EP1601831A1

EP1601831A1 - Method for dyeing a mixture of at least two different types of fibre

Info

Publication number: EP1601831A1
Application number: EP04719330A
Authority: EP
Inventors: Jörg Schlangen; Marina Crnoja-Cosic; Christian Baumgartinger
Original assignee: Lenzing AG; Chemiefaser Lenzing AG
Current assignee: Lenzing AG
Priority date: 2003-03-13
Filing date: 2004-03-11
Publication date: 2005-12-07
Also published as: TW200427896A; ATA4002003A; TR200503591T1; CN1759217A; WO2004081279A1; AT413825B; CN100346029C; US20060085926A1

Abstract

The invention relates to a method for dyeing a mixture of at least two different types of fibre, using at least one dye. Said method is characterised in that the mixture contains a quantity of cationised cellulosed fibres. The invention also relates to fibre blends which can be obtained by means of the inventive method.

Description

Process for dyeing a mixture of two or more different types of fibers

The present invention relates to a method for dyeing a mixture of two or more different types of fibers and fiber mixtures.

It is known to manufacture textile surfaces such as e.g. Weaving, knitting or knitting with mixtures of fibers of different origins to work. Furthermore, it is known to achieve color effects in the textile surfaces due to the use of differently colored fibers or yarns.

It is complex that the starting products for the manufacture of the textile surface, i.e. the fibers or the yarns must be dyed separately from one another with different dyes in order to produce the desired effect in the fabric.

Particularly in the production of so-called denim fabric, the warp yarn must be warp dyed in the indigo dyeing process, i.e. no finished fabrics can be dyed.

These problems arise particularly when using cellulosic fibers, e.g. Viscose fibers, Lyocell fibers but also cotton fibers.

The present invention has for its object to provide a method for dyeing a mixture of two or more different types of fibers with one or more dyes, with which these disadvantages can be overcome.

This object is achieved with the method according to the invention, which is characterized in that the mixture contains a proportion of cationized cellulosic fibers.

It has been shown that the use of cationized cellulosic fibers can solve various problems in the manufacture of textile products with color effects or open up new possibilities, in particular: • Achieving color intensity differences (differential dyeing) between two fiber types (cationized cellulosic fiber and other, especially cellulosic fiber) when using only one dye

• Achieving mixed colors when dyeing with several dyes, the different types of fibers being dyed differently or not at all with the dyes used

Accelerating the dyeing process when dyeing mixtures of cationized cellulosic fibers and synthetic fibers, e.g. Polyester fibers or polyamide fibers.

Cationized cellulose fibers are known per se. Fibers which contain the cationic groups incorporated are particularly preferred for use in the process according to the invention. Such fibers are produced by adding a cationizing agent which is stable in the production process in question to the spinning solution for producing the fiber or a precursor to the spinning solution.

It is also known that cationized cellulose fibers have special dyeing properties that differ from non-cationized cellulose fibers.

Cationized viscose fibers are particularly preferred for use in the process according to the invention, i.e. Fibers made by the viscose process and bearing cationic groups.

The production of cationized cellulosic fibers is known per se and e.g. in JP-A 61-258801, JP-A 52-26561, JP-A 2-274738, EP-A 0 683 251, EP-A 0 690 166 or WO 96/26220.

In a preferred embodiment of the process according to the invention, the mixture contains a proportion of non-cationized cellulosic fibers. The non-cationized cellulosic fibers can be selected from the group consisting of standard viscose fibers, modal fibers, lyocell fibers, cotton fibers and linen fibers.

Due to the different dyeing properties of cationized cellulose fibers and non-cationized cellulose fibers, interesting color effects can easily be achieved, for example when dyeing with only one dye. The process according to the invention can be carried out effectively by dyeing the mixture with a direct dye and / or a reactive dye.

Cationized cellulose fibers, in particular cationized viscose fibers, are more strongly stained by direct dyes and reactive dyes than non-cationized cellulose fibers.

Surprisingly, the achievable mixed color effect depends particularly strongly on the salt concentration used in the dyeing (less strongly on the pH and the temperature of the dyeing). The concentration of the dye in the liquor also plays a role, the greater the dye concentration, the smaller the difference in color depth between the fibers.

When dyeing with direct dyes, the mixed color effect is particularly pronounced at low salt concentrations of 3 to 5 g / 1. At higher salt concentrations up to 25 g / 1, on the other hand, almost the same color depths of the cationized and non-cationized cellulose fibers are achieved.

