WO2012171638A1

WO2012171638A1 - Acid dye mixtures for polyamide and wool, containing dimer acid dyes

Info

Publication number: WO2012171638A1
Application number: PCT/EP2012/002497
Authority: WO
Inventors: Helmut Sieber; Rainer Nusser; Rino Marazzi
Original assignee: Clariant International Ltd
Priority date: 2011-06-16
Filing date: 2012-06-13
Publication date: 2012-12-20
Also published as: CN103619962A; MX2013014769A; JP2014519543A; TW201313840A; KR20140041744A; BR112013032249A2; EP2721113A1

Abstract

The invention relates to an acid dye mixture comprising a) between 70 and 95 wt. % of at least one dye A of general structure (A), and b) between 5 and 30 wt. % of at least one dye B of general structure (B).

Description

Acid-dye mixtures for polyamide and wool containing dimeric acid dyes

Acid dyes are mainly used to dye wool, others

Animal hair, silk and polyamide used. Although these fibers are similar in chemistry (polyaminocarboxylic acids), the physical difference between wool and hair on the one hand and polyamide and silk on the other is very high. As a result, the properties of a

Acid dye on polyamide can differ significantly from those on wool. These are, for example, the color itself

the light fastness (usually worse on polyamide than on wool) the structure (usually worse on polyamide than on wool)

- the wet fastness

Similarly, wool acts in dyeing and in some finishing steps

reducing, which can lead to the "coking" of many suitable for polyamide acid dyes in dyeing and color changes in the equipment.

It is also known that many acid dyes stain the point of the wool fiber significantly differently than the root, which can only be corrected insufficiently with certain aids. For a nice appearance on woolen textiles but a very good balance between root and lace is a prerequisite. Therefore, often several acid dyes are mixed in one product to get a nice appearance on wool. However, these mixtures are not suitable for dyeing on polyamide for medium or deep combination dyeings, since there are blockages by the various components, due to the low construction of some of the necessary mixing components.

Thus, there are very few acid dye blends recommended for both polyamide and wool, and especially for a blend of both fibers. The few examples that are known in the market are low-wet "leveling dyes" for dyeing polyamide / wool carpet yarns. For dyeing clothing textiles made of wool and polyamide is especially missing a blue component, which is suitable both with good appearance for wool and polyamide, can be used for reproducible combination dyeings with a yellow and a red component and the necessary washing, welding and Has process fastness.

It has now surprisingly been found that the below described

Acid dye mixture on polyamide, wool and on polyamide / wool blended fibers provides good reproducible colorations with good wet fastness.

The present invention is an acid dye mixture comprising

a) 70 to 95 wt .-%, preferably 80 to 95 wt .-%, particularly preferably 85 to 90% by weight, of at least one dye A with the general

Structure (A)

wherein

R1 is H, d-Ce-alkyl; and

R 2 is H, C 1 -C ₆ alkyl; b) from 5 to 30% by weight, preferably from 5 to 20% by weight, particularly preferably from 10 to 15% by weight, of at least one dye B having the general structure (B)

wherein

R 3 is H, phenyl, where phenyl is substituted or unsubstituted,

R4 H, sulfo,

R5 H, C C Ikoxy,

or R4 and R5 form together with the adjacent one

C = C double bond an unsubstituted or substituted phenyl ring, R6 H, sulfo;

M H, alkali metal, ammonium or a simple negative charge

mean,

where the weight percentages are based on the total weight of the

Acid dye mixture are related. The positive charge in formula (B) is usually substituted by a negative charge of a sulfo group contained in the molecule or by an equivalent of an anion, e.g. B. Cl ^" , VT S0 ₄ ^2" neutralized.

In the above definitions, sulfo is a radical of formula S0 ₃ M. M is preferably a single negative charge, hydrogen, an alkali metal or ammonium.

In the above definitions, alkali metal preferably means Li, Na, or K, especially Na.

