EP1934292A1

EP1934292A1 - Dyes and dye mixtures for dying polymers, method for the production thereof and their use

Info

Publication number: EP1934292A1
Application number: EP06793836A
Authority: EP
Inventors: Gunter GÖRLITZ; Markus Arnold
Original assignee: Dystar Textilfarben GmbH and Co Deutschland KG
Current assignee: Dystar Textilfarben GmbH and Co Deutschland KG
Priority date: 2005-10-01
Filing date: 2006-09-26
Publication date: 2008-06-25
Also published as: AU2006298740A1; WO2007039525A1; DE102005047290A1; CN101268153A; NO20082070L; US20080312352A1; KR20080047586A; JP2009510204A; RU2008116835A; BRPI0616792A2; CA2624474A1; TW200714671A

Abstract

The invention relates to dyes of general formula (I) in which R1 to R12 and r have the meanings cited in Claim 1, to dye mixtures containing more than one dye of general formula (1), to the production thereof and to their use for dying polymers, particularly polyurethane and polyurethane foam.

Description

Dyes and dye mixtures for polymer dyeing, process for their preparation and their use

Polymers can be dyed with dyes in a variety of ways. This includes the mass coloration of polymers, wherein z. B. a pigment or a dye is mixed with the polymer and the dye passes by melting the polymer in the polymer matrix. In other methods, the polymer is dyed by diffusing the dyes from a solution or dispersion, such as e.g. B. in the dyeing of polymer fibers from z. As polyester, polyacrylonitrile, polyurethane, cellulose or polyamide using z. As disperse dyes, basic dyes, acid dyes, metal complex dyes or reactive dyes, wherein when using reactive dyes, a covalent bond between the dye and the substrate is built, whereby particularly high fastnesses of the dyeings are achieved. Another possibility for dyeing polymers is to add the dye to the monomers or oligomers before or during the production of a polymer. If the dyes can form covalent bonds with the polymer backbone, dyeings of high fastness can also be obtained. For this purpose, the dyes used or their chromophores must be sufficiently stable under the conditions of the polymerization. Depending on the type of polymerization, these requirements vary. In the production of polyurethanes, essentially diisocyanates are polymerized with diols or polyols. To produce polyurethane foam, water is added to the reaction mixture or a propellant gas is used. Furthermore, the starting materials before the polymerization stabilizers and activators, such as. As amines, silicones and tin compounds added. The polymerization proceeds at elevated temperatures in the presence of highly reactive compounds and intermediates. For the preparation of colored polyurethanes, it is possible to add to the diol or polyol component, prior to the polymerization, dyes which contain at least two hydroxyl groups, so that the dye can be covalently bonded into the polymer chains during the polymerization without any chain termination taking place. The dye used must not alter the mechanical properties of the polyurethane. Is it correct? the dye used to a solid, it is previously advantageously dissolved in a solvent or used as a dye dispersion, for example in a polyol.

Such dyes are known and are described in DE2259435, DE2357933. However, the known dyes do not meet all the requirements regarding the stability of the dyes under the respective polymerization conditions. In the case of the production of polyurethane foams, some dyes affect the foam structure and thus the mechanical properties of the foam, so that the dyed foam has different mechanical properties than the undyed foam, which is undesirable. The actually available suitable disperse dyes for the production of colored polyurethane foam do not allow to achieve any desired range in the color space. There is therefore a need for dyes which have the properties mentioned and are thus suitable for the coloring of polyurethane.

It has now been found that dyes of the general formula (1) overcome the abovementioned disadvantages in the dyeing of polyurethane: They have a high stability under the conditions of use and give dyeings having high fastness properties.

The present invention therefore relates to the dyes of the general formula (1)

in which R is at least one hydroxy-substituted aryl, which is additionally substituted by alkoxy, hydroxy (Ci-C ₄₀ ) alkyl, (Ci-C ₄₀ ) alkyl, aryl, (C ₂ -C ₄₀ ) alkylene, halogen, carboxylic acid ester , Carbonamido or cyano may be substituted by at least one hydroxy-substituted (CrC ₆ o) - Alkyl, which is additionally substituted by alkoxy, hydroxy (Ci-C ₄₀ ) alkyl, (CrC ₄₀ ) alkyl, aryl, (C ₂ -C ₄₀ ) alkylene, halogen, carboxylic acid esters, carbonamido or cyano or by oxygen , Alkoxylene, arylene, carbonyl, carboxylic acid ester, carbonamido, sulfone or NR ¹³ may be interrupted, wherein R ^{13 is} hydrogen, aryl, alkoxy, hydroxyalkyl, alkyl or interrupted by oxygen, alkoxylene, arylene, carbonyl, carboxylic acid ester, carbonamido or sulfone Alkyl; R ² is hydrogen, aryl, substituted by hydroxy, alkoxy, hydroxy (Ci-C ₄₀₎ alkyl, (Ci-C ₄₀₎ alkyl, aryl, (C ₂ -C ₄₀₎ -alkylene, halogen, Carbonsäureester, carboxamido or cyano, substituted aryl, (C 1 -C ₆ ) -alkyl, by hydroxy,