When dyeing with reactive dyes, the mixed color effect is particularly pronounced at salt concentrations of up to 20 g / 1. At higher salt concentrations up to 80 g / 1, almost the same color depths of the cationized and the non-cationized cellulose fiber are achieved.

It also shows that the mixed color effect is more pronounced when using modal fibers or cotton fibers than non-cationized cellulosic fibers than when using standard viscose fibers or lyocell fibers.

Interesting effects are also achieved when dyeing a mixture of cationized cellulose fibers and non-cationized cellulose fibers with two different reactive dyes. It can first be dyed with one reactive dye under conditions in which only the cationized cellulose fiber is dyed. The second reactive dye is then added and dyeing is carried out under conditions in which both the cationized cellulose fiber and the non-cationized cellulose fiber are dyed. Another aspect of the method according to the invention is characterized in that the mixture is colored with a wool dye and at least one other dye, in particular a direct dye and / or a reactive dye.

In this embodiment too, the use of a fiber mixture containing cationized cellulose fibers and non-cationized cellulose fibers is particularly favorable.

The skilled person understands wool dyes as dyes with which wool or polyamide can be dyed. These include acid dyes, metal complex dyes and acid reactive dyes. A metal complex dye is particularly preferably used as the wool dye.

While in a mixture of cationized cellulose fibers and non-cationized cellulose fibers, the non-cationized cellulose fibers are practically not dyed by the wool dye, the cationized cellulose fibers are dyed by the wool dye.

The non-cationized cellulose fibers are dyed by the second dye used (preferably a direct dye or a reactive dye) under appropriate dyeing conditions. This second dye optionally also at least partially stains the cationized cellulose fiber.

On the one hand, this results in a mixed dyeing between cationized and non-cationized cellulose fiber. On the other hand, there may also be a mixed color in the cationized cellulose fiber itself, due to the dyeing with the wool dye and the competitive dyeing with the second dye.

If a metal complex dye is used as a dye, the use of lyocell fibers as non-cationized cellulosic fibers in the mixture has proven to be favorable, since these fibers are least contaminated by the metal complex dye.

Another preferred embodiment of the method according to the invention is characterized in that the fiber mixture contains a proportion of non-cellulosic fibers. Polyester fibers (PES) or polyamide fibers (PA) are particularly interesting for various applications. Mixtures of two components (cationized cellulose fiber / synthetic fiber) or three components (cationized cellulose fiber / non-cationized cellulose fiber / synthetic fiber) are particularly advantageous.

It has been shown, for example, that the duration of the dyeing process when dyeing a mixture of cationized cellulose fibers and polyester fibers with reactive dyes can be drastically reduced under reactive dyeing conditions.

The effects that can be achieved depend on various parameters, depending on the components used and the types of dyes used. The following table shows the influence of the dyeing temperature and the pH on various embodiments of the process according to the invention.

Table 1

The table shows in particular that in the case of mixtures of cationized and non-cationized cellulose fibers, there are differences in the dyeing behavior above and below a dyeing temperature of 100 ° C. The fiber mixture can be dyed in the form of a yarn or part of a chamois or a textile surface or part of a textile surface.

The fiber mixture is particularly preferably dyed in the form of a fabric in order to achieve a denim effect.

The indigo effect desired for jeans is currently achieved by indigo dyeing. If you want to dye indigo continuously on cellulosic fibers, a complex, multi-stage process is necessary. Warp dyeing must be carried out, i.e. no finished fabrics can be dyed.

It has been shown that, in particular, blended fabrics made of cationized cellulose fibers, polyester fibers and cotton fibers can be dyed so that the specific indigo effect can be achieved without multi-stage indigo dyeing and on an already finished fabric.

Certain and targeted melange effects can also be achieved. The comfort of clothing made from blended fabrics of this type is also better, since a softer and more pleasant feel can be achieved. In addition, there is better wash resistance compared to standard indigo products.

It can be seen that the mixed colorings which can be achieved with the process according to the invention are extremely reproducible.

The invention further relates to a fiber mixture which can be obtained by the process according to the invention.

In particular, the invention further relates to a fiber mixture containing a portion of cationized cellulosic fibers and a portion of non-cationized cellulosic fibers, which is characterized in that the portion of cationized cellulosic fibers and the portion of non-cationized cellulosic fibers with one and the same direct dye and / or a reactive dye is dyed and that there is a difference in the intensity of the dyeing between the proportion of cationized cellulosic fibers and the proportion of non-cationized fibers. As described above, the different degree of staining can be controlled in particular by the choice of the salt concentration in the coloring.