In the above definition, ammonium is preferably NH ₄ ⁺ ,

(C 1 -C ₄ -alk) NH ₃ ⁺ . In the above definitions, "substituted phenyl" or

"Substituted phenyl ring" preferably denotes a phenyl radical which is mono- or polysubstituted, preferably mono-, di- or trisubstituted, by one or more substituents selected from the group consisting of C 1 -C ₄ -alkyl, halogen, C 1 -C ₄ -alkoxy, hydroxy, sulfo , Amino or nitro are particularly preferred substituents are methyl, Cl, amino, methoxy, ethoxy and sulfo.

In a preferred embodiment, R 1 and R 2 independently of one another are hydrogen or methyl.

In a preferred embodiment, R 3 is hydrogen, unsubstituted phenyl or phenyl substituted with amino, sulfo and / or ethoxy.

In a preferred embodiment, R5 is hydrogen or methoxy, or in a likewise preferred embodiment, R4 and R5

together with the adjacent C = C double bond, an unsubstituted or sulfo-substituted phenyl ring.

Preference is given to dyes of the formula (A) in which the radicals R1 and R2 are each hydrogen.

Preference is furthermore given to those dyes of the formula (A) in which R 1 is methyl and R 2 is hydrogen.

Preferred dyes of the formula (B) are those in which

R3 unsubstituted phenyl,

R4 and R5 together with the adjacent C = C double bond form a phenyl substituted with a sulfo group, and R6 is hydrogen, and

M is as defined above.

Further preferred dyes of the formula (B) are those in which

R3 is hydrogen or unsubstituted phenyl,

R4 is hydrogen or sulfo, R5 is hydrogen or methoxy, and

R6 is hydrogen or sulfo, and

M is as defined above. Further preferred dyes of the formula (B) are those in which

R3 is phenyl substituted with amino, sulfo and / or ethoxy,

R4 is hydrogen or sulfo,

R5 hydrogen,

R6 is hydrogen, and

M is as defined above.

The dyes of the formulas (A) and (B) are known per se and can be prepared by known methods, for example as described in: Ulimann, 6.Aufl., 0.1002 / 14356007. a02_355, pages 1 - 68

Ullmann, 6th ed., 10.1002 / 14356007.a03_213.pub3, pages 1 - 42.

Another object of the present invention is a process for the preparation of the acid dye mixture described above, by mixing the at least one dye A with the at least one dye B in the weight ratios indicated above, for example in the form of their dry powder, press cake or preferably aqueous solutions. The dyes A and B can also be mixed together only in the dyebath. The dye mixtures according to the invention are particularly suitable for fibrous material which consists of natural and / or synthetic

Polyamides consists of dyeing or printing in blue tones. The dye mixtures according to the invention are also suitable for producing inkjet printing inks and for printing with these fibrous material which consists of natural and / or synthetic polyamides or cellulose (eg paper). Another object of the invention is the use of said

Dye mixtures for dyeing and / or printing fiber-containing

Materials made from natural or synthetic polyamides or mixtures thereof, e.g. As polyamide / wool exist.

Another object of the invention is the use of said

Dye mixtures for the production of inkjet printing inks and their

Use for printing fibrous materials, which consist of

natural or synthetic polyamides or blended fabrics of these fibers, eg. As nylon / wool exist.

The dyeing is carried out according to known methods, such as. B. the

Continuous process, exhaust process, foam dyeing process and inkjet process.

Preferably, in the exhaust process at a temperature of 30 to 140 ° C, more preferably 80 to 120 ° C, most preferably in a

Temperature of 80 to 100 ° C, and dyed at a liquor ratio of 1: 3 to 1: 40.

The substrate to be dyed z. B. in the form of yarn, fabric, knitted or carpet. Fully-fashioned dyeings are also on delicate substrates, eg. Lambswool, cashmere, alpaca and mohair very well possible. Particularly suitable are the dye mixtures according to the invention for dyeing fine-denier fibers (microfibers). The dye mixtures according to the invention show good compatibility with known acid dyes. Accordingly, the dye mixtures may be used alone in a dyeing or printing process or as a blue component in a combination dyeing or printing composition along with other acid dyes of the same class, i. H. With