Alkoxy, hydroxy (C _r C ₄ o) alkyl, (C _r C ₄ o) alkyl, aryl, (C ₂ -C ₄₀ ) alkylene, halogen, carboxylic acid ester, carbonamido or cyano substituted (Cr C ₆ o) -Alkyl or by oxygen, alkoxylene, arylene, carbonyl, carboxylic acid ester, carbonamido, sulfone or NR ¹⁴ interrupted (Cr C ₆ o) alkyl, wherein R ^{14 is} hydrogen, aryl, alkoxy, hydroxyalkyl,

Alkyl, or alkyl interrupted by oxygen, alkoxylene, arylene, carbonyl, carboxylic acid ester, carbonamido or sulfone; R ³ and R ⁴ are independently hydrogen, aryl, substituted by hydroxy, alkoxy, hydroxy- (CrC ₄₀₎ alkyl, (C _r C o ₄₎ alkyl, aryl, (C ₂ -C ₄₀₎ -alkylene, halogen, Carbonsäureester , Carbonamido or cyano-substituted aryl, (CrC ₆₀ ) -

Alkyl substituted by hydroxy, alkoxy, hydroxy (CrC ₄₀ ) alkyl, (CrC ₄₀ ) alkyl, aryl, (C ₂ -C ₄₀ ) alkylene, halogen, carboxylic acid ester, carbonamido or cyano substituted (CrC ₆ o) alkyl or is interrupted by oxygen, alkoxylene, arylene, carbonyl, carboxylic acid ester, carbonamido, sulfone or NR ¹⁵ (CrC ₆ o) -alkyl, where R ^{15 is} hydrogen, aryl,

Alkoxy, hydroxyalkyl, alkyl or by oxygen, alkoxylene, arylene, carbonyl, carboxylic acid ester, carbonamido or sulfone interrupted alkyl; R ⁵ and R ⁶ are independently hydrogen, aryl, substituted by hydroxy, alkoxy, hydroxy- (CrC ₄₀₎ alkyl, (CrC ₄₀₎ alkyl, aryl, (C ₂ -C ₄₀₎ -alkylene, halogen,

Carbonsäureester, carboxamido or cyano substituted aryl, (CrC ₆₀₎ - alkyl, by hydroxy, alkoxy, hydroxy- (CrC ₄₀₎ alkyl, (CrC ₄₀₎ alkyl, aryl, (C ₂ -C ₄ o) -alkylene, halogen , Carboxylic acid ester, carbonamido or cyano-substituted (C 1 -C ₆ ) -alkyl or by oxygen, alkoxylene, arylene, Carbonyl, carboxylic acid ester, carbonamido, sulfone or NR ¹⁶ interrupted (CrC ₆ o) alkyl, wherein R ^{16 is} hydrogen, aryl, alkoxy, hydroxyalkyl, alkyl or by oxygen, alkoxylene, arylene, carbonyl, carboxylic acid ester, carbonamido or sulfone interrupted alkyl stands;

R ^{7 is} hydrogen or (C 1 -C ₄ ) alkyl; R ^{8 is} cyano, carbamoyl or sulfomethyl; R ⁹ to R ¹² are independently hydrogen, aryl, substituted by hydroxy, alkoxy, hydroxy (Ci-C ₄₀₎ alkyl, (CrC ₄₀₎ alkyl, aryl, (C ₂ -C ₄₀₎ -alkylene, halogen, Carbonsäureester, Carbonamido or cyano substituted aryl, hydroxy,

Alkoxy, (C ₂ -C _4O ) alkylene, halogen, carboxylic acid esters, carbonamido, cyano, (Ci-C ₆₀ ) alkyl, by hydroxy, alkoxy, hydroxy (C _r C ₄ o) alkyl, (C _r C ₄ o) -alkyl, aryl, (C ₂ -C ₄₀ ) -alkylene, halogen, carboxylic acid ester, carbonamido or cyano-substituted (C ₁ -C ₆ o) -alkyl or by oxygen, alkoxylene, arylene, carbonyl,

