US3030227A

US3030227A - Changeable color textile fabric and process for causing color to change

Info

Publication number: US3030227A
Application number: US664516A
Authority: US
Inventors: Alfred T Clifford; Amanda J Owens
Original assignee: Riegel Textile Corp
Current assignee: Riegel Textile Corp
Priority date: 1957-06-10
Filing date: 1957-06-10
Publication date: 1962-04-17
Anticipated expiration: 1979-04-17

Description

P 3,030,227 Ice Patented Apr. 17, 1962" This invention relates to the coloring of textile fabrics with colors which may be changed by a simple home treatment, and more particularly to a process by which a series of textile colors may be applied by conventional printing or pigment dyeing techniques and the colored fabrics used and laundered repeatedly, after which each color in the series may be changed to an entirely different color by a simple home treatment with safe, easily available materials.

This invention comprises generally the formulation and application of a series of colors, either resin-bonded pigment print colors or resin-bonded pigment dyeing colors, containing a pigment comprising zeolitic aluminum silicate containing interstitial polyatoms of one or more elements from the group comprising sulfur, selenium, and tellurium which is capable of being changed by the application of a relatively weak acid, such as citric acid.

Ultramarine blue is the most common member of the series of zeolitic aluminum silicate pigments. However, other members of the series such as ultramarine violet, ultramarine red, and zeolitic ultramarine yellow, are decomposed by acid and may be used as'the decomposable color in the present invention.

It has been known heretofore that certain colors might be weakened or stripped from a fabric by acid treatment.

But it has not heretofore been found feasible to eifect a complete change to a characteristically different color in this manner. Although ultramarine blue has been used as a self shade, or as a blue shade even when slightly tinted with other pigments, it has not heretofore been used as the blue component of a combination shade adapted for decomposing in accordance with the present invention. The novel utilization of ultramarine blue as the blue component in green, brown, black, lavender, etc., in the present invention is made possible by its unique property of decomposability in dilute acid solution.

The present invention has practically unlimited application to all types of fabrics and articles made therefrom including ladies and childrens dresses, garments of all types, sheets, pillowcases, drapery and upholstery materials, tablecloths, etc. One simple and practical example of the usefulness of the present invention is in connection with sheets, pillowcases and various articles of clothing for babies. These may be dyed and sold to the consumer in blue colors, which are traditionally used for boys. to pink, which is traditionally associated with baby girls, by a simple home treatment, either before use, or after a long period of use.

Perhaps more significant, however, is the application of our invention to articles of clothing for ladies, e.g., dresses and blouses, or to decorators fabrics, such as drapery and upholstery materials, where the ability to change solid colors or vari-colored patterns by a simple treatment at home will enhance the value of these fabrics to the consumer. For example, a fabric printed in four colors, namely, maroon, dark green, brown and blue may be used and laundered repeatedly, and thereafter subjected to the dilute acid treatment, which changes the above-mentioned colors to red, yellow, orange, and light green, respectively, by virtue of the decomposition of the blue component, Ultramarine blue, in the several The purchaser may, if desired,.change the color colors. When the blue component is decomposed, this changes the original colors to characteristically different colors.

A large series of colors may be formulated with a pigment comprising zeolitic aluminum silicate containing interstitial polyatoms of one or more elements from the group comprising sulfur, selenium, and telluriu'm as one of the components, and any one or more of these colors may be applied to a fabric and subseqently changed to another color or colors by treatment with dilute acid, which changes the zeolitic aluminum silicate pigment into a substantially colorless form.

The colors as applied have good fastness to light, crocking, laundering and dry cleaning, and the fabrics to which they are applied may be used and laundered over long periods of time. Subsequently, at any time during the life of the fabric, they may be treated with a dilute solution of a weak acid, such as citric acid, to effect a complete change of any or all of the original colors.

With regard to the application of the color, any resinbonded pigment printing or dyeing process which will work satisfactorily with the zeolitic aluminum silicate pigment and with the other components, may be used to apply these new colors, as will appear hereafter in the examples, and any person skilled in the art Will easily be able to determine the proper printing or dyeing process.