Acid dyes, which have comparable dyeing properties, such as fastness properties and Ausziehraten from Därbebad on the substrate. In particular, the dyes of the present invention may be used in conjunction with other acid dyes. The ratio, in the dye mixture according to the invention in a combination dye or printing composition together with other acid dyes

is dictated by the hue one wishes to obtain. The dye mixtures according to the invention are particularly suitable for dyeing wool, silk and all nylon types on which dyeings having a high level of fastness, in particular good light fastness and good

Wet fastness (laundry, alkaline sweat) to be obtained. The dye mixtures show a high Ausziehrate. The buildability of the dye mixtures is also very good. Tone-on-tone staining on the substrates mentioned shows excellent quality. All colors also show a constant shade under artificial light. To mention are also the good

Dekatur- and Verkochbeständigkeit. A decisive advantage of the dye mixtures according to the invention is that they are metal-free and are very level on wool and polyamide

Deliver dyeings.

The dye mixtures according to the invention can also be used as blue components in the trichromatic dyeing process or trichromatic printing process. For Trichromiefärben or printing can be used on all conventional and known dyeing and printing methods, such as. B. the

Continuous process, exhaust process, foam dyeing process and inkjet process.

The composition of the individual dye components in the

Trichromatic dye mixture used in the process of the invention depends on the desired shade. For a shade of brown you can

For example, 20-40% by weight of a yellow component, 40-60% by weight of an orange or red component and 10-20% by weight of an acid dye mixture according to the invention are used as the blue component. In the following examples, parts are parts by weight and percentages are by weight.

Example 1a (PA staining):

A dyebath of 40 ° C consisting of 2000 parts of water, 1 part of a weakly cationic, dye-affinity leveling agent based on an ethoxylated aminopropyl fatty acid amide, 0.25 parts of the following

Dye mixture, consisting of 9 parts

when adjusted to pH 5 with 1 - 2 parts of 40% acetic acid, 100 parts of polyamide 6 fabric are added. After 10 minutes at 40 ° C, the dyebath is heated to 98 ° C with a temperature increase of 1 ° C per minute and then left at boiling temperature for 45-60 minutes. It is then cooled to 70 ° C within 15 minutes. The dyed polyamide fabric is removed from the bath, rinsed with warm and then cold water and dried. The result is a blue level polyamide dyeing, which shows good light and wet fastness.

Example 1b (wool dyeing):

A dyebath of 40 ° C, consisting of 4000 parts of water, 1 part of a weakly dye affinity leveling agent with amphoteric character on the basis of a sulfated, ethoxylated fatty acid amide, 0.4 parts of the dye mixture of Example 1a, with 1 - 2 parts 40% Acetic acid was adjusted to pH 5, 100 parts of wool fabric are added. After 10 minutes at 40 ° C, the dyebath with a temperature increase of 1 ° C per minute on

Boiling heated and then left at boiling temperature 40-60 minutes. The mixture is then cooled to 70 ° C within 20 minutes. The dyed

Wool fabric is taken out of the bath, rinsed with warm and then cold water and dried. The result is a blue level wool dyeing with good light and wet fastness with excellent levelness within the fiber (root-tip).

Examples 2 to 18:

The dyes of Examples 2 to 18 listed in the table below are mixed in the ratio Dye B: Dye A of 1: 9 or of 2: 8 and used for dyeing in analogy to Examples 1a and 1b. The dye mixtures of the invention provide on the respective substrate (polyamide or wool) well reproducible, level dyeings with very good wet and light fastness. 10

Example 19

A dye bath of 40 ° C, consisting of 2000 parts of water, 1 part of a weakly cationic dye-like leveling agent based on an ethoxylated Aminopropylfettsäureamids, 0.3 parts of a dye mixture from Example 1a, with 1-2 parts of 40% acetic acid to pH 5.5, 100 parts of nylon 6,6 fabric are added. After 10 minutes at 40 ° C, the dyebath is heated with a temperature increase of 1.5 ° C per minute to 120 ° C and then left for 15-25 minutes at this temperature.

