JP2014522443A - Acid dye mixtures for polyamide and wool - Google Patents

Abstract

The invention comprises a) 20 to 95% by weight of at least one dye A having the general structure (A), and b) 5 to 80% by weight of at least one dye B having the general structure (B) The acid dye mixture.

Description

Acid dyes are mainly used for dyeing wool, other animal hair, silk and polyamide. Although such fibers are similar in terms of chemical properties (polyaminocarboxylic acids), the physical differences between wool and animal hair on the one hand and polyamide and silk on the other hand are very large. As a result, the characteristics of acid dyes in polyamide may differ from those in wool. For example,
-Color itself-Light fastness (usually worse in polyamide than in wool)
-Composition (usually worse in polyamide than in wool)
-Wet fastness.

  Wool also has a reducing action during dyeing and in several finishing steps. This can cause a number of acid dyes suitable for polyamides to be “over-boiled” during dyeing and to cause a color change during finishing.

  Furthermore, many acid dyes are known to color the tips of wool fibers in a state that is clearly different from the root. This can only be corrected inadequately with certain aids. However, for the beautiful fabric appearance of wool textiles, it is a prerequisite that the roots and tips are very well even. Therefore, in order to obtain a beautiful fabric appearance in wool, a plurality of acid dyes are often mixed in one product. However, such mixing is not suitable for intermediate or dark composite colors when dyeing polyamides. This is because blocking by a wide variety of components occurs due to the fact that some of the required mixed components are only slightly constituted. Therefore, very few acid dye mixtures are recommended for polyamides and wool, and especially for blends of both fibers. A few examples known on the market are “Egalisierfarbstoffe”, which has a low wet fastness for dyeing polyamide / wool (carpet yarn). For dyeing garment textiles consisting of wool and polyamide, among other things, it has the following blue components, ie good fabric appearance and is suitable for wool and polyamide, and is reproducible with yellow and red components It lacks the blue component that can be used for composite colors and also has the necessary wash fastness, sweat fastness, and process fastness.

  It has now surprisingly been found that the acid dye mixtures described below give polyamides, wool, and polyamide / wool blend fibers a well-reproducible color with good wet fastness.

The subject of the present invention is an acid dye mixture,
a) General structure (A):

[Where:
R1, R2, R3, R4 independently of one another, H, C ₁ -C ₆ - means an alkylene -NR12R13 alkyl, C ₁ -C ₆ - - alkoxy, -NR12R13, C ₁ -C _6;
R5 is, H, C ₁ -C ₆ - means alkylene -NR12R13, sulfoalkyl, C ₁ -C ₆ - - alkoxy, -NR12R13, C ₁ -C _6;
R50 is, H, C ₁ -C ₆ - alkyl, C ₅ -C ₆ - means a cycloalkyl;
R12 represents H, C ₁ -C ₆ -alkyl;
R13 means —CO—CH ₂ —Cl, —SO ₂ -phenyl, where phenyl is substituted or unsubstituted;
M means H, alkali metal, ammonia]
Having
20 to 95% by weight, preferably 30 to 95% by weight, particularly preferably 50 to 90% by weight of at least one dye A, and b) the general structure (B)
[Where:
R6 means H, phenyl, which is substituted or unsubstituted;
R7 means H, sulfo,
R8 represents H, C ₁ -C ₄ -alkoxy, or R 7 and R 8 together with the adjacent C═C double bond form an unsubstituted or substituted phenyl ring;
R9 means H, sulfo,
M means H, alkali metal, ammonium, or a single negative charge]
Having
5 to 80% by weight, preferably 5 to 70% by weight, particularly preferably 10 to 50% by weight, of at least one dye B
Including
Each weight percent is the acid dye mixture based on the total weight of the acid dye mixture.

Positive charge in the formula (B) is usually by the negative charge of the sulfo groups contained in the molecule, or 1 anion equivalent, for example Cl ^-, it is neutralized by the ^1/2 SO ₄ ^2-.

In the above definition, sulfo means a residue of the formula SO ₃ M. M is preferably a single negative charge, hydrogen, alkali metal, or ammonium.