The dilute acid color changing treatment can be easily performed in the home using a simple pan, laundry tub, or automatic home laundry. Enameled equipment should be used only when the enamel is known to be acid resistant. Citric acid, acetic acid, or lactic acid are preferred because they are cheap, readily available, and safe even when used by inexperienced persons. However, other water soluble acids having a dissociation constant. of 1X10 or higher may be used,peven such strong acids as hydrochloric or sulfuric acid, if proper precautions are taken to neutralize the fabric before allowing it to dry. I

If desired, lemon juice may be used as a convenient source of citric acid and vinegar may be used as aconvenient source of acetic acid.

The speed of the color changing process is greatly in creased if a wetting agent is added to the acid solution. Examples of good wetting agents which are effective in concentrations of about 0.l% are. the polyoxyethylene ester of nonyl alcohol, and the sodium ,salt of the dioctyl ester of sulfosuccinic acid. If desired, any of the neutral nonionic household detergents, preferably in a concentration of about 0.3%, may be used.

The concentration of acid, the time of treatment, and the temperature of treatment for the color changing process are not critical. In solutions of acids containing a wetting agent, the concentration of acid may conveniently vary from about 0.1% to about 6%, the exact concentration required depending on the time and temperature of the treatment.

The temperature may conveniently vary between room temperature and the boiling point, the exact temperature required depending on the concentration of the acid and the timeof treatment.

The time may vary between about one minute and 24 hours, the exact time required depending on the acid concentration and the temperature of the treatment.

If citric, lactic, or acetic acids are used, the recommended concentration for acid and wetting agent, and the recommended conditions of time and temperature for the color changing process are given in the following table. 5% citric acid (or lemon juice); no wettinglagent:

V 10 minutes at F.

30 minutes at room temperature dyes or azoic dyes. zeolitic aluminum silicate pigment, using resin-bonded citric acid (or 100% lemon juice); 0.1% wetting agent:

5 minutes at 160 F. 15 minutes at room temperature 1% citric acid (or 20% lemon juice); 0.1% wetting agent:

minutes at 160 F. 30 minutes at room temperature 0.1% citric acid (or 2% lemon juice); 0.1% wetting agent:

30 minutes at 160 F. 12 hours at room temperature 5% lactic acid; 0.1% wetting agent:

5 minutes at 160 -F. minutes at room temperature 1% lactic acid; 0.1% wetting agent:

10 minutes at 160 F. 30 minutes at room temperature 0.1% lactic acid; 0.1% wetting agent:

2 hours at 160 F. 12 hours at room temperature 5% acetic acid (or 100%vinegar); 0.1% wetting agent:

15 minutes at 160 F. 30 minutes at room temperature 1% acetic acid (or vinegar); 0.1% wetting agent:

1 hour at 160 F. 5 hours at room temperature 0.5% acetic acid (or 10% vinegar); 0.1% Wetting agent:

2 hours at 160 F. 12 hours at room temperature In the changeable color process disclosed in this invention, the usual procedure is to use a resin-bonded pigment or a combination of resin-bonded pigments, at least one of which is a pigment comprising zeolitic aluminum silicate containing interstitial polyatoms of one or more elements from the group comprising sulfur, selenium, and tellurium. However, it is not necessary that the acid fast color be a resin-bonded pigment. Thus a fabric may be dyed by conventional procedure for applying vat Then it may be over dyed with the pigment techniques. The combination color so obtained may be changed by decomposing the zeolitic aluminum silicate pigment by dilute acid treatment.

Is so desired the color changing acid treatment may be localized. In this case the acid solution is best prepared with a thickener such as methyl cellulose or starch. The acid may then be applied by brush, pen, or special applicator to produce designs in the fabric. Such a procedure would ordinarily be used on novelty garments, which have been made from fabrics colored in a solid shade in accordance with the present invention, either by pad dyeing or blotch printing processes.