Carboxylic acid ester, carbonamido, sulfone or NR ¹⁷ interrupted (CrC ₆ o) alkyl, wherein R ^{17 is} hydrogen, aryl, alkoxy, hydroxyalkyl, alkyl or by oxygen, alkoxylene, arylene, carbonyl, carboxylic acid ester, carbonamido or sulfone interrupted alkyl; or two of the radicals R ⁹ to R ¹² together with the carbon atoms to which they are attached form a ring by hydroxy, alkoxy, hydroxy (Cr _C40) alkyl, (C _r C o ₄₎ -alkyl, Aryl, (C ₂ -C ₄₀ ) -alkylene, halogen, carboxylic acid esters, carbonamido or cyano may be substituted; and r is 0 or 1 wherein at least one of R ² to R ¹⁷ each contains at least one hydroxy group.

In preferred dyes of the general formula (1), R ^{1 is} preferably hydroxy (C ¹ -C ₄ ) -alkyl or hydroxy- (C ¹ -C ₄ ) -alkoxy- (C 1 -C ₄ ) -alkyl; R ² is hydrogen, (C _r _C4) alkyl, hydroxy (C _r _C4) alkyl or hydroxy (Ci-C ₄₎ alkoxy- (C _r C ₄₎ alkyl; R ³ and R ^{4 are} hydrogen; R ⁵ and R ⁶ independently of one another are hydrogen, (C 1 -C ₄ ) -alkyl, hydroxy- (C 1 -C ₄ ) -alkyl or hydroxy- (C 1 -C ₄ ) -alkoxy- (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) - alkoxy (C _r C ₄₎ alkyl, phenyl or (CrC ₄₎ alkyl or (CrC ₄₎ alkoxy substituted phenyl; R ^{7 is} (C _r C ₄ ) alkyl; R ⁸ cyano; and

R ⁹ to R ^{12 are} independently hydrogen, (C 1 -C ₄ ) -alkyl or (C 1 -C ₄ ) -alkoxy; and r is 0 or 1.

(C 1 -C ₄ ) -Alkyl groups may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl. The same applies to (C 1 -C ₄ ) -alkoxy groups.

Preference is further given to those dyes of the general formula (1) in which R ³ or R ^{4 is} hydrogen or at least one of the substituents R ⁵ or R ⁶ independently of one another carries a hydroxyl group.

Dyes of the general formula (1) according to the invention in which r is 0 have the general formula (1a)

wherein R ¹ to R ¹² are defined as indicated above. Compounds of the general formula (1a) are preferred and particularly preferred, provided that R ¹ to R ^{12 have} the meanings described above as being preferred.

Dyes of the general formula (1) according to the invention in which r is 1 have the general formula (1b)

wherein R> 1 u b: is ~ D R 12 as defined above.

Particularly preferred dyes according to the invention correspond to the general formula (1c)

wherein

R ^{1 is} hydroxyethyl, hydroxypropyl or hydroxyethoxyethyl, R ^{2 is} methyl, ethyl, hydroxyethyl, hydroxypropyl or hydroxyethoxyethyl,

R ⁵ and R ^{6 are} independently hydrogen, (C 1 -C ₄ ) alkyl, hydroxyethyl, hydroxypropyl, hydroxy (C 1 -C ₄ ) alkoxyethyl, ethoxy (C 1 -C ₄ ) alkyl, methoxy (C 1 -C ₄ ) alkyl, phenyl, methylphenyl or methoxyphenyl; and R ⁹ and R ^{10 are} independently hydrogen, methyl or methoxy.

The compounds of the general formula (1) according to the invention can be obtained, for example, by reacting a compound of the general formula (D1) wherein R ¹ , R ² , R ⁹ to R ¹² and r are as defined above, diazotized and to a compound of general formula (K1)

wherein R ³ to R ⁸ are defined as defined above, is coupled. Diazotization and coupling are generally carried out by methods known to those skilled in the art. Thus, for example, the diazotization is carried out with sodium nitrite in an acidic medium, while the coupling is carried out, for example, at -5 to 80 ^° C., preferably at 0 to 40 ^° C. and pH values of <0 to 10, preferably at pH values of 0 to 5, he follows.

The compounds of the general formula (D1) can be obtained by reacting a [2- (aminoarylsulfonyl) ethyl] sulfuric acid monoester of the general formula (A1)

or an alkali salt thereof, wherein r and R ⁹ to R ^{12 have} the abovementioned meaning with an amine of the general formula HNR ¹ R ² , wherein R ¹ and R ^{2 have} the meaning given above, is reacted.

