LAUK URS (DE)
PFISTER SIMON (CH)
NOWACK PATRIC (DE)
MURER KEVIN (CH)
DREIER ROMEO (CH)
ANDREOLI ANTON (CH)
SITKOWSKA KAJA DOROTA (CH)
| WO2012032512A2 | 2012-03-15 | |||
| WO2002044156A2 | 2002-06-06 |
| US3758270A | 1973-09-11 | |||
| US3758270A | 1973-09-11 | |||
| DE2612964A1 | 1976-10-07 | |||
| DE2643801A1 | 1977-04-14 | |||
| US1503984A | 1924-08-05 | |||
| US1947819A | 1934-02-20 | |||
| DE561425C | 1932-10-14 | |||
| CN101830766A | 2010-09-15 |
F. URSEANU ET AL., REVISTA DE CHIMIE, vol. 36, no. 6, 1985, pages 450 - 495
H. WOODBURN, J. OF THE AMERICAN CHEM. SOCIETY, vol. 72, 1950, pages 1361 - 1364
T. SONE, CHEMISTRY LETTERS, vol. 8, 1982, pages 1259 - 1262
| Claims 1. Azo dye of formula wherein Ri denotes hydrogen, halogen, nitro, cyano or Ci-C4alkoxy, and D denotes a radical of formula wherein X1 denotes one or more substituent(s) selected from hydrogen, halogen, Ci-Ce alkyl, trifluoro methyl, Ci-Ce alkoxy, cyano, nitro or COOQ3 and SO2Q3 wherein Q3 means Ci-Cealkyl which is unsubstituted or substituted by cyano, halogen, carboxy, hydroxy or phenoxy, and wherein Y1 denotes one or more substituent(s) selected from hydrogen, halogen, Ci-Ce alkyl, trifluoro methyl, Ci-Ce alkoxy, cyano, nitro, -CONH2, or COOQ3 and SO2Q3 wherein Q3 means Ci-Cealkyl which is unsubstituted or substituted by cyano, halogen, carboxy, hydroxy or phenoxy or wherein D denotes a radical of formula wherein X2 denotes one or more substituent(s) selected from hydrogen, halogen, Ci-Ce alkyl, trifluoro methyl, Ci-Ce alkoxy, cyano, nitro or COOQ3 and SO2Q3 wherein Q3 means Ci-Cealkyl which is unsubstituted or substituted by cyano, halogen, carboxy, hydroxy or phenoxy, and wherein Y2 denotes one or more substituent(s) selected from hydrogen, halogen, Ci-Ce alkyl, trifluoro methyl, Ci-Ce alkoxy, cyano, nitro, -CONH2 or COOQ3 and SO2Q3 wherein Q3 means Ci-Cealkyl which is unsubstituted or substituted by cyano, halogen, carboxy, hydroxy or phenoxy or wherein D denotes a radical of formula wherein X3 denotes one or more substituent(s) selected from hydrogen, halogen, Ci-Ce alkyl, trifluoro methyl, Ci-Ce alkoxy, cyano, nitro or COOQ3 and SO2Q3 wherein Q3 means Ci-Cealkyl which is unsubstituted or substituted by cyano, halogen, carboxy, hydroxy or phenoxy, and wherein Y3 denotes one or more substituent(s) selected from hydrogen, halogen, Ci-Ce alkyl, trifluoro methyl, Ci-Ce alkoxy, cyano, nitro, -CONH2 or COOQ3 and SO2Q3 wherein Q3 means Ci-Cealkyl which is unsubstituted or substituted by cyano, halogen, carboxy, hydroxy or phenoxy. 2. Azo dye of formula (1) according to claim 1, wherein Ri is hydrogen, halogen or C1-C4 alkoxy, preferably hydrogen, bromine or methoxy. 3. Azo dye of formula (1) according to any of the preceding claims, wherein X1, X2 or X3 denotes one or more substituent(s) selected from hydrogen, halogen, preferably chlorine, nitro or Ci-Ce alkyl, preferably methyl. 4. Azo dye of formula (1) according to any of the preceding claims, wherein D denotes a radical of formula (2), wherein X1 denotes one or more substituent(s) selected from hydrogen, halogen, preferably chlorine, nitro or Ci-Ce alkyl, preferably methyl and Y1 is defined as above. 5. Azo dye of formula (1) according to any of the preceding claims, wherein D denotes a radical of formula (3), wherein X2 denoted one or more substituent(s) selected from hydrogen or halogen, preferably chlorine, and Y2 is defined as above. 