US3310361A

US3310361A - Process for the production of multi-colored woolen goods

Info

Publication number: US3310361A
Application number: US322071A
Authority: US
Inventors: John R Stewart
Original assignee: GEIGY CHEMICAL Co
Current assignee: GEIGY CHEMICAL Co
Priority date: 1963-11-07
Filing date: 1963-11-07
Publication date: 1967-03-21
Anticipated expiration: 1984-03-21

Description

United States Patent 3,310,361 PROCESS FOR THE PRODUCTION OF MULTI- COLORED WOOLEN GOODS John R. Stewart, Pointe Claire, Quebec, Canada, assignor to Gelgy Chemical Company, Greenburgh, N.Y., a corporation of Delaware No Drawing. Filed Nov. 7, 1963, Ser. No. 322,071 14 Claims. (Cl. 8-15) This invention relates to the dyeing of woolen goods. More particularly, the present invention pertains to a process for dyeing woolen goods so as to obtain multicolored etfects and especially two-tone or tone-on-tone effects with excellent light and wet fastness.

'Heret-ofore, woolen materials exhibiting multi-colored effects could be produced only by first preparing dyed materials of different colors and then weaving these into the desired color patterns. It is at once obvious that such a dyeing method is involved and costly as it is necessary to anticipate a multitudeof color combinations in advance, thereby creating large quantities of stock which, if color demands change, may no longer be useful, or to bear the consequence of long delays in deliveries because of the processing necessary to produce the desired color patterns. According to another present practice for achieving two-tone effect, Woolen materials are treated so as to make some residues of amino acids found in wool wholly or partially resistant to selected dyestuffs which normally dye wool (see Canadian Patent No. 519,099, issued Dec. 6, 1955). The disadvantage which inheres in this method is the difiiculty of obtaining reproducible results and the limitation to color effects in the nature of heather (ingrain or melange) effects. Still another method which may be employed for limited multi: color dyeing o-f woolen materials is the chlorination method, i.e. the treatment of wool with hypochlorites and dyeing such wool in combination with untreated wool. Col-or effects by this method are produced, however, at the expense of the durability and adequate wet fastness of the treated fibers.

In contrast thereto, it has now surprisingly been found that two-tone woolen goods which are commercially acceptable and competitively producible on a large scale and which are free of any of the disadvantages enumerated above, can conveniently and readily be produced by a process which consists of a combination of sequential steps: first the pre-treatment of the given woolen material by mordanting with a chromate o-r bichrornate fixed on the wool fiber by means of a sulfite or bisulfite salt as reducing agent; secondly, the removal of unfixed chrome by rinsing; thirdly, the combining of the woolen materials so treated withuntreated woolen materials; fourthly, the dyeing of the composite with a mordant dye or a combination of mordant dyes; and lastly, an aftertreatment which involves addition of the above chrome mordants to the dyebath.

More specifically, the process of this invention contemplates first the mordanting of woolen materials by an improved bottom chroming procedure which yields surprising and unexpected results. The woolen materials are treated in an aqueous solution containing 0.5 to 2% and preferably not over 1.5 %on the weight of wool, of

a chromate, such as, potassium or sodium chromate or bichr-omate and an organic or inorganic non-chelatin-g acid, preferably formic, acetic or sulfuric acids, giving a pH in the range of between 2 and 6 .and preferably about 4.5 to maintain the wool in optimum condition. The amount of the chromate used, as indicated by the above range of from 0.5 to 2% on the weight of wool, is important: if less than 0.5% is employed an insuflicient amount of chrome may become fixed onto the fiber for 3,310,361 Patented'Mar. 21, 1967 ICC production of heavy shades; if more than 2% is used, the durability and quality of the wool may be deleteriously affected. It has been found that 1.5% of the chromate is preferable as it will insure complete chroming of the fiber even for the heaviest shades desired.

