DE1444262A1 - Method of making multi-colored wool material - Google Patents

Description

Dr. F. Zumstefη - Dr. B. Assmann Dr. R. Koenlgsberger A L. L · Δ O ß

JR GEIGY AG Patent Attorneys JHtHiOi

Munich 2, Bräuhaueetraße 4 / ill Basel 16 (Switzerland) Method of making multi-colored wool material

The present invention relates to a method for dyeing wool materials, in particular piece dyeing Whole-wool carpets to achieve multi-color effects and especially two-tone and contrast effects.

Until now, such multicolored woolen materials could only be obtained by first dyeing or printing them Made materials of different colors and then woven them into the desired color patterns. It is clear that a such a method is cumbersome because it is necessary to consider a variety of color combinations, whereby large stocks must be created. Another method to achieve two-tone effects consists in treatment of wool materials in such a way that amino acids are formed, the residues of which are then not or only in the wool some can be dyed with selected dyes which normally dye wool. The disadvantages of this method are difficult to obtain reproducible results and the limitation of color effects. Yet another method, which is used for two-tone coloring of wool materials can be used is the chlorination method, i.e. the treatment of wool with hypochlorites, which are based on the depth of the hues affects the way that two-tone effects can be achieved by dyeing such wool in combination with untreated wool. However, such color effects come at a cost

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the durability of the treated fibers _? and, moreover, this method is unsuitable for providing contrast effects.

It has now surprisingly been found that wool materials can be obtained in a variety of color combinations by one process without the aforementioned disadvantages consisting firstly of pre-treating the wool material by any of the known metal pre-pickling processes disclosed in Pickling the wool with metal salts, such as salts of chromium, copper, cobalt, manganese, iron, aluminum; secondly, in the combination of the previously treated wool materials with untreated wool materials; and thirdly in dyeing the resulting wool blend either with mordant dyes or a combination of mordants and acidic dyes to achieve the desired multicolored, contrasting or two-tone color effects.

The first step of the process according to the invention consists in a staining process for wool, such as, for example, the pre-chromating process. Accordingly, the wool is treated in a solution which contains 0.5 to 5%, based on the wool weight, of potassium or sodium dichromate or an equivalent metal salt and an organic or inorganic acid, to a pH value in the range between 2 and 6 to achieve. This treatment then requires boiling for 30 to 60 minutes and then adding a reducing agent such as sodium bisulphite, potassium bitartrate, sodium thiosulphate, sodium hydrosulphite in a concentration of 0.5-1 %, based on the weight of the wool, depending on the agent used. Another possibility

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consists in adding the reducing gown along with the applied metal salt. Treatment is through continued boiling for 15 to 30 minutes, rinsing the material in water at approximately 40 ° C and then drying.

It is possible to carry out the pickling process without adding a reducing agent. However, the addition serves of a reducing agent for the purpose of bringing the reduction to completion, for example of chromium to the trivalent cationic form with maximum pickling effect, and the migration of unreduced bichromate to the untreated wool in the the following staining operation. The advantages achieved in this way consist in a significant reduction in staining of the untreated wool material by the stain dye and in the reproducibility from batch to batch when dyeing the pieces.

As a second step, the pre-treated Wool materials combined with untreated wool materials e.g. by carding, combing, spinning, twisting, weaving, knitting.

The wool mixture obtained in this way is then dyed as a third step in the production of multicolored wool materials according to the invention either with mordant dyes or a combination of mordant and acidic dyes. This dyeing is carried out according to the usual wool dyeing process. Such a method consists, for example, in the preparation of a dyebath at a temperature of 40 to 50 ° C, which contains 5 to 10 $, based on the weight of the wool, of anhydrous Glauber's salt, enough acetic acid to achieve a pH of 4 to 5.5 and 0.5 to 2% of a condensation product of stearyl diethylene triamine and

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Ethylene oxide ("Tinegal W" from J.R. ■ Gelgy A.G., Basel) contains. It is then stirred for 10 to 15 minutes and the desired stain dyes or a combination of stain and acidic dyes are dissolved and added. The temperature of the dyebath is then raised to boil 'and kept the bath boiling for 30 to 60 minutes. Additional dye can be added if necessary to achieve the desired result desired color is necessary and cooked for another 15 to 30 minutes. After all, the woolen goods are rolled into one rinsed fresh bath at 40 to 50 ° C for 15 minutes and dried.

