cellulosics. By forming a unique alkaline complex of a chromic chloride with ammonium oxalate and zircon-yl ammonium carbonate, a single dye bath is produced, enabling the dyes to apply the pearl gray" chrome green mineral dyeing by a simple pad, dry, cure, and wash procedure. The dyeings are uniform and the cellulosic is not tendered or physically degraded. Not only does this invention reduce processing steps, but it eliminates the conventional problem of tendering resulting from drying the chromic chloride on cellulosics prior to processing through a second bath of soda ash and soap. The invention makes it possible to prepare a modified chromic chloride stock solution that can be used for either the conventional pearl gray" processing or the single bath process described above.

6 Claims, No Drawings hereby granted to the Government of the United States of America.

It has been known from prior art that chromic chloride reacts with alkali hydroxides and carbonates to produce a precipitate of hydrated chromium oxide, having a grayish-green color, and referred to in mineral dyeing terminology as pearl gray. When a cellulosic is wetted with chromic chloride, dried, and then wetted with an alkali hydroxide or carbonate solution, this precipitated hydrated chromium oxide is desposited in the cellulosic to attribute a gray-green color (mineral dyeing). The prior art teaches that this wet dyed cellulosic must then be washed, treated with fungicide and then dried. I

The present invention consists of treating the chromic chloride with ammonium oxalate and an ammoniacal solution, which produces an'alkaline aqueous soluble complex of hydrated chromium oxide with ammonium oxalate. When zirconyl ammonium carbonate is used with ammonium hydroxide, a water soluble chromium zirconium hydrated oxide complex is produced with the excess ammoniacal alkalinity. When this solution (bath) is applied to cellulosics, and the cellulosics heated to dryness and cured at temperatures of 130C to 150C, the hydrated zirconia and green chromium oxide are deposited as an insoluble residue to produce a uniform mineral dyeing. When copper metaborate, copper hydroxide, or copper carbonate is solubilized in the ammonium hydroxide, priorto addition to the formulation, the bath is compatible, and a fungicidal pearl gray mineral dyeing is deposited in cellulosics by heat curing.

The main object of the invention is to provide a single-bath chrome mineral dye bath from conventional chromic chloride to eliminate double decomposition baths and produce uniform pearl-gray" mineral dyeings by a simple pad, dry, and cure procedure, followed by wash and dry to remove byproducts.

A second object of the invention is to provide a single modified chromic chloride stock solution, which can be used for single bath or conventional pearlgraymineral dyeing.

A third object of the invention is to provide a single dye bath from chromic chloride and 'copper compounds, to produce fungicidal pearl-gray mineral dyeings by a simple pad, dry, and cure procedure.

I A fourth object of the invention is to provide a single bath from chromic chloride, copper compounds, and paraffin-ammonium stearate emulsion components to deposit a fungicidal pearl-gray mineral dyeing with water repellent finish, by a simple pad, dry, and cure procedure.

The prior art teaches that chromic chloride will degrade and tender cellulosics when heat dried on them. This invention enables the use of chromic chloride in ammoniacal zirconium complex without tendering or degrading the cellulosic. The prior art also teaches that conventional pearl-gray mineral dyeing requires a double decomposition procedure, followed by a treatment with fungicide. the present invention applies the mineral dyeing and fungicide from the same single bath system. The prior art teaches that conventional water repellent finishes are applied last to the dye and fungicide treated cellulosic. The present invention incorporates the wax finish in with the dye and fungicide, in a single bath, to produce fungicidal mineral dyeings with water repellent finish by a simple pad, dry, and cure procedure.

Utility of the invention is obviously in the field of mineral dyeings and weatherable goods, such as for tents, sails, tarpaulins, umbrellas, awnings, rope, shoe lining, rainwear, boat covers, canvas shoes, upholstery, 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 also applied to paper, porous ceramics, wood,.and other fabrics having cellulosic compositions.