This mordanting treatment then involves boiling for from 30 to 60 minutes and the subsequent additionof sodium or potassium sulfite or bisulfite as reducing agent in a concentration of fro-m 0.5 to 1%and preferably 0.75 %on the weight of wool. The treatment is continued by further boiling for from 15 to 30 minutes until the appearance of the wool fiber is a uniform greenishgray (without a yellowish tint) indicating the substantially complete fixation of the chrome on the fiber The presence of any of the above reducing agents is critical as it serves the purpose of substantially completing the re-' duction of the chrome in hexavalent form to its trivalent cationic stable form for maximum mordanting action and to minimize the migration of unreduced (labile) chrome to the untreated Wool in the subsequent cross-dyeing operation. The advantages achieved thereby are substantial reduction of staining of the untreated woolen material by the mordant dyestutf and reproducibility from lot to lot in subsequent dyeing. The amount of reducing agent used is also important: if less than 0.5% on the weight of wool is used incomplete reduction and fixation of the chrome will be achieved, if more than 1% is em ployed, however, the cystine linkages of the wool fiber may be deleteriously affected.

After the above-described mordanting procedure is concluded, the material treated must be rinsed thoroughly in water at approximately F. to remove any unfixed chrome present. The material is subsequently dried.

The wo-olen materials so treated can then be combined in Whatever form is suitable (e.g. by carding, combing, spinning, twisting, and notably weaving, knitting, tufting, assembling, etc.) with untreated woolen materials as a second step.

It is then possible to dye the composite thus obtained with a mordant dye or a combination of mordant dyes. This dyeing procedure, for instance, involves the preparation of a dye bath at a temperature of from 100 to F. containing from 5 to 10% on the weight of the wool of anhydrous Glauberssalt, sufiicient acetic acid (or any other organic or inorganic non-chelating acids, such as, formic acid, sulfuric acid, etc.) to obtain a pH of 2 to 6, and 0.5 to 2% of Tinegal Wa condensate of stearyl diethylene triamine and ethylene oxide. In addition to Tinegal W, Irgasol SW, the condensate of N -stearyl-N N -bis-(fi-phenol hydroxyethyl)-diethylene triamine and ethylene oxide may also be used to particular advantage. (See Example 3, Belgian Patent 592,741.) This liquor is then circulated for from 10 to 15 minutes and any of the desired mordant dyes-or combinations thereof is dissolved and added. The temperature of the dye bath is then raised to the boil and it is boiled for from 30 to 60 minutes.

Mordant dyes, and particularly chrome dyes which can be employed in the practice of this invention are illustrated in the examples below. Further chrome dyes that can be used are the following:

C.I. Mordant Black 1 (Color Index No. 15710) C.-I. Mordant Black 9 (Color Index No. 16500) C.I. Mordant Black 13 (Color Index No. 63615) C.I. Mordant Black 17 (Color Index No. 15705 C.I. Mordant Black 38 (Color Index No. 18160) C.I. Mordant Blue 9 (Color Index No. 14855 CI. Mordant Blue 47 (Color Index No. 43855) C.'I. Mordant Brown 1 (Color Index No. 20110) C.I. Mordant Brown 19 (Color Index No. 14250) C.I. Mordant Brown 23 3 C.I. Mordant Brown 33 (Color Index No. 13250) C.I. Mordant Brown 40 (Color Index No. 17590) C. I. Mordant Brown 63 C.I. Mordant Orange 1 (Color Index No. 14030) C.I. Mordant Orange C.I. Mordant Orange 6 (Color Index No. 26520) C.I. Mordant Red 3 (Color Index No. 58005) C.I. Mordant Red 17 (Color Index No. 18750) C.I. Mordant Violet 28 (Color Index No. 43570) C.I. Mordant Yellow 14 (Color Index No. 14055) C.I. Mordant Yellow 30 (Color Index No. 18710) The employment of one or more fast wool colors or the acid type in conjunction with the above-mentioned chrome colors brings about an extension of the contrast range obtainable by means of the chrome colors themselves and also serves in practice the important purpose of permitting shading corrections and alterations of a minor nature to be effected once the major contrast has been established by means of chrome colors. Acid dyestuffs suitable for such purposes should be selected from those that are fast to chrome well known in the art, that is to say, those which do not suffer any adverse change on either shade or fastness properties by the subsequent top chroming procedure.

For example, acid dyes of the following groups may be used:

1. 1:2 pre-metallized acid dyes (i.e. one atom of metal complexed with two molecules of dyestuff) normally applied from weak acid solutions, pH 6.

2. Acid dyes which are normally applied with weak acids of a pH of 4.5 to 6.

3. Fibre reactive dyes which are normally applied to wool from weak acid baths (pH 3 to 5).

The above dyestuffs whether mordant or acid, may be used in any of the following concentrations: 0.001% to 6% depending on the shade of color desired and the strength of the dyestuffs used.