The following are typical and illustrative, but nonlimiting examples of this invention, the amounts indicated being parts by weight.

EXAMPLE 1 The following color concentrates are prepared by mixing the ingredients indicated.

Color Concentrate A (Blue) Ultramarine Blue pigment 30.00 Butylated melamine formaldehyde resin (65% Color Concentrate C (Yellow) Benzidine Yellow, Prototype 518 18.00 Butylated melamine formaldehyde resin (65% solution in xylene) 13.80 Pine oil 10.00 Mineral Spirits 58.20

100.00 Color Concentrate D (Orange) Molybdated Orange 25.00 Butylated melamine formaldehyde resin (65% solution in xylene) 19.20 Pine oil 10.00 Mineral spirits 45.80

Color Concentrate E (Green) Phthalocyanine Green, Prototype 483 20.00 Butylated melamine formaldehyde resin (65% solution in xylene) 13.80 Pine oi] 10.00 Mineral spirits 56.20

A water-in-oil printing emulsion (clear) was prepared as follows:

(1) Drying oil modified glycerol phthalate resin (50% solution in xylene) 1.50 (2) Mineral spirits 29.00 (3) Ammonium sulfate 1.00 (4) Water 68.50

Color Concentrate A, Blue 4.00 Color Concentrate B, Red 13.00 Clear 80.50 Latex 2.50

100.00 PRINT COLOR II (DARK GREEN) Color Concentrate A, Blue 20.00 Color Concentrate C, Yellow 5.00 Clear 65.00 Latex 10.00

100.00 PRINT COLOR III (BROWN) Color Concentrate A, Blue 11.00 Color Concentrate D, Orange 4.00 Clear 79.00 Latex 6.00

100.00 PRINT COLOR IV (BLUE) Color Concentrate A, Blue 12.00 Color Concentrate E, Green 0.75 Clear 81.25 Latex 6.00

- Cotton or rayon dress goods are printed with these colors using intaglio rolls. The printed goods are dried on steam cans and cured by exposing the goods to a temperature of 300 F. for one minute in a gas fired oven. After the usual finishing operation, application of starch,

The following solution is prepared. Citric acid- 1.0 Wetting agent (polyoxyethylene ester of nonyl alcohol or equivalent) 0.1 Water 98.9

The fabric or garment is immersed in this solution at room temperature for 30 minutes.

Color I (Maroon) changes to red.

Color I'I (Dark Green) changes to yellow. Color III (Brown) changes to orange. Color IV (Blue) changes to light green.

EXAMPLE 2 This example illustrates the procedure for using water dispersed pigments to prepare water-in-oil printing emulsions in which the pigment is dispersed inthe oi or solvent resin phase. Ultramarine blue is a hydrophilic pigment which flushes from the water to oil phase with difiiculty. -It is therefore not practical to use water dispersed ultramarine blue. In preparing Concentrate A (Blue), therefore, a solvent-resin dispersed ultramarine blue is used. In preparing the other color concentrates, B, C, and D, water dispersed pigments are used.

Concentrated pigment emulsions (water-in-oil) are prepared by premixing and homogenizing the following:

Color Concentrate A (Blue) Ultramarine Blue dispersion as described in Example 1, above *Drying oil modified glycerol phthalate resin (50% in xylene). 1.00 Ethyl cellulose (4% ethoxy) (10% in xylene) 1.00 Mineral spirits (KB45) 10.00 Butadiene styrene copolymer latex (50% solids) 12.00 Ammonium sulfate (20% in water) 0.25 Water 45.75

Color Concentrate B (Red) Oleic acid 0.25

Drying oil modified glycerol phthalate resin in xylene 1.00 Pine oil 5.00 Mineral spirits (KB45) 35.00 Ethyl cellulose (49% ethoxy) (10% in xylene) 1.00 Permanent Carmine 15.00 Butadiene styrene copolymer latex (40% solids) 6.00 Water 36.50 Ammonium sulfate (20% in water) 0.25