6. Azo dye of formula (1) according to any of the preceding claims, wherein D denotes a radical of formula (4), wherein X3 denoted hydrogen, and Y3 is defined as above. 7. A process for the preparation of an azo dye of formula (1) according to any of claims 1 to 6, which comprises diazotizing an amine compound D-NH2 in accordance with a customary procedure, and then coupling the diazotized amine compound to a BON-acid (2-hydroxynaphthalene-3-carboxylic acid) coupling component of the formula (la), wherein D and Ri are as defined above. 8. Dye mixtures, wherein the dye of formula (1) according to any of claims 1 to 6 is used in admixture with at least one further dye selected from the group consisting of C.I. Disperse Red 050, C.I. Disperse Red 060, C.I. Disperse Red 072, C.I. Disperse Red 082, C.I. Disperse Red 86: 1, C.I. Disperse Red 167, C.I. Disperse Red 277, C.I. Disperse Red 279, C.I. Disperse Red 302, C.I. Disperse Red 302: 1, C.I. Disperse Red 342, C.I. Disperse Red 349, C.I. Disperse Red 356, C.I. Disperse Red 362, C.I. Disperse Red 376, C.I. Disperse Red 377, C.I. Disperse Red 378, C.I. Disperse Red 380, C.I. Disperse Red 383, C.I. Disperse Red 385 and/or the dye of formula 9. Use of a dye of formula (1) according to any of claims 1 to 6 or a dye mixture according to claim 8 in dyeing or printing semi-synthetic or synthetic hydrophobic fibre materials, and especially synthetic hydrophobic fibre materials, more especially textile polyester materials. 10. A semi-synthetic or synthetic hydrophobic fibre material, especially a textile polyester material, dyed or printed by the dye of formula (1) according to any of claims 1 to 6 or by the dye mixture according to claim 8. |
Description
The present invention relates new disperse azo dyes based on BON-acid (2-hy- droxynaphthalene-3-carboxylic acid) a process for the preparation of such azo dyes, a dye mixture comprising such azo dyes, the use of such azo dyes in dyeing or printing semi-synthetic or synthetic hydrophobic fibre materials and to a semisynthetic or synthetic hydrophobic fibre material dyed or printed by said azo dyes or said dye mixture.
Azo dyes based on BON-acid as the coupling component are known for many years. The dyes come into consideration for various dyeing applications. The salts of some BON-acid monoazo dyes, such as the copper or barium salts, are used as lake, for example, Pigment Red 64.
So far, BON-acid azo dyes are rarely described for the coloring of textile materials. Related technical literature dates back to the 1960ies and 1970ies. Textile applications using BON-acid azo dyes in the free acid form or as the alkaline- or earth alkaline metal salt are limited to the coloring of poly propylene fibers as described, for example, in US 3 758 270. However, these attempts turned out to be not very successful. Some azo dyes based on BON-acid are described for the dyeing of polyester fibers. However, in this case the BON-acid coupling component is used as the amide as described, for example, in DE 2 612 964 and DE 2 643 801. The documents are almost silent on the dyeing of polyester fibers using BON-acid azo dyes in the free acid form. In one instance, F. Urseanu et al. Revista de Chimie, 36 (6), 450-495 (1985) describe a single azo dye synthesized by coupling 4-aminobenzylaniline on BON-acid, which has a poor build up on polyester substances. Therefore, rendering it is unsuitable for practical applications.