The after-treatment then involves an addition to the dyebath of between 0.1 and 1.5% and preferably about 0.25 to 1% of a chromate, such as sodium or potassium chromate or dichromate. This addition is made after the mordant dye or combination of mordant dyes has been exhausted onto the composite of treat-ed and untreated woolen material; it serves the purpose of topchroming the mordant dye present on the untreated fiber, converting this dye into an insoluble metal lake. After this addition, boiling is continued for another 30 to 60 minutes. Certain selected mordant dyes, well known in the art, for example, such as are applicable by meta-chrome dyeing methods, permit the simultaneous presence of mordant in the application bath. In such cases it is possible to add the mordant to the dye bath at the beginning of the dyeing operation. By making an addition of mordant to the dye bath in either or both of the above ways an increased all-round fastness, particularly, light and wet fastness, of the unmordanted portion of the composite is achieved.

Lastly, the dyed woolen goods are rinsed in a fresh bath at 100 to 120 F. for approximately 15 minutes and dried.

The following examples will illustrate the invention in greater detail, but should be taken to limit the invention in any way. The percentages given are percentages by weight calculated on the weight of wool.

A. MORDANTING PROCEDURE Example I Wool yarn was treated in a dyeing vessel at a liquor ratio of 25 parts of water to one part of wool. Sodium bichromate (1.5%) and 2% of formic acid 85%, were added. This was boiled for 45 minutes and 0.75% of sodium bisulfite was then added and the boiling continued for 15 minutes. The yarn was then rinsed in water at F. and dried.

B. COMBINING THE TREATED AND UNTREATED WOOLEN MATERIALS Example 11 A dye bath was prepared at a temperature of F. with 10% of Glaubers salt, anhydrous, 3% of acetic acid 56% and 0.5% of Irgasol SW. The liquor was circulated for 10 minutes and 0.04% of C.I. Mordant Black 13 (Color Index No. 63615) and 0.01% of C.I. Mordant Violet 28 (Color Index No. 43570) were dissolved in water and added. The temperature was raised to the boil and the liquor was boiled for 30 minutes. Then 0.5% of sodium bichromate was added and the boiling continued for another 45 minutes. The fabric was then rinsed in a fresh bath at 100 F for 15 minutes and dried.

A fabric having dark gray and light gray shades was obtained, the pre-treated yarn exhibiting the darker shade.

In the following examples the procedure of Example II was repeated with the substitution, however, of other mordant dyes to obtain various other two-tone effects.

Example III A dark green (pre-treated yarn) and light green fabric was obtained.

Example IV Percent C.I. Mordant Violet 1 (Color Index No. 43565) 0.50 Acetic acid 56% 2.00 Glaubers salt 10.00 Irgasol SW 0.25

A violet (treated yarn) and bluish grey fabric was obtained.

Example V Percent C.I. Mordant Orange 8 1.00 Irgasol SW 0.25 Glaubers salt 10.00 Acetic acid 56% 2.00

A dark orange (treated yarn) and light pink fabric was. obtained.

Example VI w Percent C.I. Mordant Blue 1 (Color Index No. 43830) 0.50 Glaubers salt 10.00 Irgasol SW 0.125 Formic acid 85% 1.00

A dark royal blue (treated yarn) and bluish grey fabric was obtained.

Example VII Percent C.I. Mordant Green 5 0.50 Glaubers salt 10.00 Irgasol SW 0.25

Acetic acid 56% 2.00

'trast color effects.

form can be spun into singles yarn and used either as A dark green (treated yarn) and light green fabric was obtained.

Example VIII 1 Percent C.I. Mordant Green 26 (Color Index No. 18180) 0.75 Glaubers salt 10.00 Formic acid 85% 2.00 Tiuegal W 0.50

A heavy olive-green (treated yarn) and light blue-grey fabric was obtained.

Example IX Percent ClI. Mordant Red 7 (Color Index No. 18760) 0.75 Glaubers salt 10.00 Tine-gal W 0.50 Acetic acid 56% 2.00

A heavy bordeaux (treated yarn) and pink fabric was obtained.

The CI. Acid Yellow 79 in this formula is not chromed but produces a fastyellow shading component on the untreated wool and the top chroming procedure intensifies this contrast as well as producing the best all-round fastness of the composite. A grey green (chromed) and beige (unchromed) contrast pattern is obtained.