Except for the condensation product of stearyl diethylenetriamine and ethylene oxide, which is used as an aid in the dye bath to reduce the staining of the untreated material proved to be advantageous due to the stain or chrome dyes, other agents can be used, such as the condensation products of naphthalene sulfonic acid and formaldehyde ("Irgasol DA" from J.R. Geigy A. G., Basel) of naphthalenesulfonic acid-formaldehyde and Dioxydiphenylsulfon ("Eriönal! W", the company J.R. Geigy A.G., Basel), of 3,4-dichlorophenyl isocyanate and 4,4'-dichloro-2-amino-diphenylether-2'-sulfonic acid ('Mitin FF ", from J.R. Geigy A.G., Basel) or ("Irgasol SW", from J.R. Geigy A.G., Basel), and also non-ionic agents, such as ethoxylated nonylphenols and the like.

Because of the large number of well-known mordant dyes and chromium dyes in particular are not listed. The following examples demonstrate a representative number. However, this is to be understood in such a way that all such dyes, which are mentioned e.g. in the "Color Index" can be used.

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As for the acidic dyes, which in the present invention Procedures can be used so is it. turn clear that not only through the following Examples · documented, acidic dyes can be used, but also all acidic dyes from the following groups:

1) Acid dyes which are normally applied at pH 2 to 4, i.e. "acid leveling dyes" or "strongly acidic dyes" such as "Erio" dyes (Trade Mark from J.R. Geigy A.G., Basel).

2) 1: 1 pre-metallized acidic dyes (i.e. those containing one atom of metal complexed with one molecule of dye), which is a strong acid with a pH of 1.8 to 3 too require their use, such as "Glycolan" dyes (trademark of J.R. Geigy A.G., Basel).

3) Trichloropyrimidine reactive dyes, which normally

for wool from weakly acidic baths (pH 3 to 5), such as "Reacton" dyes (trademark of J.R. Geigy A.G., Basel).

4) 1: 2 pre-metallized acidic dyes (i.e. those which

one atom of metal complexed with two molecules of dye), which are normally applied from neutral or weakly acidic baths (pH 6 to 7), such as "Irgalan" dyes (Trademark of J.R. Geigy A.G.).

5) Acid dyes, which are normally applied from neutral baths or with weak acids at a pH of 4.5 to 7 such as "Irganbl" and "Polar" dyes (trademarks of J.R. Geigy A.G., Basel).

The last two groups of dyes mentioned, the so-called "neutral coloring types", are particularly preferred.

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The above dyes, be they mordants or acidic dyes, can be used in concentrations from $ 0.001 to $ 10, depending on the desired shade and the strength of the dyes used. Also other dyes that are suitable for wool can be used.

Further, it is clear that the staining and coloring process can be carried out by any of the usual printing processes with the following Steaming can be replaced. The term "dyeing" should therefore be understood to include the printing of fabric Includes use of dyes and / or stains.

The achieved with the inventive method The benefits are many and amazing compared to previous ones Working methods. It is now possible to keep uncolored materials in stock and to order them conveniently and quickly to dye. The present invention also enables efficient and short dyeing with two different classes of dyes in a dye bath and makes it possible to obtain distinct two-tone or contrast effects with a single dye.

The following examples illustrate the invention without restricting it, with particular consideration of contrast and two-tone piece dyeing of all-wool carpets. The percentages given are percentages by weight, calculated on the weight of the wool. The temperatures are given in degrees Celsius.

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A. Pickling process example 1

Wool yarn is treated in a dye tub in a liquor ratio of 25 parts water to one part wool by adding $ 1.5 potassium dichromate and 3% formic acid ($ 85) and boiling for 45 minutes, adding 1% sodium bisulfite and boiling for a further 15 minutes. The yarn is then rinsed with water at 40 ° and dried. In the above process, sodium thiosulfate and sodium hydrosulfite can also be used in place of sodium bisulfite.
Example 2

The procedure is as described in Example 1, but instead of potassium dichromate, formic acid and sodium bisulfite, 2% sodium dichromate and 5% potassium bitartrate are added to the bath. The woolen yarn is then shrunk at 60 °, the bath temperature is slowly increased to boiling and, after 1 1/2 hours of boiling, the yarn is rinsed and dried.