This embodiment of the fiber mixture according to the invention is preferably characterized in that the difference in the intensity of the coloration between the cationized cellulosic fibers and the non-cationized fibers is 5 to 50 CIELAB units according to the measurement method given below.

Another preferred embodiment of the present invention relates to a fiber mixture containing a portion of cationized cellulosic fibers and a portion of non-cationized cellulosic fibers, which is characterized in that the portion of cationized cellulosic fibers with a wool dye and optionally at least partially with another dye , in particular a direct dye and / or a reactive dye, is colored, while the proportion of non-cationized fibers is only colored by the other dye.

As already described above, interesting color effects can be achieved in a simple manner with such fiber mixtures.

Non-cationized cellulosic fibers can include fibers from the group consisting of standard viscose fibers, modal fibers, lyocell fibers, cotton fibers and linen fibers.

The cationized cellulosic fibers preferably contain the cationic groups in the fiber mixtures according to the invention.

The cationized cellulosic fibers are furthermore preferably cationized viscose fibers.

The fiber mixtures according to the invention preferably contain a proportion of non-cellulosic fibers, e.g. Polyester fibers or polyamide fibers.

A particularly preferred embodiment of the fiber mixture according to the invention is in the form of a denim fabric. Preferred embodiments of the present invention are explained in more detail below on the basis of exemplary embodiments.

All of the cationized viscose fibers mentioned in the examples below were produced by methods which are described in WO 96/26220.

Example 1 :

A fabric made from a mixture of standard viscose fibers and cationized viscose fibers was dyed at a dyeing temperature of 80 ° C. with a dye liquor containing 2% dye (Sirius Rubin K-2BL - direct dye, manufacturer DyStar) based on 20 g of fabric (600 ml liquor) and colored a nonionic wetting agent at various salt concentrations (Na ₂ SO ₄ ).

The brightness of the colored standard viscose fibers or the cationized viscose fibers was measured using the following measurement method:

The CIELAB whiteness of the fibers was determined using the following method: The color coordinates of the fibers were determined according to R _x , R _y R _z according to DIN 6174 and DIN 5033 with illuminant D65 and at 10 ° observation angle. The CIE whiteness and the color cast in the red / green axis are calculated from these color coordinates according to DIN 55981 (^ color deviations according to Gärtner / Griesser) as follows:

CIE- whiteness: W = Y + 800 * (x ₀ -x) + 1700 (y ₀ -y) color cast (= tint): T = 900 * (x _o -x) -650 * (y ₀ -y) ( Note: T negative = red stitch, T positive = green stitch)

Y ... standard color value for green sensitivity (= R _y ... reflectance value green) x ₀ , y ₀ - standard color value components of the achromatic point (with D65 / 10 ⁰ applies x ₀ = 0.3138; y ₀ = 0.3310) x, y ... standard color value proportions of the samples, calculated according to: x = X / (X + Y + Z) y = Y / (X + Y + Z) z = 1-xy The standard color values X, Y, Z, which appear in these formulas, are in turn calculated from the reflectance values (= filter values) R _x , R _y , R _z with illuminant D65 and 10 ° viewing angle according to the formulas: X = 0.94811 * R _X

Y ^: Ry z = 1.07304 * R _z

Depending on the salt concentration used, the following table shows the respective difference between the CIELAB brightness values determined for the two colored fiber types:

Table 2

Example 2

Tissues were made

• cationized viscose fibers

Low-fibrillating Lyocell fibers (type "Lyocell LF", manufacturer Lenzing AG) and

• Modal fibers (manufacturer Lenzing AG)

dyed with two types of dye each, namely a direct dye (Sirius dyes, manufacturer DyStar) and a metal complex dye (Isolan dyes, manufacturer DyStar), the dye liquor containing both dyes. The following standard parameters were adhered to:

Fleet ratio: 1 100gg G tissue with 600 ml liquor

Nonionic wetting agent

Salinity: 10 g / 1 pH: 7 Dyeing temperature 80 ° C dyeing time 45 min

Colorings with liquors containing the following dyes were carried out:

• 2.0% Sirius yellow K-GRL 0.15% Isolan dark blue 2S-GL 01

• 2.0% Sirius yellow K-GRL 0.4% Isolan dark blue 2S-GL 01

• 2.0% Sirius yellow K-GRL; 0.8% Isolan dark blue 2S-GL 01

• 2.0% Sirius yellow K-GRL 0.4% Isolan bordo R 220%

• 2.0% Sirius yellow K-GRL 0.8% Isolan bordo R 220%

• 2.0% Sirius yellow K-GRL 0.8% Sirius turquoise GL 01

• 2.0% Sirius yellow K-GRL 0.8% Isolan gray S-GL

• 1.0% Sirius blue K-GRL 1.5% Isolan yellow K-GLN 250%

• 1.0% Sirius blue K-GRL 0.5% Isolan yellow K-GLN 250% o 1.0% Sirius blue K-GRL 1.0% Isolan Sharlach K-GLS 150%

• 1.0% Sirius blue K-GRL, 0.5% Isolan Sharlach K-GLS 150%

• 1.0% Sirius blue K-GRL 1.5% Isolan gray S-GS β 1.5% Sirus Sharlach K-CF; 1.0% Isolan yellow K-GLN 250%

• 1.5% Sims Sharlach K-CF; 0.5% Isolan yellow K-GLN 250%

• 1.5% Sims Sharlach K-CF; 0.8% Isolan Oliv SG or 1.5% Sirus Sharlach K-CF; 0.2% »Isolan Oliv SG

• 1.5% Sims Sharlach K-CF; 1.5% Isolan gray S-GL

In all cases, the non-cationized cellulose fibers (Lyocell or Modal) were stained practically exclusively with the direct dye; the cationized viscose fibers were additionally dyed with the metal complex dye, which, depending on the color and concentration of the dyes used, resulted in controllable mixed dyeings in the cationized fibers.

These mixed dyeings (and the difference between the color of the cationized viscose fiber and the other cellulose fiber) produce interesting effects in fabrics which contain a mixture of these two fibers and are dyed with the dyes mentioned. Similar effects were observed in analogous tests with fabrics made from cationized viscose fibers and cotton fibers.

Example 3

Striped socks (alternating 1 cm cationized viscose fibers and 1 cm Lyocell fibers) were produced and dyed with the following dye mixtures:

3a) 2.0% Sirius yellow K-GRL; 0.15% Isolan dark blue 2S-GL 01 3b) 2.0% Sirius yellow K-GRL; 0.4% Isolan bordo R 220%

The colored striped socks had clearly different colored striped areas.

In example 3a), the sections with the Lyocell fibers were each colored yellow; the sections with the cationized viscose fibers each had a green mixed color (from the yellow direct dye and the blue wool dye).

In example 3a), the sections with the lyocell fibers were also colored yellow; the sections with the cationized viscose fibers each had an orange / reddish mixed color (from the yellow direct dye and the red wool dye).

Furthermore,

• Knitted stockings made from a yarn containing cationized viscose fibers and lyocell fibers (Nm 50/1)

• Twill 3/1 from a twine (Nm 50/2) - mixture of cationized viscose fibers and Lyocell fibers - in the weft and modal fibers in the warp and

• Fabric with herringbone pattern made from a twine (Nm 50/2) - mixture of cationized viscose fibers and Lyocell fibers - in the weft and modal fibers in the warp

dyed with the dye mixtures mentioned, which also resulted in interesting color effects. In all cases, the mixed dyeings achieved were reproducible, ie practically identical dyeing results were achieved when the test was repeated.

Example 4

A knitted fabric made of a twine - containing cationized viscose fibers and cotton fibers in a 50/50 ratio - and PES filament was first in a bath under dyeing conditions for PES fibers (ie at 130 ° C.) with a dye complex consisting of a metal complex dye and a disperse dye and then stained at 90 ° C with a direct dye at a salt concentration of 7 g / 1 salt.

The course of the coloring can be represented as follows:

• Start: temperature 50 ° C, dye liquor: metal complex dye + disperse dye; 20 g / 1 Na acetate, dispersant: Setamol NS

• Heat to 130 ° C

• dyeing for 30-45 min

• Cool to 50 ° C

• Add dye liquor with direct dye, 7 g / 1 salt

• Warm up to 90 ° C

• dyeing for 30 min o cooling

The following dye combinations were selected:

4a) 2.0% Sirius yellow K-GRL (direct dye); 0.4 Isolan bordo R 220%

(Metal complex dye) 4b) 2.0% Sirius yellow K-GRL (direct dye); 0.8% Supranol Turquise GGL

(Metal complex; manufacturer: DyStar)

A black disperse dye (Dianix Schwarz CC, manufacturer DyStar) was selected as the disperse dye for the PES fibers.