I EXAMPLE l Four stock solutions of chromic chloride, having chromium metal contents of 8, 10, 15, and 16 percent were formulated into the following formula:

25 .00 grams chromic chloride stock (8 10 percent Cr) 25.00 grams water (distilled 4.00 grams ammonium oxalate crystals (fine) 20.00 grams zirconyl ammonium carbonate (10% ZI'Oz) 5.00 grams ammonium hydroxide (29.4 percent N a) 79.00 grams single bath The 8 and 10 percent chromic chloride stock solutions were compatible while the 15 and 16 percent stock solutions produced gelatinous gray-green precipitates, and were incompatible. The chromic chloride chromium content is a limiting factor, and cannot exceed 10 percent, being desirable at 8 percent chromium.

EXAM PLE 2 results.

EXAM PLE 3 The following formulation represents a single bath system with an 8% Cr chromic chloride stock and copper metaborate to produce a fungicidal pearlgray mineral dyeing:

25.0 grams chromic chloride (8 percent Cr content) 25.0 grams water i 2.0 grams copper metaborate (40 percent Cu) 4.0 grams ammonium oxalate crystals (fine) 20.0 grams zirconyl ammonium carbonate percent ZTOz) 5.0 grams ammonium hydroxide (29.4 percent N 3) 81.0 grams single bath (fungicide-mineral dye) EXAMPLE 4 The bath from Example 1 (with 8 percent chromic chloride stock formulation) was used to wet several pieces of 4 X 8 inch scoured 9 oz. army duck. The wetted duck was blotted and oven dried at 110 to 120C. for 2 to 4 minutes, followed by oven curing at 130 to 140C for 2 to 3 minutes. The cured fabric was dyed a deep gray-gree rfminefafiyeing (pear l gray). The cured samples were washed in both hot and cold running tap water and oven dried at l10-120C for 2 to 4 minutes. The fabrics remained a deep gray-.' 1

green dyed color shade,and were stable to water washings.

EXAMPLES The bath from Example 3 was similarly applied to samples of 9 oz. army scoured duck, using the procedures of Example 4. The duck was dyed a deep grayish-green (pearl gray) mineral dyeing, having a copper (fungicidal) content of 0.5 percent Cu.

EXAMPLE6 Preparation of modified chromic chloride," which can be used for'single bathapplication per Examples 1 through 5, or for conventional pearl gray mineral dyeings:

25.00 grams percent Cr) 25.00 grams distilled water 4.00 grams ammonium oxalate crystals (fine) 54.00 grams modified stock chromic chloride The ammonium oxalate is dissolved in the 50 grams of chromic chloride and water and retained for use in conventional (double decomposition) pearl gray dyeing, or for further addition of zirconyl ammonium carbonate (10 percent ZrO2) and ammonium hydroxide (29.4 percent NH3) for single bath pearl gray mineral dyeings. The modified stock is a clear greenish-black solution, which is activated by adding the ammoniacal components, and copper metaborate (if desired).

chromic chloride stock(8l0 EXAMPLE 7 to 2 percent soft soap (potassium stearate or comparable) to the soda ash bath assures better lock-on and a greener shade of color.

b. Single Bath Dyeing: A 4 X 6 inch sample of scoured duck was treated with the further modification of the Example 6 stock:

54.00 grams modified chromic chloride" (Example 6) 20.00 grams zirconyl ammonium carbonate (10 percent ZrO 5.00 grams ammonium hydroxide (29.4 percent NHQ) 79.00 grams single bath (pearl gray) The drying and curing procedure were the same as in Example 4. A deep gray-green mineral dyeing resulted.

EXAMPLE 8 A sample of the scoured duck treated in Example 3 (with copper metaborate-chromic chloride comples with zirconium) was soil buried for one week with a piece of untreated scoured duck (control). After 4 weeks, the control fabric had-rotted out, while the treated fabric retained 20 percent strength.

EXAM PLE 9 Samples from the single bath treatments in Examples 4, 5, and 7 (conventional) were exposedon the weather rack for 6 months along with untreated scoured duck. No growths were evidenced on the treated samples, while algae and mildew growths were noted on the control sample.

The washed fungicidally dyed fabrics produced according to Examples 4 and 5 can be wax finished by conventional paddings through a 7 to 9 percent paraf- 5 fin (paraffin-ammonium stearate emulsion) to obtain 3 oven dry-cured at 135l40C for 3 to 4 minutes,

followed by a 1 to 2 minute tap water rinse and oven drying at 130C for 2 minutes. The fabric was mineral dyed a gray-green color. The addition of l to 4 percent paraffin add-ons, followed by oven dry at 1 10 to 120C for 2 minutes and oven curing at to C to melt the paraffin into the fabric and decompose the ammonium stearate. The NH, leaves the fabric as gas, and the stearic acid combines with the zirconia to produce zirconium stearate.

