Metal free acid dyes, process for the production thereof and their use

Abstract

The present invention relates to dyes of formula (1) ##STR00001##
a process for preparing them and their use for dyeing and printing hydroxyl- and/or carboxamido-containing materials.

Claims

1. A dye of formula (1) ##STR00332## wherein independent from each other G is a rest of formula (i) or (ii) ##STR00333## R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is hydrogen, (C.sub.1-C.sub.12)-alkyl, (C.sub.2-C.sub.6)-alkenyl, (C.sub.3-C.sub.8)-cycloalkyl or aryl-(C.sub.1-C.sub.12)-alkyl, with the alkyl chain being linear or branched, and optionally being interrupted by one or more heteroatoms and/or substituted by one or more substituents selected from the group consisting of hydroxy, carboxy, SO.sub.3M, halogen, cyano, nitro, acyl, trifluoromethyl, acyloxy, aryloyloxy and carbamoyl, R.sup.5 and R.sup.6 is hydrogen, (C.sub.1-C.sub.12)-alkyl, substituted (C.sub.1-C.sub.12)-alkyl with the substituents being selected from the group consisting of hydroxy, carboxy, SO.sub.3M, halogen, cyano, nitro, acyl, trifluoromethyl, acyloxy, aryloyloxy and carbamoyl, (C.sub.3-C.sub.8)-cycloalkyl, a group of formula (iii) ##STR00334## wherein R.sup.26 and R.sup.27 are identical or different and are hydrogen, (C.sub.1-C.sub.12)-alkyl, (C.sub.1-C.sub.12)-alkyl substituted by hydroxy, (C.sub.1-C.sub.12)-alkoxy, trifluoromethyl, cyano, nitro, halogen, NHCO(C.sub.1-C.sub.6)-alkyl, NHSO.sub.2(C.sub.1-C.sub.6)-alkyl, CONH.sub.2 or SO.sub.2NH.sub.2, R.sup.41 is hydrogen or (C.sub.1-C.sub.6)-alkyl, n is 0, 1 or 2, p is 0 or 1 to 6, or (C.sub.1-C.sub.12)-alkyl, whereby the alkyl chain can be interrupted by one or more heteroatoms, R.sup.7 and R.sup.8 are identical or different and are hydrogen, (C.sub.1-C.sub.6)-alkyl or phenyl, R.sup.9 and R.sup.10 are identical or different and are hydrogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkoxy, trifluoromethyl, hydroxy, cyano, nitro, halogen, NHCHO, NHCO(C.sub.1-C.sub.6)-alkyl, NHCOaryl, NHSO.sub.2(C.sub.1-C.sub.6)-alkyl or NHSO.sub.2aryl, D.sup.1 and D.sup.2 is a rest of a phenyl-, naphthyl- or heterocyclic-derivative, which comprises at least one group SO.sub.3M, wherein M is hydrogen, an alkali metal, ammonium, substituted or unsubstituted tetra(C.sub.1-C.sub.12)-alkyl ammonium or one equivalent of an alkali earth metal.

2. The dye according to claim 1, wherein independent from each other R.sup.1 to R.sup.4 are identical and are hydrogen, (C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.6)-alkyl substituted by hydroxyl or cyano, R.sup.5 and R.sup.6 are identical and are hydrogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkyl substituted by hydroxy, (C.sub.3-C.sub.8)-cycloalkyl or (C.sub.1-C.sub.6)-alkyl substituted by SO.sub.3M or a group of formula (iii) as defined in claim 1, wherein each R.sup.26 and R.sup.27 independent from each other is hydrogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkyl substituted by hydroxy, (C.sub.1-C.sub.6)-alkoxy, trifluoromethyl, hydroxy, cyano, halogen, n is 0 or 1, p is 0 or 1 to 4, R.sup.7 and R.sup.8 are identical and are hydrogen, methyl or ethyl and R.sup.9 and R.sup.10 are identical and are hydrogen, methyl, ethyl, halogen, trifluoromethyl, methoxy or ethoxy.