It has now been surprisingly found that azo dyes produced by coupling phenoxy aniline derivatives on BON-acid can nevertheless be used in the free acid form for the dyeing or printing of polyester fiber, especially in exhaust dyeing processes affording an excellent build up. This is unexpected due to the ionic property and the water solubility of the BON-acid azo dyes, which disfavors a dye/hydrophobic fibers interaction and therefore the dyeability.
Accordingly, the present invention relates to the dyeing or printing of polyester containing fiber materials, in which an azo dye according to claim 1 is used.
In particular, the present invention relates to an azo dye of formula wherein
Ri denotes hydrogen, halogen, nitro, cyano or Ci-C4alkoxy, and
D denotes a radical of formula wherein X 1 denotes one or more substituent(s) selected from hydrogen, halogen, Ci-Ce alkyl, trifluoro methyl, Ci-Ce alkoxy, cyano, nitro or COOQ3 and SO2Q3 wherein Q 3 means Ci-Cealkyl which is unsubstituted or substituted by cyano, halogen, carboxy, hydroxy or phenoxy, and wherein Y 1 denotes one or more substituent(s) selected from hydrogen, halogen, Ci-Ce alkyl, trifluoro methyl, Ci-Ce alkoxy, cyano, nitro, -CONH 2 or COOQ3 and SO2Q3 wherein Q 3 means Ci-Cealkyl which is unsubstituted or substituted by cyano, halogen, carboxy, hydroxy or phenoxy or wherein
D denotes a radical of formula wherein X 2 denotes one or more substituent(s) selected from hydrogen, halogen, Ci-Ce alkyl, trifluoro methyl, Ci-Ce alkoxy, cyano, nitro or COOQ3 and SO2Q3 wherein Q 3 means Ci-Cealkyl which is unsubstituted or substituted by cyano, halogen, carboxy, hydroxy or phenoxy, and wherein Y 2 denotes one or more substituent(s) selected from hydrogen, halogen, Ci-Ce alkyl, trifluoro methyl, Ci-Ce alkoxy, cyano, nitro, -CONH 2 or COOQ3 and SO2Q3 wherein Q 3 means Ci-Cealkyl which is unsubstituted or substituted by cyano, halogen, carboxy, hydroxy or phenoxy or wherein
D denotes a radical of formula wherein X 3 denotes one or more substituent(s) selected from hydrogen, halogen, Ci-Ce alkyl, trifluoro methyl, Ci-Ce alkoxy, cyano, nitro or COOQ3 and SO2Q3 wherein Q 3 means Ci-Cealkyl which is unsubstituted or substituted by cyano, halogen, carboxy, hydroxy or phenoxy, and wherein Y 3 denotes one or more substituent(s) selected from hydrogen, halogen, Ci-Ce alkyl, trifluoro methyl, Ci-Ce alkoxy, cyano, nitro, -CONH 2 or COOQ3 and SO2Q3 wherein Q 3 means Ci-Cealkyl which is unsubstituted or substituted by cyano, halogen, carboxy, hydroxy or phenoxy.
In one embodiment, each of X 1 , X 2 or X 3 denotes one of the substituents as listed above.
In one embodiment, each of X 1 , X 2 or X 3 denotes two of the substituents as listed above that can be chosen independently.
In one embodiment, each of Y 1 , Y 2 or Y 3 denotes one of the substituents as listed above.
In one embodiment, each of Y 1 , Y 2 or Y 3 denotes two of the substituents as listed above that can be chosen independently.
Generally, Ci-Ceal kyl may be a straight-chain or branched and means, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n- pentyl, isopentyl, neopentyl or n-hexyl, particularly methyl, ethyl, n-propyl or n- butyl.