It is then cooled to 70 ° C within 25 minutes. The dyed

Polyamide 6,6 fabric is removed from the dyebath, rinsed with warm and then cold water and dried. It results in a blue one

Polyamide dyeing of good levelness, which has good light and wet fastness properties. Example 20

100 parts of a polyamide 6 woven fabric are made up with a fleet of 50 ° C

40 parts of a dye mixture from Example 1a,

100 parts urea, 20 parts of a non-ionic solubilizer based on

diglycol,

15-20 parts of acetic acid (to adjust the pH to 4),

10 parts of a weakly cationic, dye-affinity leveling agent based on an ethoxylated Aminopropylfettsäureamids and

810 - 815 parts of water (addition to 1000 parts padding fleece) padded. The product impregnated in this way is rolled up and fixed in a steaming chamber under saturated steam conditions at 85-98 ° C. during

Let rest for 3 - 6 hours. Subsequently, the dyed fabric is rinsed with warm and cold water and dried. This gives a blue polyamide dyeing with good Flächenegalität and good light and wet fastness. Example 21

A textile velor fabric of polyamide 6 with a synthetic base fabric, which consists of cotton, polyamide or polyester, is padded with a liquor, which in 1000 parts 1 part of a dye mixture from Example 1a

4 parts of a commercial thickener based Kernmehlätherbasis 2 parts of a non-ionic Äthylenoxydadduktes a higher

alkylphenol

1 part of acetic acid contains 60%.

Subsequently, a paste containing 1000 parts of the following components is printed:

Parts of commercially available alkoxylated fatty alkylamine (Displace product) Parts of a commercial thickener based on core flour ether. The pressure is fixed for 6 minutes in saturated steam at 100 ° C, rinsed and dried. You get an equally colored blue and white patterned

Upholstery fabric. Example 22 (trichromatic coloration)

A dyebath of 40 ° C, consisting of 2000 parts of water, 1 part of a weakly cationic dye-like leveling agent based on an ethoxylated Aminopropylfettsäureamids, 0.2 parts of the red dye from Example 8 of WO2002 / 46318, 1, 5 parts of a commercial preparation 236 of Cl Acid Yellow (Nylosan Yellow ^® FL), and 0.5 parts of the blue

Dye mixture from Example 1a, which was adjusted to pH 5 with 1 to 2 parts of 40% acetic acid are added to 100 parts of polyamide 6.6 fabric. After 10 minutes at 40 ° C, the dyebath is heated with a temperature increase of 1 ° C per minute to 98 ° C and then left for 45 to 60 minutes at boiling temperature. It is then cooled to 70 ° C within 15 minutes. The dyed fabric is removed from the bath, rinsed with warm and then cold water and dried. The result is a level gray polyamide dyeing, which shows good light and wet fastness. Example 23

3 parts of a dye mixture from Example 1 are divided into 82 parts

demineralized water and 5 parts of diethylene glycol dissolved at 60 ° C. After cooling to room temperature, a blue printing ink is obtained, which is very well suited for inkjet printing on paper or polyamide and wool textiles.

Examples 10 to 14 are carried out with the dye mixtures of Examples 2 to 9 with comparably good results.

Example 24 (wool / polyamide blended fabric dyeing)

A dyebath of 40 ° C, consisting of 4000 parts of water, 1 part of a weakly dye affinity leveling agent with amphoteric character on the basis of a sulfated, ethoxylated fatty acid amide, 0.4 parts of the dye mixture of Example 1a, with 1 - 2 parts 40% Acetic acid adjusted to pH 5 100 parts of wool / polyamide blended fabric are added. After 10 minutes at 40 ° C, the dyebath is heated to boiling temperature with a temperature increase of 1 ° C per minute and then left for 40 - 60 minutes at boiling temperature. The mixture is then cooled to 70 ° C within 20 minutes. The dyed wool / polyamide blend is removed from the bath, rinsed with warm and then cold water and dried. The result is a blue level wool / polyamide blend fabric dyeing with good light and wet fastness properties with excellent levelness within the wool fiber (root-lace) and equal shade on nylon and wool fibers.