This reaction is preferably carried out in water at preferably 25 to 95 ⁰ C, in particular at 35 to 60 ⁰ C, and at a pH of preferably 9 to 11, 5, in particular from 10 to 11. The compounds of the general formula (K1) can be prepared in known manner from dichloropyridines of the general formula (C1)

wherein R ⁷ and R ^{8 are} as defined above and amines of the formulas HNR ³ R ⁵ and HNR ⁴ R ⁶ , wherein R ³ to R ⁶ are defined as indicated above, are prepared. Optionally, further substitutions can be carried out on the radicals R ³ to R ⁸ , such as, for example, saponifications, esterifications, etherifications, amidation, alkylations and halogenations, as described, for example, in DE 3025904.

In a further process for the preparation of the compounds of the general formula (1) according to the invention, a compound of the general formula (ZP1)

wherein R ³ to R ¹² , and r are as defined above, with an amine of the formula HNR ¹ R ² , wherein R ¹ and R ² are defined as defined above, reacted.

The compounds of the general formula (ZP1) can be obtained by diazotization of a compound of the general formula (A1) and coupling to a compound of the general formula (K1) by methods known per se.

The sulfuric acid ester group HO ₃ SOCH ₂ CH ₂ SO ₂ - may, if desired, be present both in the compound of general formula (A1) and in the compound of general formula (ZP1) before its reaction with the amine of general formula HNR ¹ R ² by the addition of alkali in the vinyl form H ₂ C = CHSO ₂ - transferred. Examples of compounds of general formula (D1) are listed below.

-6

D1-11 2

D 1-20 D1-21 Examples of compounds of the general formula (K1) are listed below.

H _{K1 -1}

K1-5 K1-6

K1-15 -16 _8th

As a rule, the compounds of the general formula (K1) are in the form of mixtures, for example the compound of the formula K1-2a in mixture with the compound of the formula K1-2b. When using such mixtures in the process according to the invention, corresponding mixtures of compounds of the general formula (1) are formed.

Furthermore, the dyes of the general formula (1) or mixtures thereof according to the invention may contain synthesis-related by-products, for example hydrolyzates. Such hydrolyzates may be formed, for example, when the sulfuric acid half-ester group in the compound of the general formula (A1) is hydrolyzed or the vinyl compound which can be obtained from the compound of the general formula (A1) attaches water, or when the dyes of the general formula (1) Replace amine of general formula HNR ¹ R ² with water. Furthermore, hydrolyzates are also understood to mean products which, due to the hydrolysis or saponification of further functional groups, such as, for example, As nitrile, acid amide or ester groups can arise.

The present invention accordingly also dye mixtures containing more than one dye of the general formula (1). The dyes and dye mixtures according to the invention can be obtained as solids or liquids or solutions.

They can accordingly be isolated by suction and drying, spray drying, evaporation or extraction and evaporation.

The dyes and dye mixtures according to the invention can be used directly for the polymer dyeing or they are subjected to finishing. Finishing can be done from a single dye or a mixture of several dyes as well as blends with other classes of dyes, e.g. Pigments or solvent dyes, optionally with the aid of auxiliaries, such as. As surface modifiers, dispersants by dispersing, suspending or dissolving in a liquid or solid carrier material and optionally adjusting to a desired color intensity and a desired hue and optionally drying the preparation thus obtained. In the latter case dedusting can be added in addition. If the dye is dispersed or suspended, comminution of the dye particles by milling, e.g. done in a bead mill.

The invention further relates to the use of the dyes and dye mixtures according to the invention for the dyeing of polymers. It can be proceeded so that the dyes of the invention and

Dye mixtures of the reaction mixture are dosed during the polymerization or admixed to one of the starting materials before the polymerization. The dyes and dye mixtures according to the invention are preferably used for dyeing polyurethane by either adding the compounds according to the invention during the polymerization of diol or polyol and isocyanate or adding them to one of the starting materials before the polymerization. For example, the dye of the general formula (1) of the present invention may be blended with a polyether polyol or a polyester polyol, and this preparation may then be used for polymerization with a diisocyanate.

In the polymerization, the abovementioned stabilizers, activators or catalysts are usually used.

The dyes and dye mixtures according to the invention are particularly preferably used for dyeing polyurethane foam. The Production of polyurethane foam is carried out according to the principle described above for polyurethane, wherein the foam is produced by the addition of propellant gas or by the addition of water to the diol or polyol component, which leads to the formation of carbon dioxide as a propellant gas. It can be so using the dyes of the invention and

Dye mixtures produce colored polyurethane foams, which have no disturbances of the foam structure and good fastness properties and are also the subject of the invention.