  In the above definition, alkali metal preferably means Li, Na or K, in particular Na.

In the above definition, ammonium preferably denotes NH ₄ ⁺ , (C ₁ -C ₄ -alkyl) NH ₃ ⁺ .

In the above definition, “substituted (substituted) phenyl” or “substituted (substituted) phenyl ring” is preferably C ₁ -C ₄ -alkyl, halogen, C ₁ -C ₄ -alkoxy, hydroxy, It means a phenyl residue that is substituted one or more times, preferably once, twice or three times by one or more substituents selected from a sulfo, amino or nitro group. Particularly preferred substituents mean methyl, Cl, amino, methoxy, ethoxy, and sulfo.

In a preferred embodiment, independently R1, R2, R3, R4 are each preferably hydrogen, methyl, methoxy, NR12R13, or C ₁ -C ₂ - means an alkylene -NR12R13, R12 is preferably hydrogen or methyl And R13 means —CO—CH ₂ —Cl or —SO ₂ -phenyl, where phenyl is substituted or unsubstituted.

  In preferred embodiments, R5 is hydrogen, methyl, or sulfo.

In a preferred embodiment, R50 is hydrogen, methyl, ethyl, branched C ₃ -C ₆ - means alkyl, cyclopentyl or cyclohexyl, in particular methyl, isopropyl or cyclohexyl.

  In a preferred embodiment, R6 represents hydrogen, unsubstituted phenyl, or phenyl substituted with amino, sulfo and / or ethoxy.

  In a preferred embodiment, R8 represents hydrogen or methoxy, or in a likewise preferred embodiment, R7 and R8 are substituted with an unsubstituted phenyl ring or a sulfo group together with an adjacent C═C double bond. A phenyl ring is formed.

Preferred are one residue of the residues R1~R4 is NR12R13, C ₁ -C ₂ - means an alkylene -NR12R13, R12 is hydrogen or methyl, R13 is -SO ₂ - (4-methyl Phenyl), the other residues among the residues R1 to R4 are the same or different and each represents hydrogen or methyl, and R5 represents hydrogen, methyl, or sulfo; And R50 is a dye of formula (A), as defined above.

Particularly preferred, R2, or R3 is NR12R13, or C ₁ -C ₂ - means an alkylene -NR12R13, R12 is hydrogen or methyl, R13 is -SO ₂ - is a (4-methylphenyl), the remaining The other residues of the groups R1 to R4 are the same or different and each represents hydrogen or methyl, and R5 represents hydrogen, methyl, or sulfo, and M and R50 are as described above. It is a dye of the formula (A) as defined.

Particularly preferred, R2, or R3 is meant NR12R13, or CH ₂ -NR12R13, R12 is hydrogen or methyl, R13 is -SO ₂ - is a (4-methylphenyl), the residue R1~R4 Each of the other residues is hydrogen, and R5 is hydrogen, methyl, or sulfo, and M and R50 are dyes of formula (A), as defined above.

Although more preferred two of the residues R1~R4, C ₁ -C ₂ - means an alkylene -NR12R13, R12 is hydrogen or methyl, R13 is -CO-CH ₂ -Cl, and the The other residues out of residues R1-R4 are the same or different, meaning hydrogen or methyl, and R5 is hydrogen, methyl, or sulfo, and M and R50 are as described above. It is a dye of the formula (A) as defined.

Particularly preferred, R2 and R4 are each C ₁ -C ₂ - means an alkylene -NHCO-CH ₂ -Cl, and R1, R3 and R5 is a hydrogen or methyl respectively, and M and R50 are the Is a dye of formula (A).

Particularly preferred is that R2 and R4 each represent —CH ₂ —NHCO—CH ₂ —Cl, and R1, R3 and R5 each represent methyl, and M and R50 are defined as above, It is a dye of the formula (A).

Preferred dyes of formula (B) are
R6 means unsubstituted phenyl,
R7 and R8 together with the adjacent C = C double bond form a phenyl ring substituted with a sulfo group, and R9 means hydrogen, and M is defined as above,
It is a dye.