It will be readily appreciated by skilled colorists that the above examples are merely illustrative and that numerous other color combinations can easily be achieved.

Further interesting color combinations exhibiting threecolor effects have been produced by combining treated and untreated woolen materials, described above, with woolen materials which have been separately dyed or pre dyedwith fastness to cross dyeing-in very dark shades, such as, black, deep navy blue, dark .brown and dark green. The resulting composite is then piece-dyed.

It is alsoreadily apparent to men skilled in the art that g the above-described mordanting and dyeing procedure may be applied to woolen materials in any form. For example, wool in loose form, i.e. raw stock, can be so treated and combined with loose untreated wool and dyed in loose form or spun into yarn and dyed or the yarn thus obtained can be converted to fabric and then dyed. Such fibers, yarns or fabrics exhibit heather color effects. Furthermore, wool in loose form which has been so treated, can be spun into singles yarn and plied with untreated yarns and dyed in yarn form or incorporated in a fabric and piece-dyed. These yarns or fabrics given con- In addition, treated wool in loose singles or plied yarn to be made into fabrics together with untreated yarn and then piece-dyed to give multi-color or two-tone effects as indicated and shown above.

Altcrnately, woolen materials in yarn form can be processed in accordance with this invention and treated singles yarns can be plied with untreated singles and yarn dyed novelty fleck and slub yarfi. These are likewise within the scope of the present invention.

' What is claimed is:

1. A process for producing multi-colored woolen goods which comprises treating woolen material by boiling in an aqueous solution containing 0.5 to 2% on the weight of wool of a chromate selected from the group consisting of sodium and potassium chromate and bichromate, 0.5 to 1% on the weight of wool of a reducing agent selected from the group consisting of sodium and potassium sulfite and bisulfite and a non-chelating acid giving a pH in the range of between 2 and 6, rinsing the mordanted Woolen material, combining the woolen material so treated with untreated Woolen material, dyeing the composite in a dye bath containing at least one mordant dye and adding to said dyebath when exhausted 0.1 to 1.5% on the weight of wool of the said chromate.

2. A process according to claim 1 wherein 1.5%-on the weight of wool of the chromate and 0.75% on the weight of Wool of the reducing agent is present in said solution and wherein 0.25 to 1% on the weight of wool of the chromate is added to said dyebath.

3. A process according to claim 1 wherein said composite is dyed in a dye bath which contains also at least one acid dye.

4. A process for producing multi-colored Woolen goods which comprises treating woolen material by boiling in an aqueous solution containing 0.5 to 2% on the weight of wool of a chromate selected from the group consisting of sodium and potassium chromate and bichromate, 0.5 to 1% on the weight of wool of a reducing agent selected from the group consisting of sodium and potassium sulfite and bisulfite and a non-chelating acid giving a pH in the range of between 2 and 6, rinsing the mordanted woolen material, combining the Woolen material so treated with untreated woolen material, dyeing the composite by boiling in a dye bath containing at least one mordant dye and 0.1 to 1.5 on this weight of wool of said chromate.

5. A process according to claim 3 wherein 1.5% on the weight of wool of the chromate and 0.75% on the weight of wool of the reducing agent is present in said solution and wherein 0.25 to 1% on the weight of wool of the chromate is added to said dye bath.

6. A process according to claim 4 wherein said composite is dyed in a dye bath which contains also at least one acid dye.

7. A process for producing multi-colored woolen goods which comprises mordanting woolen material by boiling in an aqueous solution containing 0.5 to 2% on the weight of wool of a chromate selected from the group consisting of sodium and potassium chromate and bichromate and a non-chelating acid giving a pH in the range of between 2 and 6, adding to said solution 0.5 to 1% on the weight of Wool of a reducing agent selected from the group consisting of sodium and potassium sulfite and bisulfite, continuing said boiling, rinsing the mordanted woolen material thoroughly with water of about F., combining the woolen material so treated with untreated woolen material, dyeing the composite by boiling in a dyebath containing at least one mordant dye and adding 0.1 to 1.5 on the weight of wool of the said chromate to the dye bath when exhausted and continuing said boiling.

8. A process according to claim 5 wherein 1.5% on the Weight of wool of the chromate and 0.75% on the Weight of wool of the reducing agent is present in said solution and wherein 0.25 to 1% on the weight of wool of the chromate is added to said dye bath.