Generally, Ci-Cealkoxy may be a straight-chain or branched and means, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, iso-butyloxy, sec- butyloxy, tert-butyloxy, n-pentyloxy, neopentyloxy or n-hexyloxy, particularly methoxy or ethoxy.
Generally, any radical denoting halogen may be fluorine, chlorine or bromine.
Ri in the meaning of Ci-C4alkoxy may be a straight-chain or branched and means, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, iso-bu- tyloxy, sec-butyloxy, or tert-butyloxy, particularly methoxy or ethoxy.
Ri in the meaning of halogen may be fluorine, chlorine or bromine, preferably chlorine or bromine and more preferably bromine.
In a preferred embodiment, Ri is hydrogen, halogen or C1-C4 alkoxy, preferably hydrogen, bromine or methoxy.
Ci-Ceal kyl with respect to each of X 1 , X 2 , X 3 or Y 1 , Y 2 and Y 3 , independently includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-bu- tyl, tert-butyl, n-pentyl, isopentyl, neopentyl and n-hexyl. Ci- Cealkyl may unsubstituted or substituted by cyano, halogen, carboxy, hydroxy or phenyloxy, for example, 2 -hydroxyethyl, 2-phenoxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, 2-cy- anoethyl, 2-cyanopropyl, 2-chloroethyl, 4-cyanobutyl or 2 -carboxyethyl. Ci-Ceal- kyl may be interrupted one or more times by -O-, -S-, -CO-, -COO- or -OOC-, for example, 2-methoxyethyl, 2-methoxypropyl, 4-methoxybutyl, 2-ethoxyethyl, 2- ethoxypropyl, -(CH 2 )2OCH 2 COOCH 3 , -(CH 2 ) 2 OCH 2 COOCH 2 CH 3 , - (CH 2 ) 2 COOCH 3 , -(CH 2 ) 2 COO(CH 2 ) 2 OCH 3 , -(CH 2 ) 2 OOCCH 3 or -(CH 2 ) 2 OOCCH 2 CH 3 ., - (CH 2 ) 2 OOCC 6 H 5 .
In a preferred embodiment each of X 1 , X 2 or X 3 , independently, denotes one or more substituent(s) selected from hydrogen, halogen, preferably chlorine, nitro or Ci-Ce alkyl, preferably methyl.
In a preferred embodiment D denotes a radical of formula Wherein X 1 denotes one or more substituent(s) selected from hydrogen, halogen, preferably chlorine, nitro or Ci-Ce alkyl, preferably methyl and Y 1 is defined as above.
Preferably, when D denotes a radical of formula (2), X 1 denotes hydrogen, halogen, preferably chlorine, nitro or Ci-Ce alkyl, preferably methyl and Y 1 denotes one or more substituent(s) selected from hydrogen, cyano, trifluoro methyl, COOQ3 wherein Q 3 means Ci-Cealkyl, preferably methyl, ethyl or propyl, or halogen, preferably chlorine.
Preferably, when D denotes a radical of formula (2), X 1 denotes hydrogen, halogen, preferably chlorine, nitro or Ci-Ce alkyl, preferably methyl, Y1 denotes one or more substituent(s) selected from hydrogen, trifluoro methyl, COOQ3 wherein Q3 means Ci-Cealkyl, preferably methyl ethyl or propyl, or halogen, preferably chlorine and Ri denotes hydrogen, halogen or C1-C4 alkoxy, preferably hydrogen, bromine or methoxy.
In a preferred embodiment, D denotes a radical of formula
Wherein X 2 denoted one or more substituent(s) selected from hydrogen or halogen, preferably chlorine, and Y 2 is defined as above.
Preferably, when D denotes a radical of formula (3), X 2 denoted one or more substituents) selected from hydrogen or halogen, preferably chlorine, and Y 2 denotes one or more substituent(s) selected from hydrogen, halogen, preferably bromine or fluorine, trifluoro methyl, -CONH2, cyano or COOQ3 wherein Q3 means Ci-Cealkyl, preferably methyl or ethyl.