The following examples serve to illustrate the invention without being limited to these examples. The parts are by weight, the percentages are by weight unless otherwise stated. Parts by weight refer to parts by volume such as kilograms to liters.

example 1

To a solution which was prepared from 281 parts of parabase ester and 1000 parts of water and was adjusted to pH 5 with 55 parts of soda, are added 75 parts of 2-methylamino-ethanol, heated to 40 ⁰ C, with sodium hydroxide solution pH value of 10 - 11, stirred at 40 ⁰ C and keeps the pH with sodium hydroxide until complete conversion to the target product. The complete conversion to the target product is determined by chromatography. The reaction time is about 4 h. It is then acidified with 250 parts of 31% hydrochloric acid, so that the pH drops to less than 1. There are 2342 parts of a solution containing the amine (D1-1) or its protonated form. The (D1-1) contained in 234.2 parts of the solution thus obtained is with

Sodium nitrite solution diazotized in the usual manner at 0 - 5 ⁰ C and added to half of the resulting reaction mixture 11.6 parts of the coupler (K1-1). Within 30 minutes, the pH is adjusted to 2.5 with 57 parts of 15% sodium carbonate solution and stirred until complete reactivation of the educts at this pH, wherein the temperature of the reaction mixture rises to room temperature. The product thus obtained is filtered off with suction, the resulting presscake is stirred in water, the suspension adjusted to pH 7-8, filtered off with suction, the presscake with water washed salt-free, dried at 50 ⁰ C in a vacuum and ground. 24.3 parts of the yellow dye of the formula (1-1) are obtained.

Example 2

Analogously to Example 1 is obtained from 281 parts of parabase ester and 105 parts of 2- (2-hydroxy-ethylamino) ethanol, the amine (D1-2), dissolved in 2515 parts of solution. The amine (D1-2) contained in 251, 1 parts of the solution thus obtained with sodium nitrite solution in the usual manner at 0 - diazotized 5 ⁰ C and added to the half of the reaction mixture obtained 11.6 parts of the coupler (K1-1). Within 30 minutes, the pH is adjusted to 2.5 with 15% sodium carbonate solution and stirred until complete reactivation of the educts at this pH, wherein the temperature of the reaction mixture rises to room temperature. The suspension thus obtained is adjusted to pH 7 to 8, filtered off with suction, the presscake is washed free of salt with water, dried at 50 ^° C. in vacuo and ground. This gives 25.6 parts of the yellow dye of formula (1-2).

Example 3 Analogously to Example 1, 56 parts of parabase ester and 27 parts of 1- (2-hydroxy-propylamino) -propan-2-ol are used to obtain the amine (D1-3) as an acidic solution with sodium nitrite solution in the usual manner at 0 - 5 ⁰ C diazotized and one-fourth of the resulting reaction mixture 11.8 parts of the coupler K1-1 (2,6-bis (2-hydroxy-ethylamino) -4-methyl-nicotinonitrile) is added , Within 90 minutes, the pH is adjusted to 2.5 with 15% sodium carbonate solution and stirred until complete reactivation of the reactants at this pH, wherein the temperature of the reaction mixture rises to room temperature. The suspension thus obtained is adjusted to pH 7 to 8, filtered off with suction, the presscake is washed free of salt with water, dried at 50 ^° C. in vacuo and ground. This gives 27 parts of the yellow dye of formula (1-3) as a mixture of stereoisomers.

H ₍₁ _ ₃₎

Example 4

The amines (D1-4), (D1-5) and (D1-6) are prepared analogously to the amines D1-1 to D1-3 and dissolved acidic. A mixture of 116 parts of the amine D1-4, 159 parts of D1-5 and 166 parts of D1-6 is acidified as described above and diazotized in the usual manner at 0 - 5 ⁰ C. To the resulting solution of diazonium salts is added a mixture of 78.8 parts of coupler K1-2 (consisting of the isomer mixture of 2-amino-6- [2- (2-hydroxy-ethoxy) ethylamino] -4-methyl nicotinonitrile and 6-amino-2- [2- (2-hydroxy-ethoxy) ethylamino] -4-methyl-nicotinonitrile) and 176 parts of the coupler K1-3 (consisting of the mixture of isomers of 2-amino-6- [ 2- (4-hydroxybutoxy) ethylamino] -4-methyl nicotinonitrile and 6-amino-2- [2- (4-hydroxybutoxy) ethylamino] -4-methyl nicotinonitrile). The reaction mixture is stirred for 8 h, warmed to 40 ⁰ C, stirred for a further 3 h, cooled to room temperature, adjusted to a pH of 8.5 with sodium hydroxide solution and extracted with chloroform. The chloroform phase is washed with water, with

Dried sodium sulfate, filtered and the chloroform evaporated in vacuo. The oily residue contains the dye mixture 1-4.