3. The dye according to claim 1, having formula (1a), (1a.sup.1), (1a.sup.2) or (1a.sup.3) ##STR00335## wherein R.sup.5a and R.sup.6a are hydrogen, (C.sub.1-C.sub.6)-alkyl, (C.sub.1-C.sub.6)-alkyl substituted by hydroxy, (C.sub.3-C.sub.8)-cycloalkyl or (C.sub.1-C.sub.6)-alkyl substituted by SO.sub.3M, R.sup.9a and R.sup.10a are identical and are hydrogen or methoxy, each of R.sup.26a, R.sup.27a, R.sup.26b and R.sup.27b is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, trifluoromethyl, cyano, nitro or halogen, R.sup.43a and R.sup.43b is hydrogen or (C.sub.1-C.sub.4) alkyl, s is 0 or 1 to 6 and D.sup.1 and D.sup.2 are as defined in claim 1.

4. The dye according to claim 1, in which independent from each other D.sup.1 and D.sup.2 is selected from the group consisting of groups of formula (I) to (XIV): ##STR00336## wherein R.sup.11 and R.sup.30 independent of each other is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, trifluoromethyl, cyano, nitro, NHC(O)R.sup.31, CONH.sub.2, S(O).sub.2R.sup.32 or halogen, R.sup.31 and R.sup.32 is hydrogen, (C.sub.1-C.sub.4)-alkyl or (C.sub.1-C.sub.4)-alkyl substituted by hydroxyl, M is hydrogen, an alkali metal, ammonium or one equivalent of an alkali earth metal, ##STR00337## wherein R.sup.12 is hydrogen or (C.sub.1-C.sub.4)-alkyl, n is 0 or 1 and M is defined as given above, ##STR00338## wherein R.sup.13 is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, cyano, nitro, CONH.sub.2 or halogen and M is defined as given above, ##STR00339## wherein R.sup.14 is hydrogen, cyano, CONH.sub.2, C(O)R.sup.33 or COOR.sup.34, R.sup.33 is hydrogen or (C.sub.1-C.sub.4)-alkyl, R.sup.34 is hydrogen or (C.sub.1-C.sub.4)-alkyl, R.sup.15 is hydrogen, CHO or a group of formula (a) or (c) ##STR00340## wherein R.sup.16, R.sup.35 and R.sup.36 independent of each other is hydrogen, halogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, SO.sub.3M or CONH.sub.2, m is 0 or 1 and M is defined as given above, ##STR00341## wherein M is defined as given above, ##STR00342## wherein R.sup.17 is SO.sub.3M, CHO, CHC(CN).sub.2, a group of formula (a) as defined above or a group of formula (b) or (d) ##STR00343## wherein R.sup.37, R.sup.38 and R.sup.39 independent of each other is hydrogen, halogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, SO.sub.3M or CONH.sub.2, R.sup.18 is SO.sub.3M, (C.sub.1-C.sub.4)-alkyl, sulfophenyl (C.sub.1-C.sub.4)-alkylamino, (C.sub.1-C.sub.12)-alkylamino, (C.sub.5-C.sub.6)-cycloalkylamino, morpholino or piperidino and M is defined as given above, ##STR00344## wherein R.sup.19 is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, nitro, NHC(O)R.sup.40, NHSO.sub.2R.sup.47 or halogen, R.sup.40 is hydrogen or (C.sub.1-C.sub.6) alkyl, R.sup.47 is (C.sub.1-C.sub.6)-alkyl, ##STR00345## wherein R.sup.20 is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, cyano, nitro, CONH.sub.2 or halogen, ##STR00346## wherein R.sup.21 is hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, halogen, cyano, nitro or CONH2 and E is sulphur or oxygen, ##STR00347## wherein R.sup.22 and R.sup.23 independent of each other is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, halogen, cyano or CONH.sub.2 and U is methylene or CO, ##STR00348## wherein R.sup.24 and R.sup.25 independent of each other is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, halogen, cyano, nitro, trifluoromethyl or CONH.sub.2, ##STR00349## wherein R.sup.44 and R.sup.45 independent of each other is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, halogen, cyano, nitro, trifluoromethyl, CONH.sub.2 or SO.sub.3M, ##STR00350## wherein R.sup.46 is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, halogen, cyano, nitro, trifluoromethyl, CONH.sub.2 or SO.sub.3M and ##STR00351## wherein R.sup.48 is hydrogen, (C.sub.1-C.sub.4)-alkyl, (C.sub.1-C.sub.4)-alkoxy, nitro, NHC(O)R.sup.49, NHSO.sub.2R.sup.50 or halogen, R.sup.49 is hydrogen or (C.sub.1-C.sub.6)-alkyl, R.sup.50 is (C.sub.1-C.sub.6)-alkyl; and M is defined as given above.