I 100.00 Color Concentrate C (Yellow) Oleic acid 0.25

Drying oil modified glycerol phthalate resin (50% V in xylene) 1.00 Pine V p 5.00 Mineral spirits (KB45) 35.00 Ethyl cellulose (49% ethoxy) 10% in xylene) 1.00 Benzidine Yellow,"special 15.00 Butadiene styrene copolymer latex (40% solids) 6.00 Water 36.50 Ammonium sulfate (20% in water) 0.25

6 Color Concentrate D (Green) Oleic acid- 0.25

Drying oil modified glycerol phthalate resin 50% in xylene) 1.00 Ethyl cellulose (49% ethoxy) (10% in xylene) 1.00 Pine oil 5.00 Mineral spirits (KB45) 35.00 Phthalocyanine Green (20% dispersion in water)- 15 .00 Butadiene styrene copolymer latex (40% solids) 6.00 Water -L 36.50 Ammonium sulfate (20% in water) 0.25

Print colors are prepared by mixing various proportions of these color concentrates with the emulsion clear described in Example 1.

PRINT COLOR I (DARK GREEN) Color Concentrate A (Blue) Q 52.00

Color Concentrate C (Yellow) 1.. 22.00 Clear 26.00

100.00 PRINT COLOR II (LIGHT GREEN) Color Concentrate A (Blue) 8.60 Color Concentrate C (Yellow) 4.00 Clear 87.40

100.00 PRINT COLOR III (LAVENDER) Color Concentrate A (Blue) 33.30 Color Concentrate E (Red) 8.00 Clear 58.70

PRINT COLOR IV (BLUE) Color Concentrate A (Blue) 8.60 Color Concentrate D (Green) on. 4.00 Clear -2. 87.40

Cotton or rayon drapery fabric is printed with these colors using intaglio rolls. The goods are dried on steam cans. The color is set by passing the printed goods through a gas fired curing oven at a speed which will give a 1 minute cure at 300 F. The goods are then soaped and finished in the usual manner. The goods may be fabricated into draperies. These draperies may be used and laundered when necessary. At any time, even after repeated launderings, by giving the citric acid treatment described in Example 1, the colors may be caused to change as follows:

Print Color I (Dark Green) To Dark Yellow. Print Color 11 (Light Green) To Light Yellow. Print Color HI (Lavender) To Bright Red. Print Color IV (Blue) To Green.

EXAMPLE 3 Stabilized Azoic Red R., Prototype 169 20.00 Starch-tragacanth print paste 80.00

A cotton drapery fabric is printed with these five colors EXAMPLE 4 SCREEN PRINT IN ALL WATER PRINT PASTE Pigment colors suitable for screen printing are prepared by mixing the following:

Screen Print Color I (Brown) Ultramarine Blue (50% dispersion in water) 11.00 Lithol Red R, Color Index 189 dispersion in water) 2.00 Molybdated Orange (complex of lead chromate and lead molybdate, dispersion in water) 4.50 Ammonium salt of polymeric carboxylic acid 1.00 Latex, acrylic ester-acrylic acid copolymer (50% solids) 12.00 Trimethoxytrimethylol melamine resin (60% solution in water) 6.00 Water 63.50

100.00 Screen Print Color H (Green) I Ultramarine Blue (50% dispersion in water) 7.00 Phthalocyanine Green, Pr. 483 (20% dispersion in water) 3.50 Benzidine Yellow, special (20% dispersion in water) 2.50 Ammonium salt of polymeric carboxylic acid 1.00 Latex, acrylic ester-acrylic acid copolymer (50% solids) 8.00 T rimethoxytrimethylol melamine resin (60% solution in water) 4.00 Water 74.00

, 100.00 Screen Print Color III (Rust) Ultramarine Blue (50% dispersion in water) 3.00 Molybdated Orange (complex of lead chromate and lead molybdate, 30% dispersion in water) 5.00 Benzidine Yellow, special (20% dispersion in water) 10.00 Ammonium salt of polymeric carboxylic acid 1.00 Latex, acrylic ester-acrylic acid copolymer (50% solids) 10.00 Trimet-hoxytrimethylol melamine resin (60% solution in water) 8.00 Water 63.00