More preferred dyes of formula (B) are
R6 represents hydrogen or unsubstituted phenyl,
R7 means hydrogen or sulfo,
R8 represents hydrogen or methoxy, R9 represents hydrogen or sulfo, and M is as defined above,
It is a dye.

More preferred dyes of formula (B) are
R6 represents phenyl substituted with amino, sulfo, and / or ethoxy,
R7 means hydrogen or sulfo,
R8 represents hydrogen, R9 represents hydrogen, and M is as defined above,
It is a dye.

The dyes of the formulas (A) and (B) are known per se, for example:
Ullmann, 6th edition, 10.1002 / 14356007.a02_355, pp. 1-68
As described in Ullmann, 6th edition, 10.1002 / 14356007. A03_213.pub3, pages 1-42, it can be prepared according to known methods.

  A further object of the present invention is to mix the acid by mixing at least one dye A and at least one dye B with each other in the above weight ratio in the form of a dry powder, a press cake, or preferably an aqueous solution. A method for producing a dye mixture. Dyes A and B can also be mixed together for the first time in the dyebath.

  The dye mixtures according to the invention are particularly suitable for dyeing and / or printing in blue shades on fiber-containing materials made of natural and / or synthetic polyamides. The dye mixtures according to the invention are also suitable for producing ink jet printing inks and using such inks for printing on fiber-containing materials made of natural and / or synthetic polyamides or celluloses (eg paper). .

  A further subject of the present invention is the use of said acid dye mixtures for dyeing and / or printing natural or synthetic polyamides or mixtures thereof, for example fiber-containing materials consisting of polyamide / wool.

  A further object of the present invention is to produce ink jet printing inks and to use such ink jet printing to print on fiber-containing materials consisting of natural or synthetic polyamides or mixed woven fabrics of these fibers, such as nylon / wool. Is to use ink.

  The dyeing is carried out according to well-known methods, for example the continuous method, the drawing method (Ausziehverfahren), the bubble dyeing method (Schaumfaerbeverfahren) and the ink jet method.

  Dyeing is preferably carried out in a drawing method at a temperature of 30 to 140 ° C., particularly preferably 80 to 120 ° C., more preferably 80 to 100 ° C., and a dye liquor ratio of 1: 3 to 1:40.

  The substrate to be dyed may be in the form of, for example, a yarn, a woven fabric, a knitted product or a carpet. Full-fashioned dyeing can be performed very well on delicate substrates such as lamb wool, cashmere, alpaca and mohair. In particular, the dye mixtures according to the invention are suitable for dyeing fine fibers (microfibers).

  The dye mixtures according to the invention show good compatibility with known acid dyes. Correspondingly, the dye mixture can be used alone in a dyeing or printing process, or together with another acid dye of the same class as a blue component in a composite dyeing composition or composite printing composition, That is, it can also be used with acid dyes having comparable dye properties, such as fastness and withdrawal speed from the dye bath to the substrate. The dyes according to the invention can be used in particular with other acid dyes. The proportion of the dye mixture according to the invention used in the composite dyeing composition or the composite printing composition together with another acid dye is determined by the color tone to be obtained.

  The dye mixtures according to the invention are suitable for dyeing wool, silk and all types of nylon in order to obtain high fastness levels, in particular good light fastness and good wet fastness (laundry, alkaline sweat). Especially suitable. The dye mixture exhibits a high drawing speed. The constructability of the dye mixture is also very good. The tone-in-tone dyeing on the substrate shows excellent quality. All staining also shows a certain nuance under artificial light. It should be further mentioned that there is good resistance to decating and excessive boiling.

  The decisive advantage of the dye mixtures according to the invention is that they are metal-free and provide uniform and even dyeings on wool and polyamide.

  The dye mixture according to the invention can also be used as a blue component in a three-color dyeing method or a three-color printing method. For the three-color dyeing method or the three-color printing method, it is possible to go back to the usual well-known dyeing and printing methods, for example, the continuous method, the drawing method, the bubble dyeing method and the ink jet method.

  The composition of the individual dye components in the three-color dye mixture used in the process according to the invention depends on the desired color tone. For brown shades, for example, 20 to 40% by weight of a yellow component, 40 to 60% by weight of an orange or red component, and 10 to 20% by weight of an acid dye mixture according to the invention as a blue component are used. be able to.