As a result, fabrics with interesting mixed dyes were obtained, the PES filament being dyed black with the disperse dye; the cationized viscose fiber was mixed-dyed with the metal complex dye and the direct dye; the cotton fibers were dyed only with the direct dye. Example 5

To achieve a denim effect, a fabric consisting of a mixture of cationized viscose fibers and PES fibers (60/40) in the warp and cotton fibers in the weft was first, as described in Example 4, under dyeing conditions for PES fibers with a dye mixture of one Disperse dye and a metal complex dye colored.

The samples colored in this way correspond to the results of a standard indigo denim production if the same color tones were used for the disperse and the metal complex dyes. If you use different shades of color, this creates melange optics that would be very difficult and expensive to achieve with standard indigo technology. Subsequently, a few samples were dyed with direct dyes immediately after the PES staining in the same bath. It is also possible to dye the cotton component in the same dyeing process.

The described one-bath, approx. One-hour competition dyeing can be seen as an interesting alternative to the complex and technically demanding indigo dyeing. The dyeing processes according to the invention for producing a denim effect also offer particularly good flexibility, since no previous warp dyeing is necessary and this enables rapid and efficient market adaptation.

Claims

Claims:

1. A method for dyeing a mixture of two or more different types of fibers with one or more dyes, characterized in that the mixture contains a proportion of cationized cellulosic fibers.

2. The method according to claim 1, characterized in that the cationized cellulosic fibers incorporated the cationic groups.

3. The method according spoke 1 or 2, characterized in that the cationized cellulosic fibers are cationized viscose fibers.

4. The method according to any one of the preceding claims, characterized in that the mixture contains a proportion of non-cationized cellulosic fibers.

5. The method according to any one of the preceding claims, characterized in that the mixture is colored with a direct dye and / or a reactive dye.

6. The method according to claim 5, characterized in that when dyeing with a direct dye with a salt concentration of 2 to 25 g / 1, preferably 3 to 5 g / 1, is carried out.

7. The method according to claim 5, characterized in that when dyeing with a reactive dye with a salt concentration of up to 80 g / 1, preferably less than 20 g / 1, is carried out.

8. The method according to any one of claims 1 to 4, characterized in that the mixture is colored with a wool dye and at least one other dye, in particular a direct dye and / or a reactive dye.

9. The method according to claim 8, characterized in that the wool dye is a metal complex dye.

10. The method according to any preceding claim, characterized in that the mixture contains a proportion of non-cellulosic fibers.

11. The method according to any one of the preceding claims, characterized in that the fiber mixture is dyed in the form of a yarn or a part of a yarn or a textile surface or a part of a textile surface.

12. The method according to claim 11, characterized in that the fiber mixture is dyed in the form of a fabric to achieve a denim effect.

13. Fiber mixture, obtainable by a method according to any one of the preceding claims.

14. Fiber mixture containing a portion of cationized cellulosic fibers and a portion of non-cationized cellulosic fibers, characterized in that the portion of cationized cellulosic fibers and the portion of non-cationized fibers are dyed with one and the same dye and that between the portion cationized cellulosic fibers and the proportion of non-cationized fibers there is a difference in the intensity of the staining.

15. A fiber mixture according to claim 14, characterized in that the difference in the intensity of the staining is 5 to 50 CIELAB units.

16. A fiber mixture containing a portion of cationized cellulosic fibers and a portion of non-cationized cellulosic fibers, characterized in that the portion of cationized cellulosic fibers with a wool dye and optionally at least partially with another dye, in particular a direct dye and / or a reactive dye , is colored, while the proportion of non-cationized fibers is only colored by the other dye.

17. Fiber mixture according to one of claims 14 to 16, characterized in that the cationized cellulosic fibers contain the cationic groups incorporated.

18. Fiber mixture according to one of claims 14 to 17, characterized in that the cationized cellulosic fibers are cationized viscose fibers.

19. Fiber mixture according to one of claims 14 to 18, characterized in that the mixture contains a proportion of non-cellulosic fibers.

20. Fiber mixture according to one of claims 14 to 19, characterized in that it is in the form of a denim fabric.