100.00 Screen Print Color IV (Blue Green) Ultramarine Blue (50% dispersion in water) 20.00 Benzidine Yellow, special (20% dispersion in water) 1.00 Ammonium salt of polymeric carboxylic acid 1.00 Latex, acrylic esteracrylic acid copolymer (50% solids) 10.00 Trimethoxytrimethylol melamine resin (60% solutionin water) 8.00

Water 60.00

Table cloths are printed with these four colors using the conventional silk screen process. The printed cloths are dried at room temperature and exposed to a temperature of 300 F. in a curing oven for 1 minute. The

8 printed table cloths are fast to washing, dry cleaning, light and crocking.

When treated with dilute citric acid using the procedure described in Example 1, even after repeated laundering, the colors change as follows:

Color I (Brown) to Red Orange Color II (Green) to Yellow Green 7 Color III (Rust) to Yellow Orange Color IV (Blue Green) to Yellow The changed colors retain their fastness properties.

EXAMPLE 5 PIGMENT PAD DYEIN G USING A WATER SYSTEM BLUE FOR BOYS-PINK FOR GIRLS LINES FOR STORK SHOWERS A padding liquor is prepared by mixing the following ingredients.

Cotton sheeting is padded with this liquor using a threetrol-l padder. The padded fabric is dried by passing through a gas fired pro-drying oven at about 250 F. It is then cured by passing through a gas fired curing oven at about 300 F. The finished fabric is evenly colored and has satisfactory fastness properties.

The sheeting may be fabricated into sheets or pillow cases which, being blue, are traditionally suitable for baby boys. If so desired, these may be changed to pink, traditionally suitable for baby girls, by the citric acid treatment described in Example 1.

In the above example, cotton sheeting was used to prepare changeable color baby linens. The same procedure may also be used for coloring other fabrics, for example, diaper fabric or baby dress goods.

EXAMPLE 6 Pad dyeing in which the acid resistant color component is furnished by an azoic dye, not by a resin-bonded pigment. Blue-for-Boys-Pink-for-Girls lines for stork showers.

Cotton sheeting is dyed in a light pink shade by applying on a three roll padder a solution containing 0.01% of Naphthol AS-ITR, Pr. 310, and drying.

The fabric is then passed through a solution of diazotized Red ITR Base, Pr. 378, to form a pink, acid resisting color within the fibers. The fabric is then soaped, rinsed, and dried.

A padding liquor for applying an acid sensitive resinbonded pigment color is prepared by mixing the following ingredients.

Water This padding liquor is applied with a three roll padder to the fabric which has already been dyed to a light pink shade with the azoic color. The padded fabric is 9. dried by passing through a housed tenter frame at about 300 F. It is then dried completely and cured by passing through a gas fired curing oven at about 300 F. The finished fabric is evenly colored and has satisfactory fastness properties.

The sheeting may be fabricated into sheets or pillowcases which being blue (although the color contains a small amount of red component) are traditionally suitable for baby boys. If so desired these may be changed to pink, traditionally suitable for baby girls, by the following procedure.

The following solution is prepared:

Vinegar 20.00 Neutral nonionic household detergent 0.30 Water 79.70

The sheets or pillow cases may be changed from blue to pink by immersing them in this solution for hours at room temperature.

EXAMPLE 7 A fabric dyed in a solid color which can be decorated in various designs by the localized application of an acid solution.

A printing color containing ultramarine blue pigment alone is prepared by mixing the following ingredients.

Color Concentrate A, Blue (as in Example I) 20.00 Clear (as in Example I) 70.00

Latex, acrylonitrile-butadiene copolymer (40% solids) 10.00

Shirting fabric is blotch printed with this color, using intaglio rolls.

The printed goods are dried on steam cans and cured by exposing the goods to a temperature of 300 F. for 1 minute in a gas fired oven. The fabric is finished by the application of a softener, starch, etc. The evenly colored fabric may then be fabricated into shirts.