H H H

, ^

HN ^ * = HO 'OH or HO ^s -' or HO '

_/ ^ OH or ^{^} OH

R ³ = ^{^} O (1-4)

Example 5

The amine (D1-4) is prepared and diazotized in the usual way. To the diazonium salt solution obtained from 35 parts of the amine (D1-4) were added 31 parts of the coupler mixture (K1-4) previously dissolved in hydrochloric acid. The reaction mixture is stirred until complete reactivation of the reactants, the temperature being allowed to rise to room temperature. The pH of the reaction mixture is adjusted to 8.5 with sodium hydroxide solution, the dye is filtered off with suction, washed free of salt with water, dried at 50 ^° C. in vacuo and ground. The resulting dye mixture corresponds to the formulas (1-5).

(1-5) Example 6

Analogously to Examples 1-5, the dye mixture (1-6) is obtained from the amine (D1-6) and the coupler (K1-4).

Example 7

The dye mixture 1-7 is obtained analogously to Example 4 or Example 5 using the solution of diazonium salts described in Example 3 and reaction of the diazonium salts with the coupler (K1-4).

H H H

/ R '

HN _ HO 'OH or HO or HO'

(1-7)

Example 8

20 parts of the dye mixture (1-5) from Example 5 are suspended in 80 parts Ultramoll® and then ground in a bead mill (Sussmeyer SME-Mk II with 273 parts 0.4-0.7 mm ZrO2 beads). The resulting dye dispersion is heated to 60 ^° C. and centrifuged off from the beads. 100 parts of the polyol component Elastopan S 7521/102 Elastogran GmbH are submitted. To do this, give part of the color paste described above. It is stirred vigorously for 20-30 seconds using a dissolver disc. Then 60 parts of the diisocyanate IsoMMDl 92220 Elastogran GmbH are added quickly and stirred vigorously for 7 seconds by means of the dissolver disk. Then, it is poured into a vessel for forming the foam, whereby paper or cardboard containers are suitable. After about 5 minutes, the components have reacted and after a further 10 minutes, the foam is cured. Allow to cool to room temperature. 20 minutes after cooling, the foam can be sawn to assess the color. It is obtained a brilliant, reddish orange foam having good fastness to perchlorethylene.

Example 9 0.17 parts of the dye mixture corresponding to the formulas (1-5) from Example 5 are dissolved in one part of N-methylpyrrolidone (NMP).

100 parts of the polyol component Elastopan S 7521/102 Elastogran GmbH are submitted. This is done by adding part of the dye-NMP solution described above. It is stirred vigorously for 20-30 seconds by means of a dissolver disc. Then 60 parts of the diisocyanate IsoMMDl 92220 Elastogran GmbH are added quickly and stirred vigorously for 7 seconds by means of the dissolver disk. Then, it is poured into a vessel for forming the foam, whereby paper or cardboard containers are suitable. After about 5 minutes, the components have reacted and after a further 10 minutes, the foam is cured. Allow to cool to room temperature. 20 minutes after cooling, the foam can be sawn to assess the color. It is obtained a brilliant, reddish orange foam having good fastness to perchlorethylene.

Example 10

Using Example 8, using 0.2 parts of the dye mixture (1-6) of Example 6 gives a golden yellow foam having good fastness to perchlorethylene. Example 11

70 parts of the dye mixture (1-4) from Example 4 are dissolved in 70 parts Ultramoll ^®. By adding 0.3 part of this Ultramoll dye solution to the polyol component, polyurethane foam is prepared as described above. It is obtained a golden yellow foam, which has good fastness to perchlorethylene.

Analogously to the procedures described in the preceding examples, it is also possible to obtain the dyes or dye mixtures of Examples 12 to 31 below.