5. The dye according to claim 4, wherein D.sup.1 and D.sup.2 are identical.

6. A chemical composition comprising one or more dye(s) according to claim 1.

7. A chemical composition consisting of two or more dyes according to claim 1.

8. An aqueous solution for dying comprising one or more chemical compounds according to claim 1.

9. Process for the production of the dye according to claim 1, comprising a) diazotizating compounds of formulae (2) and (3)
D.sup.1-NH.sub.2(2)
D.sup.2-NH.sub.2(3), wherein D.sup.1 and D.sup.2 are defined as given in claim 1, b) reacting the products obtained in step a) with a compound of formula (4) ##STR00352## wherein R.sup.1 to R.sup.10 and G are defined as given in claim 1.

10. A process for dyeing or printing carboxamido- and/or hydroxyl-containing material, comprising contacting the carboxamido- and/or hydroxyl-containing material with the dye according to claim 1.

11. An ink for digital textile printing comprising the dye according to claim 1.

12. A process for dying a fiber or blend which comprises contacting the fiber or blend of fibers with the dye according to claim 1.

13. The process according to claim 12, wherein the fiber is selected from the group consisting of: synthetic fiber materials; nylon materials; nylon-6; nylon-6,6; aramid fibres; vegetable fibres; seed fibres; cotton; organic cotton; kapok; coir from coconut husk; bast fibers; flax; hemp; jute; kenaf; ramie; rattan; leaf fibres; sisal; henequen; banana; stalk fibres; bamboo; fibres from animals; wool; organic wool; silk; cashmere wool; alpaca fiber; mohair; Angora fibre; fur and leather materials; manufactured, regenerated and recycled fibres; cellulosic fibres; paper fibres; cellulosic regenerated fibres; viscose rayon fibres; acetate and triacetate fibers; Lyocell fibers and mixtures thereof.

14. A fiber or blends comprising one or more dye(s) according to claim 1 either in chemically and/or physically bound form.

15. The fiber or blends as claimed in claim 14, wherein the fiber is selected from the group consisting of: synthetic fiber materials; nylon materials; nylon-6; nylon-6,6; aramid fibres; vegetable fibres; seed fibres; cotton; organic cotton; kapok; coir from coconut husk; bast fibers; flax; hemp; jute; kenaf; ramie; rattan; leaf fibres; sisal; henequen; banana; stalk fibres; bamboo; fibres from animals; wool; organic wool; silk; cashmere wool; alpaca fiber; mohair; Angora fibre; fur and leather materials; manufactured, regenerated and recycled fibres; cellulosic fibres; paper fibres; cellulosic regenerated fibres; viscose rayon fibres; acetate and triacetate fibers; Lyocell fibers and mixtures thereof.

Description

EXAMPLE 1

(1) a) 63.22 parts of hydrochloric acid (30%) were transferred into a 250 ml round bottom flask equipped with mechanical stirrer, temperature controller and condenser. 50 parts of 3-(diethylamino)acetanilide (A) were added slowly. The reaction mixture was heated to 80 C. gradually within 1 hour. The reaction mixture was kept at 80 C. until the reaction was completed. The reaction mixture was cooled down and diluted with deionized water. After the pH was adjusted to slightly alkaline with 90 parts of 30% NaOH solution the reaction mixture was extracted with organic solvent. The organic layer was washed three times with 500 parts of deionised water and dried over anhydrous sodium sulfate. The organic layer was distilled to dryness. 35 parts of the product (B) as dark brown viscous oil were obtained. The analytic data are consistent with the assigned structure for product (B).