Comparative Example 25 (trichromatic coloration)

It is a dyebath of 40 ° C, consisting of 4000 parts of water,

2 parts C.I. Acid Orange 67,

1 part C.I. Acid Red 336 and

3 parts Optilan ^® Blue MF-GL

prepared and a polyamide 6 fabric dyed analogously to Example 1a. The

Dyeing results are poorly reproducible (blocking) and have poor wet fastness.

On the other hand, good dyeings with good wetfastness properties are obtained on wool.

Comparative Example 26 (trichromatic coloration)

It is a dyebath of 40 ° C, consisting of 4000 parts of water,

2 parts C.I. Acid Orange 67,

1 part C.I. Acid Red 336 and

3 parts Acid Blue 350

prepared and a wool fabric dyed analogously to Example 1b. It creates a restless appearance.

On the other hand, good wetfastness and well reproducible staining are achieved on nylon 6.

Example 27 (trichromatic coloration)

It is a dyebath of 40 ° C, consisting of 4000 parts of water,

2 parts of Cl Acid Orange 67, 1 part of Cl Acid Red 336 and

3 parts of a dye mixture according to the invention from each one of Examples 1 to 9 prepared.

On polyamide good, reproducible coloration with good wet fastness can be achieved. Also on wool gives a very nice appearance with good

Wet fastness.

Claims

claims:

An acid dye mixture comprising

a) 70 to 95% by weight of at least one dye A having the general structure (A)

(A)

wherein

R1 is H, d-Ce-alkyl; and

R2 is H, d-Ce-alkyl; b) 5 to 30% by weight of at least one dye B having the general structure (B)

wherein R 3 is H, phenyl, where phenyl is substituted or unsubstituted,

R4 H, sulfo,

R 5 is H, C 1 -C ₄ -alkoxy,

or R4 and R5 form together with the adjacent one

C = C double bond represents an unsubstituted or substituted phenyl ring,

R6 H, sulfo;

M H, alkali metal, ammonium or a simple negative charge

mean,

where the weight percentages are based on the total weight of the

Acid dye mixture are related.

2. Acid dye mixture according to claim 1, comprising 80 to 95 wt .-% of at least one dye A of the formula (A), and 5 to 20 wt .-% of at least one dye B of the formula (B).

3. Acid dye mixture according to claim 1 or 2, comprising 85 bis

90% by weight of at least one dye A of the formula (A), and 10 to 15% by weight of at least one dye B of the formula (B).

4. Acid dye mixture according to one or more of claims 1 to 3, characterized in that R1 and R2 are independently hydrogen or methyl.

5. Acid dye mixture according to one or more of claims 1 to 4, characterized in that R3 is hydrogen, unsubstituted phenyl or with

Amino, sulfo and / or ethoxy is substituted phenyl.

6. Acid dye mixture according to one or more of claims 1 to 5, characterized in that R5 is hydrogen or methoxy.

7. Acid dye mixture according to one or more of claims 1 to 6, characterized in that in the dye of the formula (B)

R3 unsubstituted phenyl, R4 and R5, together with the adjacent C = C double bond, form a sulfo-substituted phenyl ring, and R6 is hydrogen

mean.

8. Acid dye mixture according to one or more of claims 1 to 6, characterized in that in the dye of the formula (B)

R3 is hydrogen or unsubstituted phenyl,

R4 is hydrogen or sulfo,

R5 is hydrogen or methoxy, and

R6 is hydrogen or sulfo

mean.

9. Acid dye mixture according to one or more of claims 1 to 6, characterized in that in the dye of formula (B)

R3 is phenyl substituted with amino, sulfo and / or ethoxy,

R4 is hydrogen or sulfo,

R5 is hydrogen and

R6 hydrogen

mean.

10. A process for preparing an acid dye mixture according to one or more of claims 1 to 9, by mixing the at least one dye A with the at least one dye B with each other.

11. Use of a dye mixture according to one or more of claims 1 to 9 for dyeing and / or printing fibrous materials, which consist of natural or synthetic polyamides or mixtures thereof.

12. Use according to claim 11, characterized in that the fiber material consists of wool, silk, a synthetic polyamide or a mixture thereof.

13. Use according to claim 11 or 12 in the trichromatic dyeing process or trichromatic printing process as a blue component.