A slightly thickened solution of lactic acid is prepared by mixing the following ingredients.

Lactic acid 5.00

Solution of household transparent starch (sodium carboxy-methyl-cellulose) 93.50 Neutral nonionic household detergent 0.50 Glycerine 1.00

This solution is used to write, print, paint, or draw designs on the shirt, and allowed to remain until dry. Characteristic white designs appear where the thickened lactic acid solution is applied.

EXAMPLE 8 A pigmented padding emulsion is prepared by mixing with a high-sheer mixer the following ingredients:

Water 85.50

10 This padding liquor consists of an oil-in-water emulsion with thermosetting resin dissolved in the oil phase and with pigment dispersed in the water phase. A non- Woven cellulosic fabric is padded with this liquor using a three roll padder. The fabric is predried by passing over steam-heated drying cans. The thermosetting resin is set by passing the dried fabric through a gas fired curing oven at about 300 F. The finished fabric is evenly colored in a beige shade and has good fastness to laundering and crocking. I

The beige colored non-woven fabric, or articles prepared from it, may be caused to change color from beige to yellow by immersing for 12 hours at room temperature in a solution containing 2% lemon juice and 0.3% non-ionic household detergent.

The dyestuffs referred to in the foregoing examples, and throughout the specification and claims, are identified as follows (American Chemical Society Nomenclature):

Ultramarine Blue, Color Index Number 1290:

A blue zeolitic sulfur-containing aluminum silicate pigment. Permanent Carmine:

A pigment prepared'by coupling diazotized Red ITR Base, Prototype Number 37 8., N,N'diethyl-4-methoxymetanilamide with Naphthol AS-ITR, Prototype Number 310, 5-chloro-3-hydroxy-2,4-dimethoxy-Z-naphthanilide. Benzidine Yellow, Prototype Number 518:

A pigment prepared by coupling tetrazotized 3-3- dichlorobenzidine with o-acetoacetoanilide. BenzidinetYellow, special (except in Example 8):

A pigment prepared by coupling tetrazotized 3-3- dichlorobenzidene with o-acetoacetotoluidide. Molybdated Orange;

A pigment complex prepared from lead chromate and lead molybdate. Phthalocyanine Green, Prototype Number 483:

Chlorinated copper phthalocyanine pigment. Stabilized Azoic Red R, Prototype Number 169:

Diazotized 4-chloro-o-anisidine, Prototype Number 271, stabilized with sarcosine, and mixed with Naphthol AS-OL, Prototype-Number 311, 3 hydroxy-2-naptho-o-anisidide. Lithol Red R, Color Index Number 189:

Diazotized Z-amino-l-naphthalenesulfonic acid coupled with 2-naphthol. Ultramarine Violet:

A zeolitic sulfur-containing aluminum silicate pigment.

While this invention has been described in the foregoing examples as being applied to cotton and rayon fabrics, it is to be understood that the invention is not limited to such fabrics. Any fabrics which can be pigment printed or pigment dyed may be used. Thus fabrics made from natural fibers such as linen, wool or silk, from mineral fibers such as glass or asbestos, or from synthetic fibers such as cellulose acetate, nylon (a long chain synthetic polymeric amide), Dacron (a condensation polymer of ethylene glycol with terephthalic acid), and Orlon (acrylonitrile polymer) may also be colored with the changeable colors of our invention.

These changeable colors may be applied not only to woven fabrics but also to knit fabrics or other nonwoven fabrics. Paper can also be colored with these colors provided that it has the necessary wet strength to withstand the coloring process and the subsequent acid treatment.

This invention has been described above in detail for purposes of illustration only, and is not intended to be limited by this description or otherwise, except as defined in the appended claims.