(2) ##STR00327##

(3) b) 109 parts of acetonitrile and 109 parts of deionised water were transferred to a 1 l round bottom flask equipped with mechanical stirrer, temperature sensor and pH probe. The reaction mixture was cooled to 0 to 2 C. using an ice bath. 19.81 parts of cyanuric chloride (C) were then gradually added to the reaction mixture. 35.28 parts of 3-N,N-Diethylamino aniline (B) were dissolved in 50 parts of acetonitrile and added dropwise to the reaction mixture. The pH was maintained at values of 4 to 4.5 using sodium hydroxide solution and the temperature was maintained below 2 C. After 3 hours, the temperature was raised to room temperature and the pH was maintained at 5 to 5.5 using sodium hydroxide solution. The reaction mixture was stirred until completion. The reaction mixture was diluted with deionised water and the resulting solid was filtered and washed neutral. Upon drying 47.26 parts of solid (H) were obtained. The analytic data are consistent with the assigned structure for product (H).

(4) ##STR00328##

(5) c) A reaction mixture comprising 10 parts of intermediate (H), 50 parts of acetonitrile, 2.26 parts of sodium bicarbonate dissolved in 3 parts of water and 2.71 parts of 2-mercapto ethanol (I) was heated to 80 C. until completion. After cooling to room temperature, the reaction mixture was diluted with deionised water. The pH of the reaction mixture was adjusted to 6.5 to 7 using hydrochloric acid solution. The slurry was stirred overnight and then filtered and washed neutral with deionised water. Upon drying 10.94 parts of the product (J) as a dark grey solid were obtained. The analytic data are consistent with the assigned structure for product (J).

(6) ##STR00329##

(7) d) 8.16 parts of 3-amino-4-methyl phenylsulfanilic acid (K) were taken into 80 parts of deionised water. The pH of the mixture was adjusted to 6.3 when a clear solution was obtained. The solution was cooled down to 0 to 5 C. using an ice-salt mixture. 9.15 parts of 5N sodium nitrite solution were added dropwise into the reaction mixture, followed by fast addition of 15.07 parts of 37% HCl to the reaction mixture. The reaction mixture was stirred for 2.5 hours at 0 to 5 C. and the resulting diazonium salt was used for the following coupling step.

(8) ##STR00330##

(9) e) 10 parts of the coupler (J) and 0.36 parts of sulphamic acid were mixed with 50 ml of deionised water and 150 ml of acetonitrile. The pH of the resulting mixture was adjusted to pH 2.5 using 37% hydrochloric acid. The reaction mixture was cooled down to 0 to 5 C. using ice-salt mixture. The diazonium salt (L) was added dropwise to the coupler solution while maintaining the pH between 2.5 and 5.5 using sodium hydroxide solution. The reaction mixture was stirred for 3 hrs and the reaction was completed. After distillation under reduced pressure the pH was adjusted to 5 using hydrochloric acid. Upon addition of sodium chloride, the resulting slurry was filtered and washed neutral. Upon drying 18.22 parts of the acid dye (1-1) were obtained. The analytical data is consistent with the assigned structure for the dye (1-1).

(10) ##STR00331##

(11) Through analogy, all the inventive dyesand those in Table 1 in particularcan be obtained by processes similar to those described above in Example 1-1.

DYEING EXAMPLE 1

(12) 1 part of the dye, example 1-1 of this invention is dissolved in 2000 parts of water and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 6 parts of sodium acetate are added. The pH is then adjusted to 5 using acetic acid (80%). The dyebath is heated to 50 C. for 10 minutes and then entered with 100 parts of a woven polyamide-6 fabric. The temperature is raised to 98 C. over the course of 50 minutes and then dyeing is carried out at this temperature for 60 minutes. This is followed by cooling to 60 C. and removal of the dyed material. The polyamide-6 fabric is washed with hot and cold water, soaped and then spun dried. The scarlet dyeings obtained have very good light and wet fastness and also good levelness in the fibre.