Preferably, when D denotes a radical of formula (3), X 2 denoted one or more substituents) selected from hydrogen or halogen, preferably chlorine, Y 2 denotes one or more substituent(s) selected from hydrogen, halogen, preferably bromine or fluorine, trifluoro methyl, -CONH 2 , cyano or COOQ 3 wherein Q 3 means Ci-Ceal- kyl, preferably methyl or ethyl, and Ri denotes hydrogen, halogen or C1-C4 alkoxy, preferably hydrogen, bromine or methoxy.
In a preferred embodiment, D denotes a radical of formula
(4), wherein X 3 denoted hydrogen, and Y 3 is defined as above.
Preferably, when D denotes a radical of formula (4), X 3 denotes hydrogen and Y 3 denotes one or more substituent(s) selected from hydrogen, trifluoro methyl, cyano, halogen, preferably chlorine, nitro -CONH2 or Ci-Cealkyl which includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl and n-hexyl. Ci- Cealkyl may unsubstituted or substituted by cyano, halogen, carboxy, hydroxy or phenyloxy, for example, 2-hydroxyethyl, 2- phenoxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, 2-cyanoethyl, 2-cyanopropyl, 2- chloroethyl, 4-cyanobutyl or 2-carboxyethyl, wherein Ci- Cealkyl may be interrupted one or more times by -O-, -S-, -CO-, -COO- or -OOC-, for example, 2- methoxyethyl, 2-methoxypropyl, 4-methoxybutyl, 2 -ethoxyethyl, 2-ethoxypro- pyl, -(CH 2 )2OCH 2 COOCH 3 , -(CH 2 )2OCH2COOCH 2 CH3, - (CH 2 ) 2 COOCH 3 , -(CH 2 )2COO(CH 2 )2OCH 3 , -(CH 2 ) 2 OOCCH 3 or -(CH 2 ) 2 OOCCH 2 CH 3 ., - (CH 2 )2OOCC 6 H5, preferably -COO(CH 2 ) 2 OCH 3 ,
Preferably, when D denotes a radical of formula (4), X 3 denotes hydrogen, Y 3 denotes one or more substituent(s) selected from hydrogen, trifluoro methyl, cyano, COOQ 3 wherein Q 3 means Ci-Cealkyl which is unsubstituted or substituted by cyano, halogen, carboxy, hydroxy or phenoxy, preferably -COO(CH2)2OCH3, halogen, preferably chlorine, nitro or -CONH2, and R1 denotes hydrogen, halogen or C1-C4 alkoxy, preferably hydrogen, bromine or methoxy. The present invention also relates to a process for the preparation of an azo dye of formula (1) according to any of claims 1-3, which comprises diazotizing an amine compound D-NH2 in accordance with a customary procedure, and then coupling the diazotized amine compound to a BON-acid (2-hydroxynaphthalene-3- carboxylic acid) coupling component of the formula
(la), wherein D and Ri are as defined above.
All definitions and preferred embodiments as set forth above with respect to the azo dye of formula (1) apply analogously to the instantly described method.
The diazotisation of the amine compound D-NH2 is carried out in a manner known per se, for example with sodium nitrite in an acidic, e.g. hydrochloric-acid-containing or sulfuric-acid-containing, aqueous medium. The diazotisation may, however, also be carried out using other diazotisation agents, e.g. with nitrosylsulfu- ric acid. In the diazotisation, an additional acid may be present in the reaction medium, e.g. phosphoric acid, sulfuric acid, acetic acid, propionic acid or hydrochloric acid or a mixture of such acids, e.g. a mixture of propionic acid and acetic acid. The diazotisation is advantageously carried out at temperatures of from -10 to 30°C, for example of from -10°C to room temperature, particularly of from -5 to 10°C.