The aqueous 7 to 9 weight percent paraffin ammo nium stearate emulsion can be conveniently prepared by diluting, with effective stirring, 2,000 grams of a commercially available paraffin-ammonium stearate wax emulsion paste with 8,000 grams of water. This will produce 10,000 grams of a paraffin wax pad bath containing about 7 weight percent of paraffin wax.

EXAMPLE 10 The washed-dyed fabrics from Examples 4 and 5 were wetted with an 8 percent paraffin-paraffin ammonium stearate emulsion, blotted free of excess liquid, and oven dried for 2 minutes at 120C. The dried fabric then curved at 145 150C for 2 minutes, and allowed to condition at room temperature (250C) for l hour. Thetreated fabric was completely ater repellent, spray rating 90 to 100. This example was repeated in the pilot plant in four runs: wherein the emulsion was applied by conventional padding, and drying and curing effected in a continuous oven-tenter frame operation, using 110C for 2 minutes in drying, and 150C for 2 minutes in curing. The same excellent water repellency resulted.

I claim: I

1. An activated, water-based composition of matter useful to effect pearl gray chrome green mineral dyeing, said dyeing exhibiting fungicidal properties, which copper.

2. An activated, water-based composition of matter according to claim 1 wherein the copper compound is copper metaborate.

3. An activated, water-based composition of matter according to claim 1 wherein the copper compound is copper carbonate.

4. An activated, water-based composition of matter according to claim 1 wherein the copper compound is copper hydroxide.

5. A single bath mineral dyeing process for a cellulosic material providing ancillary fungicidal properties to the said material and consisting of the following steps:

a. wetting the cellulosic material with the water based composition of claim 1;

b. oven-drying the wetted material from step (a) at a temperatureof from 1 10to C for a period offrom 2 to 4 minutes;

c. oven-curing the dried material from step (b) at a temperature of from to C for a period of from 2 to 4 minutes:

. water washing the cured material from step (c) for a period of from 2 to 4 minutes; and e. oven-drying the washed material from step (d) at a temperature of from .1 10 to 120C for a period of from 2 to 4 minutes.

6. A process according to claim 5 wherein the dried and washed material from step (e) thereof is rendered water repellent by the steps comprising:

a. wetting the said material with a paraffinammonium stearate emulsion containing about from 7 to 9 weight percent of paraffin;

- b. drying the wetted material from step (a) at a temperature of about l20iC for about 2 minutes, and

c. curing the dried material of step (b) ata temperature of from 145 to C for a period of about 2 minutes.

Claims

2. An activated, water-based composition of matter according to claim 1 wherein the copper compound is copper metaborate.
3. An activated, water-based composition of matter according to claim 1 wherein the copper compound is copper carbonate.
4. An activated, water-based composition of matter according to claim 1 wherein the copper compound is copper hydroxide.
5. A single bath mineral dyeing process for a cellulosic material providing ancillary fungicidal properties to the said material and consisting of the following steps: a. wetting the cellulosic material with the water based composition of claim 1; b. oven-drying the wetted material from step (a) at a temperature of from 110* to 125* C for a period of from 2 to 4 minutes; c. oven-curing the dried material from step (b) at a temperature of from 130* to 145* C for a period of from 2 to 4 minutes; d. water washing the cured material from step (c) for a period of from 2 to 4 minutes; and e. oven-drying the washed material from step (d) at a temperature of from 110* to 120* C for a period of from 2 to 4 minutes.
6. A process according to claim 5 wherein the dried and washed material from step (e) thereof is rendered water repellent by the steps comprising: a. wetting the said material with a paraffin-ammonium stearate emulsion containing about from 7 to 9 weight percent of paraffin; b. drying the wetted material from step (a) at a temperature of about 120* C for about 2 minutes, and c. curing the dried material of step (b) at a temperature of from 145* to 150* C for a period of about 2 minutes.