DYEING EXAMPLE 2

(13) 1 part of the dye, example 1-1 of this invention is dissolved in 2000 parts of water and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 6 parts of sodium acetate are added. The pH is then adjusted to 5.5 using acetic acid (80%). The dyebath is heated to 50 C. for 10 minutes and then entered with 100 parts of a woven polyamide-6,6 fabric. The temperature is raised to 120 C. over the course of 50 minutes and then dyeing is carried out at this temperature for 60 minutes. This is followed by cooling to 60 C. and removal of the dyed material. The polyamide-6,6 fabric is washed with hot and cold water, soaped and then spun dried. The scarlet dyeings obtained have very good light and wet fastness and also good levelness in the fibre.

DYEING EXAMPLE 3

(14) 100 parts of polyamide-6 material are padded with a 1000 parts 50 C. liquor solution that consists of 40 parts of the dye, example 1-1, 100 parts of urea, 20 parts of a non ionic solubilizer based on butyldiglycol, 20 parts of acetic acid to adjust the pH to 4.0, 10 parts of levelling assistant (based on ethoxylated aminopropyl fatty acid amide) and 810 parts of water. The material is rolled up and placed into a steaming chamber at 85 to 98 C. for 3 to 6 hours. After fixation, the fabric is washed with hot and cold water, soaped and then spun dried. The scarlet dyeings obtained have very good light and wet fastness and also good levelness in the fibre.

DYEING EXAMPLE 4

(15) 1 part of the dye, example 1-1 of this invention is dissolved in 2000 parts of water and 5 parts of sodium sulphate, and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 5 parts of sodium acetate are added. The pH is then adjusted to 4.5 using acetic acid (80%). The dyebath is heated to 50 C. for 10 minutes and then entered with 100 parts of a woven wool fabric. The temperature is raised to 100 C. over the course of 50 minutes and then dyeing is carried out at this temperature for 60 minutes. This is followed by cooling to 90 C. and removal of the dyed material. The wool fabric is washed with hot and cold water, soaped and then spun and dried. The scarlet dyeings obtained have very good light and wet fastness and also good levelness in the fibre.

DYEING EXAMPLE 5

(16) 1 part of the dye, example 1-1 of this invention is dissolved in 1000 parts of water and 7.5 parts of sodium sulphate, and 1 part of a wetting agent (anionic) are added. 100 parts of bleached cotton knitted fabric are added to this solution. The dye bath is then heated up to 98 C. with a gradient of 2 C./min then dyeing is carried out at this temperature for 60 minutes. This is followed by cooling down to 80 C. At 80 C. the dyeing is continued for another 20 minutes. The dyed material is then removed and is washed with hot and cold water, soaped and then spun and dried. The scarlet dyeings obtained have very good light and wet fastness and also good levelness in the fibre.

DYEING EXAMPLE 6

(17) 3 parts of the dye, example 1-1 of this invention dissolved in 82 parts of deionized water are added into the dyebath with 15 parts of diethylene glycol at 60 C. On cooling, a scarlet printing ink is obtained. The scarlet printing ink can be used for ink jet printing on paper, polyamide or wool textiles.

DYEING EXAMPLE 7

(18) 4 parts of chemically bleached (pine wood) sulphite pulp is mixed up with 100 parts of 55 C. water. 1 part of the dye 1a.sup.161 of this invention is dissolved in 100 parts of hot water. 80 parts of this solution is given to the mixed-up pulp and mixed for 2 minutes. After that the mixture is sized with resin size in a conventional manner and mixed for another 2 minutes. 55 parts of this solution are then diluted with 2000 parts of cold water and the paper is produced out of this solution. The orange paper produced from the mixture has good wet fastnesses.