The coupling of the diazotised amine compound D-NH2 to the BON-Acid coupling component of formula (la) is likewise accomplished in known manner, for example in an acidic, neutral or alkaline aqueous or aqueous-organic medium, advantageously at temperatures of from 0 to 30°C, especially below 20°C. The amine compound D-NH2 is known or can be prepared in a manner known per se, as described, for example in WO 2012 032512 and H. Woodburn, J. of the American Chem. Society, 72, 1361-1364 (1950) and T. Sone, Chemistry Letters 8, 1982, 1259-1262.
The BON-acid coupling component of formula (la) is known or can be prepared in a manner known per se, as described, for example, in US 1 503 984, US 1 947 819 and DE 561 425.
The present invention also relates to the azo dyes obtained by the before mentioned process.
The inventive dye of formula (1) can advantageously be used in admixture with other dyes for the preparation of mixed shades, for example, red shades.
Accordingly, the present invention further relates to dye mixtures, wherein the dye of formula (1) is used in admixture with at least one further dye selected from the group consisting of C.I. Disperse Red 050, C.I. Disperse Red 060, C.I. Disperse Red 072, C.I. Disperse Red 082, C.I. Disperse Red 86: 1, C.I. Disperse Red 167, C.I. Disperse Red 277 , C.I. Disperse Red 279, C.I. Disperse Red 302, C.I. Disperse Red 302: 1, C.I. Disperse Red 342, C.I. Disperse Red 349, C.I. Disperse Red 356, C.I. Disperse Red 362, C.I. Disperse Red 376, C.I. Disperse Red 377, C.I. Disperse Red 378, C.I. Disperse Red 380, C.I. Disperse Red 383, C.I. Disperse Red 385 and/or the dye of formula
The amount of the individual dyes in the dye mixtures can vary within a wide range. The dyes and dye mixtures according to the invention can be used in the dyeing or printing of semi-synthetic and, especially, synthetic hydrophobic fiber materials, more especially textile materials. Textile materials composed of blends that contain such semi-synthetic and/or synthetic hydrophobic fiber materials can likewise be dyed or printed using the dyes or dye mixtures according to the invention.
The amount of the individual dyes in the dye mixtures can vary within a wide range. Dyeings obtained in accordance with the inventive process are distinguished by level colour shades having very good in-use fastness properties such as, especially, good fastness to light, fastness to heat setting, fastness to pleating, fastness to chlorine, and wet fastness, e.g. fastness to water, to perspiration and to washing; the finished dyeings are further characterised by very good fastness to rubbing. Special emphasis should be given to the good allround fastness properties of the dyeings and their outstanding brightness.
Semi-synthetic fibre materials that come into consideration are, especially, cellulose 272-acetate and cellulose triacetate.
Synthetic hydrophobic fibre materials consist especially of linear, aromatic polyesters, for example those of terephthalic acid and glycols, especially ethylene glycol, or condensation products of terephthalic acid and l,4-bis(hydroxymethyl)cy- clohexane; of polycarbonates, e.g. those of a,a-dimethyl-4,4-dihydroxy-diphenyl- methane and phosgene, and of fibres based on polyvinyl chloride or on polyamide.
The application of the dyes and dye mixtures according to the invention to the fibre materials is accomplished in accordance with known dyeing methods. For example, polyester fibre materials are dyed in the exhaust process from an aqueous dispersion in the presence of customary anionic or non-ionic dispersants and, optionally, customary swelling agents (carriers) at temperatures of from 80 to 140°C. Cellulose 272-acetate is dyed preferably at temperatures of from 65 to 85°C, and cellulose triacetate at temperatures of from 65 to 115°C.
The dyes and dye mixtures according to the invention will not colour wool and cotton present at the same time in the dyebath or will colour such materials only slightly (very good reservation) so that they can also be used satisfactorily in the dyeing of polyester/wool and polyester/cellulosic fibre blend fabrics.