Example 12

Example 13

Example 14

Example 15

Example 16

Example 17

Example 18

Example 19

Example 20

Example 21

Example 22

Example 23

Example 24

Example 25

Example 26

Example 27

Example 28

Example 29

Example 30

Example 31

Claims

claims

1. Dye of the general formula (1),

wherein

R ¹ is substituted by at least one hydroxy aryl which additionally also be substituted by alkoxy, hydroxy (Ci-C ₄₀₎ alkyl, (Ci-C ₄₀₎ alkyl, aryl, (C ₂ -C ₄₀₎ - alkylene, halogen, Carbonsäureester , Carbonamido or cyano may be substituted by at least one hydroxy-substituted (C 1 -C ₆₀ ) -alkyl, which may additionally be substituted by alkoxy, hydroxy (C 1 -C ₄₀ ) -alkyl, (C 1 -C ₄₀ ) -

Alkyl, aryl, (C ₂ -C ₄₀ ) -alkylene, halogen, carboxylic acid esters, carbonamido or cyano substituted or may be interrupted by oxygen, alkoxylene, arylene, carbonyl, carboxylic acid ester, carbonamido, sulfone or NR ¹³ , where R ^{13 is} Hydrogen, aryl, alkoxy, hydroxyalkyl, alkyl or by oxygen, alkoxylene, arylene, carbonyl, carboxylic acid ester,

Carbonamido or sulfone is interrupted alkyl; R ² is hydrogen, aryl, substituted by hydroxy, alkoxy, hydroxy (Ci-C ₄₀₎ alkyl, (CrC ₄₀₎ alkyl, aryl, (C ₂ -C ₄₀₎ -alkylene, halogen, Carbonsäureester, carboxamido or cyano substituted aryl , (C ₁ -C ₆₀ ) -alkyl, by hydroxy, alkoxy, hydroxy (C _r C ₄₀ ) -alkyl, (C _r C ₄₀ ) -alkyl, aryl, (C ₂ -C ₄₀ ) -alkylene,

Halogen, carboxylic acid ester, carbonamido or cyano substituted (Cr C ₆₀ ) alkyl or by oxygen, alkoxylene, arylene, carbonyl, carboxylic acid ester, carbonamido, sulfone or NR ¹⁴ interrupted (Cr C ₆₀ ) alkyl, wherein R ^{14 is} hydrogen, aryl , Alkoxy, hydroxyalkyl, alkyl or by oxygen, alkoxylene, arylene, carbonyl, carboxylic acid ester,

Carbonamido or sulfone is interrupted alkyl; R ³ and R ⁴ are independently hydrogen, aryl, substituted by hydroxy, alkoxy, hydroxy- (CrC ₄₀₎ alkyl, (C _r C ₄₀₎ alkyl, aryl, (C ₂ -C ₄₀₎ -alkylene, halogen, Carboxylic acid ester, carbonamido or cyano-substituted aryl, (Ci-C ₆₀ ) - alkyl, by hydroxy, alkoxy, hydroxy (Ci-C ₄₀ ) alkyl, (Ci-C ₄₀ ) alkyl, aryl, (C ₂ -C ₄ o) -alkylene, halogen, carboxylic acid ester, carbonamido or cyano substituted (CrC ₆ o) -alkyl or by oxygen, alkoxylene, arylene, carbonyl, carboxylic acid ester, carbonamido, sulfone or NR ¹⁵ interrupted (CrC ₆ o) alkyl, wherein R ^{15 represents} hydrogen, aryl, alkoxy, hydroxyalkyl, alkyl or alkyl interrupted by oxygen, alkoxylene, arylene, carbonyl, carboxylic acid ester, carbonamido or sulphone; R ⁵ and R ^{6 are} independently hydrogen, aryl, by hydroxy, alkoxy, hydroxy (Ci-C ₄₀ ) alkyl, (C _r C ₄ o) alkyl, aryl, (C ₂ -C ₄₀ ) alkylene, halogen , Carbonsäureester, carboxamido and cyano substituted aryl, (CrC ₆ o) - alkyl, by hydroxy, alkoxy, hydroxy- (CrC ₄₀₎ -alkyl, (-C ₄₀₎ alkyl, aryl, (C ₂ -C ₄₀₎ alkylene, Halogen, carboxylic acid ester, carbonamido or cyano-substituted (C 1 -C ₆ ) -alkyl or by oxygen, alkoxylene, arylene,

Carbonyl, carboxylic acid ester, carbonamido, sulfone or NR ¹⁶ interrupted (CrC ₆ o) alkyl, wherein R ^{16 is} hydrogen, aryl, alkoxy, hydroxyalkyl, alkyl or by oxygen, alkoxylene, arylene, carbonyl, carboxylic acid ester, carbonamido or sulfone interrupted alkyl stands;

R ^{7 is} hydrogen or (C _r C ₄ ) alkyl; R ^{8 is} cyano, carbamoyl or sulfomethyl; R ⁹ to R ¹² are independently hydrogen, aryl, substituted by hydroxy, alkoxy, hydroxy (Ci -C ₄₀₎ -AI alkyl, (C _r C o ₄₎ alkyl, aryl, (C ₂ -C ₄₀₎ alkylene, Halogen, carboxylic acid ester, carbonamido or cyano substituted aryl, hydroxy,