  In the following examples, “parts” means parts by weight, and percentages mean percent by weight.

Example 1a (PA staining):
2000 parts water, 1 part weakly cationic dye affinity leveling agent based on ethoxylated aminopropyl fatty acid amide, 0.25 part of the following dye mixture (9 parts

1 part adjusted to pH 5 with 1-2 parts 40% acetic acid

100 parts of polyamide 6 woven fabric is added to a 40 ° C. dyebath consisting of After 10 minutes at 40 ° C., the dyebath is heated to 98 ° C. with a temperature increase of 1 ° C. per minute and then brought to the boiling temperature for 45-60 minutes. Subsequently, it is cooled to 70 ° C. within 15 minutes. The dyed polyamide woven fabric is removed from the bath, rinsed with warm water and then with cold water and dried. The result is a blue, even polyamide dyeing that exhibits good light fastness and wet fastness.

Example 1b (wool dyeing):
Example 1a adjusted to pH 5 with 4000 parts water, 1 part amphoteric weak dye affinity leveling agent based on sulphated ethoxylated fatty acid amide and 1-2 parts 40% acetic acid 100 parts of a woolen woven fabric are added to a 40 ° C. dyebath consisting of 0.4 part of a dye mixture. After 10 minutes at 40 ° C., the dyebath is heated to the boiling temperature with a temperature increase of 1 ° C. per minute and then left at the boiling temperature for 40-60 minutes. Subsequently, it is cooled to 70 ° C. within 20 minutes. The dyed woolen fabric is removed from the bath, rinsed with warm water and then with cold water and dried. The result is a blue uniform wool dyeing with excellent uniformity inside the fiber (root-tip), good light fastness and wet fastness.

Examples 2-30:
Examples 2-30 listed in the table below are mixed in a dye B: dye A ratio of 1: 9 or 2: 8 and used for dyeing in the same manner as in Examples 1a and 1b. The dye mixtures according to the invention result in uniform dyeings which are well reproducible on each substrate (polyamide or wool) with very good wet fastness and light fastness.

Example 31
Example adjusted to pH 5.5 with 2000 parts water, 1 part weakly cationic dye affinity leveling agent based on ethoxylated aminopropyl fatty acid amide, and 1-2 parts 40% acetic acid. 100 parts of polyamide 6,6 woven fabric are added to a 40 ° C. dyebath consisting of 0.3 part of the dye mixture of 1a. After 10 minutes at 40 ° C., the dyebath is heated to 120 ° C. with a temperature increase of 1.5 ° C. per minute and then left at this temperature for 15-25 minutes. Subsequently, it is cooled to 70 ° C. within 25 minutes. The dyed polyamide 6,6 woven fabric is removed from the dyebath, rinsed with warm water and then with cold water and dried. The result is a good even blue polyamide dyeing with good light fastness and wet fastness.

Example 32
40 parts of the dye mixture of Example 1a 100 parts of urea 20 parts of non-ionogenic solvent based on butyl diglycol 15-50 parts of acetic acid (to adjust the pH value to 4)
10 parts weakly cationic dye affinity leveling agent based on ethoxylated aminopropyl fatty acid amide, and 810 to 815 parts water (supplement to 1000 parts Fullard dye liquor)
100 parts of polyamide 6 fabric is foulardieren with a dye liquor consisting of In order to wind up and fix the impregnated fabric, it is allowed to stay in a steam chamber under saturated steam conditions at 85 to 98 ° C. for 3 to 6 hours. Subsequently, the dyed woven fabric is rinsed with warm water and then with cold water and dried. A blue polyamide dyeing with good surface uniformity and good light and wet fastness is obtained.

Example 33
A textile velor surface structure of polyamide 6 having a synthetic base fabric made of cotton, polyamide or polyester,
1 part of the dyeing mixture of Example 1a in 1000 parts 4 parts of a commercially available thickener based on Kernmehlaether 2 parts of non-ionogenic ethylene oxide adducts of higher alkylphenols 1 part of 60% acetic acid Foulard treatment with a dye solution containing

Subsequently, printing is performed with a paste containing the following ingredients in 1000 parts:
20 parts of a commercially available alkoxylated aliphatic amine (substituted product)
20 parts of a commercial thickener based on guar gum ether.