The dyes and dye mixtures according to the invention are suitable for dyeing in accordance with the thermosol process, in the exhaust process and for printing processes. In such processes, the said fibre materials can be in a variety of processing forms, e.g. in the form of fibres, yarns or nonwoven, woven or knitted fabrics.
It is advantageous to convert the dyes and dye mixtures according to the invention into a dye preparation prior to use. For this purpose, the dye is ground so that its particle size is on average from 0.1 to 10 microns. Grinding can be carried out in the presence of dispersants. For example, the dried dye is ground together with a dispersant or kneaded into a paste form together with a dispersant and then dried in vacuo or by atomisation. After adding water, the resulting preparations can be used to prepare printing pastes and dyebaths.
For printing, the customary thickeners will be used, e.g. modified or unmodified natural products, for example alginates, British gum, gum arabic, crystal gum, locust bean flour, tragacanth, carboxymethyl cellulose, hydroxyethyl cellulose, starch or synthetic products, for example polyacrylamides, polyacrylic acid or copolymers thereof, or polyvinyl alcohols.
The dyes and dye mixtures according to the invention are also suitable as colorants for use in recording systems. Such recording systems are, for example, commercially available ink-jet printers for paper or textile printing, or writing instruments, such as fountain pens or ballpoint pens, and especially ink-jet printers. For that purpose, the dyes according to the invention are first brought into a form suitable for use in recording systems. A suitable form is, for example, an aqueous ink, which comprises the dyes according to the invention as colorants. The inks can be prepared in customary manner by mixing together the individual components, if necessary in combination with suitable dispersing agents, in the desired amount of water.
The dyes and dye mixtures according to the invention impart to the said materials, especially to polyester materials, level colour shades having very good in-use fastness properties such as, especially, good fastness to light, fastness to heat setting, fastness to pleating, fastness to chlorine, and wet fastness, e.g. fastness to water, to perspiration and to washing; the finished dyeings are further characterised by very good fastness to rubbing. Special emphasis should be given to the good allround fastness properties of the dyeings and their outstanding brightness.
Furthermore, the dyes and dye mixtures according to the invention are also well suited to dyeing hydrophobic fibre materials from supercritical CO2.
The present invention relates to the above-mentioned use of the dyes and dye mixtures according to the invention as well as to a process for the dyeing or printing of semi-synthetic or synthetic hydrophobic fibre materials, especially synthetic hydrophobic fibre materials, and more especially textile materials, in which process a dye according to the invention is applied to the said materials or incorporated into them. The said hydrophobic fibre materials are preferably textile polyester materials.
In the case of the ink-jet printing method, individual droplets of ink are sprayed onto a substrate from a nozzle in a controlled manner. It is mainly the continuous ink-jet method and the drop-on-demand method that are used for that purpose. In the case of the continuous ink-jet method, the droplets are produced continuously, droplets not required for the printing operation being discharged into a receptacle and recycled. In the case of the drop-on-demand method, on the other hand, droplets are generated as desired and used for printing; that is droplets are generated only when required for the printing operation. The production of the droplets can be accomplished, for example, by means of a piezo ink-jet head or by thermal energy (bubble jet). Preference is given to printing by means of a piezo ink-jet head and to printing according to the continuous ink-jet method.
The invention relates also to hydrophobic fibre materials, preferably polyester textile materials, dyed or printed by the said processes.
The dyes according to the invention are, in addition, suitable for modern reproduction processes, e.g. thermotransfer printing.
Hence, one further aspect of the instant invention it the use of a dye of formula (1) as defined above or a dye mixture as defined above in dyeing or printing semi-synthetic or synthetic hydrophobic fibre materials, and especially synthetic hydrophobic fibre materials, more especially textile polyester materials, and one further aspect of the instant invention is a semi-synthetic or synthetic hydrophobic fibre material, especially a textile polyester material, dyed or printed by the dye of formula (1) as defined above or by the dye mixture as defined above.