We claim:

1. A fabric colored with an intimate mixture of colors at least one of which is an acid resistant color and one is a resin-bonded pigment comprising zeolitic aluminum silicate containing interstitial polyatoms of one or more elements from the group consisting of sulfur, selenium, and tellurium that is decomposed by treatment with a dilute solution of an acid having a dissociation constant of 1x10 or higher, to render the zeolitic aluminum silicate pigment substantially colorless, so as to efiect thereby a characteristic color change in the fabric to the hue of said at least one acid resistant color.

2. A fabric as defined in claim 1 in which said zeolitic aluminum silicate pigment is ultramarine blue pigment.

3. A fabric as defined in claim 1 in which said zeolitic aluminum silicate pigment is ultramarine violet.

4. A fabric colored with a resin-bonded ultramarine blue pigment and an acid resisting pink color, which acid resisting pink color is used in an amount that is not sufficient to affect the blue shade of the ultramarine blue,

but that is sufficient to give a pastel pink shade when theultramarine blue pigment is rendered colorless.

5. Afabric colored with an intimate mixture of colors, said mixture comprising a color that is decomposable when acid treated, and at least one acid resistant color used in an amount that is not sufficient to affect significantly the shade of the acid decomposable color, but that is sufficient to give a characteristic shade when the acid decomposable color has been acid treated.

6. A fabriccolored with an intimate mixture of colors having a characteristic hue, said mixture comprising at least one acid resistant color and a color that is decomposable upon acid treatment, said at least one acid 'resistant color remaining when said fabricis treated with an acid and thereby said characteristic hue is changed to the hue of said at least one acid resistant color.

7. A fabric colored with an acid resisting color and over colored with resin bonded ultramarine blue pigment to produce a fabric colored with a blended color, said ultramarine blue pigment being susceptible to decomposition when treated with a solution of an acid having a pH of 3 or less, said fabric having the hue of said acid resisting color after being treated with said solution of acid.

8. A process for producing a change in the color of a 5 fabric which has been colored with an intimate mixture of an acid decomposable color and an acid resistant color comprising treating the said fabric with a solution of acid having a pH of 3 or less whereby the acid decomposable color is substantially decomposed and the acid resistant 10 color is substantially unaffected thereby changing the color of the fabric from the hue of the intimate mixture to the hue of the acid resistant color.

References Cited in the file of this patent Ridner: The Artists Chromatic Hand Book, New York, George Putnam, 155 Broadway (1850) (pp. 61-62 relied upon). 4

Standage: The Artists Manual of Pigments, London,

35 Crosby Lockwood and Co. (1886) (p. 31 relied upon).

Kumins: Am. Ink Maker 32, No. 5, page 47 relied upon.

rUNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,030,227 April 17, 1962 Alfred T. Clifford et al. It is hereby certified that e rror appears in the above numgd pa1 ent requiring correction and that the said Letters Patent shoul' ead a: corrected below.

Column 5, line 43, for "(4% ethoxy)" ethoxy) column 10,

read (49% line 26, for "2,4 2',4'

read

Signed and sealed this 28th day of August 1962.

(SEAL) Mtest:

ISTON G. JOHNSON DAVID L. LADD Lttesting Officer Commissioner of Patents

Claims

1. A FABRIC COLORED WITH AN INTIMATE MIXTURE OF COLORS AT LEAST ONE WHICH IS AN ACID RESISTANT COLOR AND ONE IS A RESIN-BONDED PIGMENT COMPRISING ZEOLITIC ALUMINUM SILICATE CONTAINING INTERSTITAL POLYATOMS OF ONE OR MORE ELEMENTS FROM THE GROUP CONSISTING OF SULFUR, SELENIUM, AND TELLURIUM THAT IS DECOMPOSED BY TRETMENT WITH A DILUTE SOLUTION OF AN ACID HAVING A DISSOCIATION CONSTANT OF 1X10-5 OR HIGHER, TO RENDER THE ZEOLITIC ALUMINUM SILICATE PIGMENT SUBSTANTIALLY COLORLESS, SO AS TO EFFECT THEREBY A CHARACTERISTIC COLOR CHANGE IN THE FABRIC TO THE HUE OF SAID AT LEAST ONE ACID RESISTANT COLOR.