  The print is fixed in saturated steam at 100 ° C. for 6 minutes, rinsed and dried. An evenly dyed cover fabric with blue and white patterns is obtained.

Example 34 (Tricolor dyeing)
2000 parts of water, 1 part of a weakly cationic dye affinity leveling agent based on ethoxylated aminopropyl fatty acid amide, and 0. 0 described in Example 8 of WO 2002/46318. 0 of Example 1a adjusted to pH 5 with 2 parts of red dye, 1.5 parts of the commercially available CI Acid Yellow 236 (Nylosan® Gelb FL) formulation and 1-2 parts of 40% acetic acid. To a 40 ° C. dyebath consisting of 5 parts of the blue dye mixture, 100 parts of polyamide 6.6 woven 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 brought to the boiling temperature for 45-60 minutes. Subsequently, it is cooled to 70 ° C. within 15 minutes. The dyed woven fabric is removed from the bath, rinsed with warm water and then with cold water and dried. The result is an even gray polyamide dyeing that exhibits good light fastness and wet fastness.

Example 35
3 parts of the dye mixture of Example 1 are dissolved at 60 ° C. in 82 parts of demineralized water and 15 parts of diethylene glycol. After cooling to room temperature, a blue printing ink is obtained which is very suitable for ink jet printing on paper or polyamide / wool textile.

  Examples 31-35 are carried out with the dye mixtures of Examples 2-30 and equally good results are obtained.

Example 36 (wool / polyamide mixed woven fabric dyeing)
Example 23 adjusted to pH 5 with 4000 parts of water, 1 part of an amphoteric weak dye affinity leveling agent based on sulfated ethoxylated fatty acid amides and 1-2 parts of 40% acetic acid. 100 parts of a wool / polyamide mixed woven fabric are added to a 40 ° C. dyebath consisting of 0.4 part of a dye mixture. After 10 minutes at 40 ° C., the dyebath is heated to the boiling temperature with a temperature increase of 1 ° C. per minute and then left at the boiling temperature for 40-60 minutes. Subsequently, it is cooled to 70 ° C. within 20 minutes. The dyed wool / polyamide mixed woven fabric is removed from the bath, rinsed with warm water and then with cold water and dried. As a result, blue uniform wool / polyamide blend with good light fastness and wet fastness, with excellent uniformity inside the wool fiber (base-tip) and the same nuance on polyamide wool fiber Textile dyeing occurs.

Comparative Example 37 (three-color dyeing)
4000 parts water 2 parts C.I. I. Acid Orange 67
1 part of C.I. I. Acid Red 336 and 3 parts Optilan® Blau MF-GL
A 40 ° C. dye bath is formed and a polyamide 6 woven fabric similar to Example 1a is dyed. The dyeing results are poorly reproducible (blocking) and poor in wet fastness.
In contrast, in wool, good dyeing with good wet fastness is achieved.

Comparative Example 38 (three-color dyeing)
4000 parts water 2 parts C.I. I. Acid Orange 67
1 part of C.I. I. Acid Red 336 and 3 parts Acid Blue 350
A 40 ° C. dye bath is formed and a woolen woven fabric similar to Example 1b is dyed. An unstable fabric appearance results.
In contrast, polyamide 6 achieves good wet fastness and good reproducible dyeing.

Example 39 (three-color dyeing)
4000 parts water 2 parts C.I. I. Acid Orange 67
1 part of C.I. I. A 40 ° C. dyebath is formed consisting of Acid Red 336 and 3 parts of the dye mixture according to the invention, each one of Examples 1-30.
In polyamide, good, reproducible dyeings are achieved with good wet fastnesses. Even in wool, a very beautiful fabric appearance with good wet fastness results.