The Examples that follow serve to illustrate the invention. Parts therein are parts by weight and percentages are percentages by weight, unless otherwise indicated. Temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is the same as between grams and cubic centimetres.
I, Preparation Examples
Preparation Example 1:
Preparation of the dyestuff of formula (101):
Step A:
The amine component of formula can be obtained, for example, in accordance with the procedure described in CN101830766A by a reaction of phenol with 2,5-dichloro nitrobenzene. Step B:
3.4 g of the amine component obtained according to step A are dispersed in 15 g of water. 4.5 g of hydrochloric acid (32%) are subsequently added and afterwards 5.0 g of glacial acetic acid. The mixture is cooled to 0 to 5°C and 4.7 g of sodium nitrite (4N) are slowly added. After completion of the reaction excess of nitrite is destroyed by addition of sulfamic acid.
Step C:
2.8 g of 2-hydroxy-3-naphthoic acid are dispersed in 40 ml of water. Subsequently, 5.7 g of sodium hydroxide (30%) are added to the mixture and coupling is affected at pH > 10.5 and a temperature of 5 to 10°C by addition of the diazotized amine component obtained according to step B to the mixture. During the addition pH and temperature of the mixture are kept in the desired range by addition of sodium hydroxide (30%) and crushed ice. After completion of the coupling reaction the slurry is suction filtered and the residue is washed and suspended in 150 ml of water, adjusting the mixture under good stirring to pH 1 by addition of hydrochloric acid (32 %). After filtration of the precipitation, washing and drying, 5.6 g of dye (7) are isolated which imparts a red hue and a good overall fastness level to polyester fibres.
Preparation Example 2:
Preparation of the dyestuff of formula (102): Step A:
The amine component of formula can be obtained, for example, in accordance with the procedure described in WO 2002/044156 A2 by a reaction of 4-fluoro nitrobenzene with 4-amino phenol.
Step B:
3.5 g of the amine component obtained according to step A are dispersed in 15 g of water. 4.5 g of hydrochloric acid (32%) are subsequently added. The mixture is cooled to 0 to 5°C and 4.7 g of sodium nitrite (4N) are slowly added. After completion of the reaction excess of nitrite is destroyed by addition of sulfamic acid.
Step C:
2.8 g of 2-hydroxy-3-naphthoic acid are dispersed in 40 ml of water. Subsequently, 5.7 g of sodium hydroxide (30%) are added to the mixture and coupling is affected at pH > 10.5 and a temperature of 5 to 10°C by addition of the diazotized amine component obtained according to step B to the mixture. During the addition pH and temperature of the mixture are kept in the desired range by addition of sodium hydroxide (30%) and crushed ice. After completion of the coupling reaction the slurry is suction filtered and the residue is washed and suspended in 150 ml of water, adjusting the mixture under good stirring to pH 1 by addition of hydrochloric acid (32 %). After filtration of the precipitation, washing and drying, 6.0 g of dye (37) are isolated which imparts a brilliant red hue and a good overall fastness level to polyester fibres. The following dyes listed in table 1 were prepared analogously to preparation examples 1 and 2
IL Application Examples
Application Example 1:
1 part by weight of the dye of formula (101) according to Preparation Example 1 is milled together with four parts of a commercially available dispersing agent and 15 parts of water.
Using this formulation, a 1% dyeing (based on the dye and the substrate) is produced on woven polyester by high temperature exhaust process at 135°C.
Test results: the light fastness of the dyeing is excellent as well as the results in the AATCC 61 and ISO 105 tests. The build up properties of the dye are very good.
Application Examples 2 to 44:
Application Example 1 is repeated by using the dyes of Preparation Examples 2 to 44 instead of the dye of formula (101) according to Preparation Example 1.
The build up properties of the dyes are very good and the dyeings exhibit good light fastness and very good results in the AATCC 61 and ISO 105 tests.