9. A process according to claim 7 wherein said composite is dyed in a dye bath which contains also at least one acid dye.

10. A process for producing multi-colored woolen goods which comprises mordanting woolen material by boiling in an aqueous solution containing 0.5 to 2% on the weight of wool of a chromate selected from the group consisting of sodium and potassium chromate and bichromate and a non-chelating acid giving a pH in the range of between 2 and 6, adding to said solution 0.5 to 1% on the weight of wool of a reducing agent selected from the group consisting of sodium and potassium sulfite and bisulfite, continuing said boiling, rinsing the mordanted woolen material thoroughly with water of about 100 F., combining the woolen material so treated with untreated woolen material, dyeing the composite by boiling in a dye bath comprising at least one mordant dye and 0.1 to 1.5% on the weight of wool of said chromate.

11. A process according to claim 7 wherein 1.5 on the weight of wool of the chromate and 0.75 on the weight of wool of the reducing agent is present in said solution and wherein 0.25 to 1% on the weight of wool of the chromate is added to said dye bath.

12. A process according to claim 10 wherein said composite is dyed in a dye bath which contains also at least one acid dye.

13. A process for producing multi-colored woolen goods which comprises mordanting woolen material by boiling in an aqueous solution containing 1.5% on the weight of wool of sodium bichrornate and about 2% on the weight of wool of formic acid, adding to said solution 0.75% on the weight of Wool of sodium bisulfite as reducing agent, continuing said boiling until the woolen material is uniformly greenish-grey, rinsing the mordanted woolen material thoroughly with water of about 'F., combining the woolen material so treated with untreated woolen material, dyeing the composite by boiling in a dyebath containing at least one mordant dye and adding 0.5% on the weight of wool of the said sodium bichromate tothe dyebath when exhausted, continuing said boiling and then rinsing and drying said composite.

14. A process according to claim 13 wherein said composite is dyed in a dye bath which contains also at least one acid dye.

References Cited by the Examiner UNITED STATES PATENTS 670,959 4/1901 Kick 815 689,559 12/1901 Meyer 815 3,006,935 10/1961 Albrecht 861 OTHER REFERENCES Townend, 1., Soc. Dyers & Col., June 1945, pp. 144-149.

Knecht, A., Manual of Dyeing, 9th ed., vol. 1, pp. 251- 259, pub. 1945 by Mapleton House, publ., Brooklyn 4, New York.

NORMAN G. TORCHIN, Primary Examiner.

T. J. HERBERT, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent Nou 3,310,361 March 21, 1967 John R, Stewart e above numbered pat- It is hereby certified that error appears in th Patent should read as ent requiring correction and that the said Letters corrected below.

In the heading to the printed specification, line 5, for "Geigy Chemical Company Signed and sealed this 7th day of November 1967.

(SEAL) Attest:

EDWARD J. BRENNER Edward M. Fletcher, Jr.

Commissioner of Patents Attesting Officer read Geigy Chemical Corporation

Claims

1. A PROCESS FOR PRODUCING MULTI-COLORED WOOLEN GOODS WHICH COMPRISES TREATING WOOLEN MATERIAL BY BOILING IN AN AQUEOUS SOLUTION CONTAINING 0.5 TO 2% ON THE WEIGHT OF WOOL OF A CHROMATE SELECTED FROM THE GROUP CONSISTING OF SODIUM AND POTASSIUM CHROMATE AND BICHROMATE, 0.5 TO 1% ON THE WEIGHT OF WOOL OF A REDUCING AGENT SELECTED FROM THE GROUP CONSISTING OF SODIUM AND POTASSIUM SULFITE AND BISULFITE AND A NON-CHELATING ACID GIVING A PH IN THE RANGE OF BETWEEN 2 TO 6, RINSING THE MORDANTED WOOLEN MATERIAL, COMBINING THE WOOLEN MATERIAL SO TREATED WITH UNTREATED WOOLEN MATERIAL, DYEING THE COMPOSITE IN A DYE BATH CONTAINING AT LEAST ONE MORDANT DYE AND ADDING TO SAID DYEBATH WHEN EXHAUSTED 0.1 TO 1.5% ON THE WEIGHT OF WOOL OF THE SAID CHROMATE.