B. Association of treated and untreated wool materials

Wool yarn that has been pretreated as described in Example 1 is processed into a jute underlay with untreated yarn, so that a carpet is created that contains alternately pre-treated and untreated yarn on the broad side. In another embodiment, raw wool prepared as in Example 1 described was pretreated, spun and woven with untreated yarn in various patterns on a loom. This fabric is then piece-dyed according to the following examples:

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"■ C. ™ *

C. Dyeing Procedure Example 3 -

A dye bath is prepared at a temperature of 50 ° with 10% anhydrous Glauber's salt, IJi acetic acid (56 %) and 1% "Tinegal W". 0.5 $ CI Mordant Orange 1, dissolved in water, is added to the bath. The temperature is then raised to a boil and cooked for 30 minutes. The fabric is then rinsed in a fresh bath at 40 ° for 15 minutes and dried. A carpet with deep orange stripes alternating with light yellow-brown stripes was obtained. The stained yarn showed the darker shade.

In the following examples the method of Example 3 is repeated but using other mordant dyes, and combinations of pickling and acid dyes, and various other contrast and Zweitoneffekte be obtained.
Example 4

$ 0.50 CI Mordant Red 7
$ 0.50 CI. Acid Blue 45
$ 2.00 acetic acid ($ 56)
$ 10.00 Glauber's Salt
$ 2.00 "Irgasol SW"

The carpet obtained showed alternating deep wine-red and light brown tones, the deeper tone corresponding to the stained yarn.
Example 5

$ 0.25 CI. Mordant Yellow 5
$ 0.20 CI. Acid Blue 45
$ 10.00 Glauber's Salt
$ 2.00 "Erional NW"
$ 2.00 acetic acid ($ 56 ig). '

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A carpet was obtained with green and blue stripes, the green stripes corresponding to the stained yarn, which was dyed both by the yellow and blue dye, while the blue dye was only drawn onto the untreated yarn.
Example 6

$ 0.25 C.I. Mordant Violet I 0.05Ji C.I. Acid Blue 45 $ 2.00 acetic acid ($ 56) $ 10.00 Glauber's salt $ 1.00 "Mitin FF" $ 2.00 acetic acid ($ 56)

A purple (pretreated yarn) and blue-gray carpet was obtained. Example 7

$ 0.200 C.I. Mordant Orange $ 0.020 CI. Acid Blue 45 $ 0.200 CI. Acid Yellow $ 0.025 CI. Acid Orange $ 2.00 "Irgasol DA" $ 10.00 Glauber's salt $ 1.00 acetic acid ($ 56) $ 2.00 acetic acid ($ 56)

A dark orange (pretreated yarn) and chartreuse colored carpet was obtained. Example 8

$ 1.00 CI. Mordant Red 3 $ 3.00 Acetic Acid (56 $ ig) $ 1.00 "Tinegal W" $ 10.00 Glauber's Salt

A sparkling red-brown (pretreated yarn) and red-violet carpet was obtained.

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Example 9

$ 0.25 C.I. Mordant Brown $ 10.00 Glauber's Salt 1.00 $ "Tinegal W" 1.50Ji acetic acid (56 $ ig)

A brown (pretreated yarn) and yellow carpet was obtained.
Example 10

0.15% CI Mordant Yellow $ 10.00 Glauber's Salt $ 1.00 "Tinegal W". - = $ 2.00 acetic acid ($ 56)

A deep yellow (pretreated yarn) and light yellow carpet was obtained. Example 11

$ 0.30 C.I. Mordant Blue I $ 0.10 C.I. Acid Blue $ 10.00 Glauber's Salt $ 1.00 "Tinegal W" $ 3.00 Acetic Acid ($ 56)

A royal blue (pretreated yarn) and blue-gray carpet was obtained. Example 12

$ 0.30 CI. Mordant Blue I $ 0.038 CI. Acid Red $ 0.040 C.I. Acid Red $ 1.00 "Tinegal W" $ 2.00 Acetic Acid ($ 56)

A royal blue (pretreated yarn) and pink carpet was obtained.

Example 13

$ 0.50 CI Mordant Yellow $ 0.05 CI Acid Blue 5 $ 0.25 CI Acid Yellow $ 10.00 Glauber's Salt $ 2.00 Acetic Acid (56 $ ig) I ₁ OOJf "Tinegal W" $ 2.00 Acetic Acid ( 56 $ ig)

A chartreuse-colored (pre-treated yarn) and light green carpet was obtained. Example 14

$ 0.75 CI. Mordant Red 7 $ 0.38 C.I. Acid Red I. $ 0.40 CI. Acid Red 37 $ 10.00 Glauber's Salt $ 1.0θ «Tinegal W" $ 2.00 Acetic acid ($ 56)

It was a deep burgundy (pretreated yarn) and bright scarlet carpet preserved.