Claims (15)

An acid dye mixture comprising:
a) General structure (A)
[Where:
R 1, R 2, R 3, R 4 independently of one another represent H, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, —NR 12 R 13, C ₁ -C ₆ -alkylene-NR 12 R 13;
R5 is, H, C ₁ -C ₆ - means alkylene -NR12R13, sulfoalkyl, C ₁ -C ₆ - - alkoxy, -NR12R13, C ₁ -C _6;
R50 is, H, C ₁ -C ₆ - alkyl, C ₅ -C ₆ - means a cycloalkyl;
R12 represents H, C ₁ -C ₆ -alkyl;
R13 means —CO—CH ₂ —Cl, —SO ₂ -phenyl, where phenyl is substituted or unsubstituted;
M means H, alkali metal, ammonia]
From 20 to 95% by weight of at least one dye A, and b) a general structure (B)
[Where:
R6 means H, phenyl, which is substituted or unsubstituted,
R7 means H, sulfo,
R8 represents H, C ₁ -C ₄ -alkoxy, or R 7 and R 8 together with the adjacent C═C double bond form an unsubstituted or substituted phenyl ring;
R9 means H, sulfo,
M means H, alkali metal, ammonium, or a single negative charge]
5 to 80% by weight of at least one dye B
Including
Each of the acid dye mixtures, wherein the weight percentages are based on the total weight of the acid dye mixture.   The acid dye according to claim 1, comprising 50 to 90% by weight of at least one dye A of formula (A) and 10 to 50% by weight of at least one dye B of formula (B). blend. R 1, R 2, R 3, R 4, independently of one another, represent hydrogen, methyl, methoxy, NR 12 R 13, or C ₁ -C ₂ -alkylene-NR 12 R 13, R 12 represents hydrogen or methyl, and R 13 represents —CO—. CH ₂ -Cl or -SO ₂ - means a phenyl, phenyl is characterized by a substituted or unsubstituted, acid dye mixture according to claim 1 or 2.   The acidic dye mixture according to claim 1, wherein R5 is hydrogen, methyl, or sulfo.   5. The acidic dye mixture according to claim 1, wherein R 6 is hydrogen, unsubstituted phenyl, or phenyl substituted with amino, sulfo and / or ethoxy. 6. R50 is hydrogen, methyl, ethyl, branched C ₃ -C ₆ - alkyl, wherein the means cyclopentyl or cyclohexyl, acid dye mixture according to any one of claims 1 to 5.   The acid dye mixture according to claim 1, wherein R 8 represents hydrogen or methoxy. In the dye of the formula (A), one of the residues R1 to R4 means NR12R13, C ₁ -C ₂ -alkylene-NR12R13, R12 is hydrogen or methyl, and R13 is —SO _2. -(4-methylphenyl), the other residues of the residues R1 to R4 are the same or different and each represents hydrogen or methyl, and R5 represents hydrogen, methyl, or sulfo The acid dye mixture according to any one of claims 1 to 7, characterized in that In the dye of formula (B),
R6 means unsubstituted phenyl,
R7 and R8 together with the adjacent C = C double bond form a phenyl ring substituted with a sulfo group, and R9 means hydrogen,
The acid dye mixture according to claim 1, wherein the acid dye mixture is a mixture of acid dyes. In the dye of formula (B),
R6 represents hydrogen or unsubstituted phenyl,
R7 represents hydrogen or sulfo,
R8 means hydrogen or methoxy, and R9 means hydrogen or sulfo,
The acid dye mixture according to claim 1, wherein the acid dye mixture is a mixture of acid dyes. In the dye of formula (B),
R6 means phenyl substituted with amino, sulfo, and / or ethoxy;
R7 represents hydrogen or sulfo,
R8 means hydrogen and R9 means hydrogen,
The acid dye mixture according to claim 1, wherein the acid dye mixture is a mixture of acid dyes.   The method for producing an acidic dye mixture according to any one of claims 1 to 11, wherein at least one dye A and at least one dye B are mixed with each other.   12. Use of the acid dye mixture according to any one of claims 1 to 11 for dyeing and / or printing fiber-containing materials consisting of natural or synthetic polyamides or mixtures thereof.   14. Use according to claim 13, characterized in that the textile material consists of wool, silk, synthetic amide or a mixture thereof.   15. Use according to claim 13 or 14 as a blue component in a three-color dyeing method or a three-color printing method.