Alkoxy, (C ₂ -C _4O) -AI kylen, halogen, Carbonsäureester, carboxamido, cyano, (C iC ₆ o) -AI alkyl, by hydroxy, alkoxy, hydroxy- (CrC ₄₀₎ alkyl, (CrC ₄₀₎ - Alkyl, aryl, (C ₂ -C ₄ 0) -alkylene, halogen, carboxylic acid ester, carbonamido or cyano-substituted (C ₁ -C ₆ o) -alkyl or by oxygen, alkoxylene, arylene, carbonyl,

Carboxylic acid ester, carbonamido, sulfone or NR ¹⁷ interrupted (C iC ₆ o) -AI kyl, wherein R ^{17 is} hydrogen, aryl, alkoxy, hydroxyalkyl, alkyl or by oxygen, alkoxylene, arylene, carbonyl, Carboxylic acid ester, carbonamido or sulfone interrupted alkyl; or two of R ⁹ to R ¹² together with the carbon atoms to which they are attached form a ring represented by hydroxy, alkoxy, hydroxy (C 1 -C ₄₀ ) alkyl, (C 1 -C ₄₀ ) alkyl, aryl , (C ₂ -C ₄₀ ) -alkylene, halogen,

Carboxylic acid ester, carbonamido or cyano may be substituted; and r is 0 or 1 wherein at least one of R ² to R ¹⁷ each contains at least one hydroxy group.

2. A dye according to claim 1, characterized in that in the general formula (1)

R ¹ hydroxy (CrC ₄₎ alkyl or hydroxy (Ci-C ₄₎ alkoxy- (C _r C ₄₎ alkyl; R ^{2 is} hydrogen, (C _r C ₄ ) alkyl, hydroxy (C _r C ₄ ) alkyl or

Hyd roxy- (Ci -C ₄₎ -AI alkoxy- (C ₁ -C ₄₎ -Alky I;

R ³ and R ^{4 are} hydrogen;

R ⁵ and R ⁶ independently of one another are hydrogen, (C 1 -C ₄ ) -alkyl, hydroxy- (C 1 -C ₄ ) -alkyl or hydroxy- (C 1 -C ₄ ) -alkoxy- (C 1 -C ₄ ) -alkyl, (C 1 -C ₄ ) - alkoxy (C _r C ₄₎ alkyl, phenyl or (CrC ₄₎ alkyl or (CrC ₄₎ alkoxy substituted phenyl;

R ^{7 is} (C _r C ₄ ) alkyl;

R ⁸ cyano; and

3. Dye according to claim 1 and / or 2, characterized in that it corresponds to the general formula (1a) (1a) wherein R ¹ to R ^{12 are} as defined in claim 1 or claim 2.

4. Dye according to one or more of claims 1 to 3, characterized in that it has the general formula (1c)

corresponds to, in which

R ⁵ and R ⁶ are independently hydrogen, (CrC ₄₎ alkyl, hydroxyethyl, hydroxypropyl, hydroxy (CrC ₄₎ alkoxyethyl, ethoxy (CrC ₄₎ alkyl, methoxy (Ci-C ₄₎ alkyl, phenyl , Methylphenyl or methoxyphenyl; and R ⁹ and R ^{10 are} independently hydrogen, methyl or methoxy.

5. A process for preparing a dye of the general formula (1) according to one or more of claims 1 to 4, characterized in that a compound of the general formula (D1) wherein R ¹ , R ² , R ⁹ to R ¹² and r are as defined in claim 1, diazotized and to a compound of general formula (K1)

wherein R ³ to R ⁸ are defined as defined above, is coupled.

6. A process for preparing a dye of the general formula (1) according to one or more of claims 1 to 4, characterized in that a compound of the general formula (ZP1)

wherein R ³ to R ¹² , and r are as defined in claim 1, with an amine of the formula HNR ¹ R ² , wherein R ¹ and R ² are defined as defined in claim 1, is reacted.

7. dye mixture, characterized in that it contains more than one dye of the general formula (1) according to one or more of claims 1 to 4.

8. Use of a dye of the general formula (1) according to one or more of claims 1 to 4 or a dye mixture according to claim 7 for dyeing polymers.

9. Use according to claim 8, characterized in that the polymer is polyurethane.

10. Use according to claim 8 and / or 9, characterized in that the polymer is polyurethane foam.