Another approach is to pay $ 0.1 to $ 5 Potassium or sodium dichromate or an equivalent metal salt dem Add dye bath. This addition is made after the mordant dye is completely on the mixture of mordant and unstained wool. It is used for re-chrome plating of the dye present on the unheated fiber by converting this dye into an insoluble metallic lacquer. Certain mordant dyes allow the simultaneous presence of Pickling in the AppÜkatlönsbad. In such cases it is possible to use the Add stain to the dye bath at the beginning of the dyeing process. By Adding stain to the dyebath in one way or another of the above ways increases the authenticity of the unheated portion of the mixture achieved.

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Example 15

$ 0.06 C.I. Mordant Green 30

$ 0.02 C.I. Mordant Yellow 5

$ 0.04 C.I. Mordant Blue 1

$ 0.02 "Irganol" Yellow 4 GLS

$ 1.00 "Irgasol SW"

$ 3.00 acetic acid ($ 56)

After 45 minutes of boiling, $ 0.5 sodium bendable is added and the mixture is boiled for a further 45 minutes. A dark green (pretreated yarn) and light green carpet was obtained. Example 16

$ 0.04 CI Mordant Black 13
$ 0.01 CI Mordant Violet 28
$ 1.00 "Irgasol SW"
$ 3.00 acetic acid ($ 56)

«After 45 minutes of treatment at boiling temperature $ 0.5 sodium bend added and cooked for another 45 minutes. The result was a gray (pretreated yarn) and light gray carpet obtain.

While a stain dye is perfectly adequate to produce a distinct two-tone color effect, it is due to The above examples indicate that the use of a combination of mordant dye and one or more acidic Dyes are used to expand the scope for contrast effects. Other interesting color combinations, which three-color effects show were pretreated by combining ν and untreated wool materials, as described above, with wool materials which are dyed separately or in very dark colors Tones such as black, navy blue, dark brown, and dark green, were pre-colored. The material obtained is then piece dyed. 80 980 9/1033

U44262

It is also readily apparent that the above-described staining and dyeing process can be used on wool materials Shape can be applied. For example, wool in loose form can be pretreated like this and with loose untreated wool combined and dyed in bulk, or spun into yarn and dyed; or it can be the yarn thus obtained fabricated into fabric and then dyed. Such fibers, yarns or fabrics show a variety of color effects. Furthermore can Wool in loose form, which has been pretreated in this way, spun into simple yarn and doubled with untreated yarn and in Dyed yarn form or processed into fabric and piece-dyed. These yarns or fabrics show contrasting color effects.

Another option is to spin pre-treated wool in loose form into plain yarn and either to be used as a single or doubled yarn together with untreated yarn for the production of Gev / even and These pieces to be milled, with multi-color or two-tone effects obtained which have already been referred to above. Then pretreated yarn can be combined with untreated yarn Combined fabric and this are piece-dyed, two-tone or contrasting color effects are obtained.

Wool materials as woven fabrics can also be pretreated in this way, with untreated woven fabrics combined Fabrics are combined and then piece-dyed to obtain pattern effects.

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Claims (6)

- 14 - 1 * 44262 Patent claims J Process for the production of multicolored wool material in loose, yarn or fabric form, characterized in that the wool material is treated with a metal salt which has pickling properties, the wool material pretreated in this way is combined with untreated wool material and the wool mixture obtained is dyed. 2. The method according to claim 1, characterized in that that the wool blend with stain dyes or a combination the same is dyed with acidic dyes or other dyes suitable for wool. 3. The method according to claim 1 for the production of multi-colored wool material, characterized in that the wool material in a solution containing a metal salt with caustic properties, a reducing agent and an acid for adjustment a pH value of 2 to 6 contains, boiled, the so pretreated wool material combined with uri-treated wool material and the resulting wool blend with mordant dyes or a combination of these with acidic dyes or other dyes suitable for wool. 4. The method according to claim 3, wherein the metal salt is a chromium salt .. 5. The method according to claim 3, wherein the metal salt Is potassium or sodium dichromate. 6. The method according to claim 3, wherein the reducing agent is sodium bisulfite, potassium bitartrate, sodium thiosulfate or sodium thiosulfate Is sodium hydrosulfite. J.R. G e i g y A.G. 809809/10 33