Title of Invention

AZO DYES AND A PROCESS FOR THEIR PREPARATION

Abstract wherein R<sub>1</sub> is the radical of a diazo component of the benzene, naphthalene, diphenyl, azobenzene, thiophene, benzothiazole, benzisothiazole, thiadiazole, indazole, benzotriazole, pyrazole, anthraquinone, naphtholic acid imide, chromone, phthalimide or diphenylene oxide series, R<sub>2</sub> is an unsubstituted or substituted aryl radical or an unsubstituted or substituted aralkyl radical and R<sub>3</sub> is an unsubstituted or substituted aryl radical or an unsubstituted or substituted aralkyl' .radical, with the proviso that when one of the substituents R<sub>2</sub>2 and R<sub>3</sub> is an unsubstituted or substituted aryl radical, the other is an unsubstituted or substituted aralkyl radical.
Full Text

Azo dyes, a process for their preparation and their use in the dyeing or printing of hydrophobic fibre materials.
The present invention relates to azo dyes, to their preparation and to their use in the dyeing or printing of semi-synthetic or synthetic hydrophobic fibre materials.
Azo dyes and their use in the dyeing of semi-synthetic or synthetic hydrophobic fibre materials are known. It has been shown, however, that such dyes do not always fully satisfy the highest demands, especially in respect of high temperature light fastness and/or colour strength. There is therefore a need for new dyes that yield tinctorially strong, alkali-stable dyeings or prints having high temperature light fastness and that exhibit good allround properties.
It has now been found, surprisingly, that the azo dyes according to the invention meet the criteria given above to a considerable degree.
The present invention accordingly relates to azo dyes of formula
(1),
wherein
Ri is the radical of a diazo component of the benzene, naphthalene, diphenyl, azobenzene,
thiophene, benzothiazole, benzisothiazole, thiadiazole, indazole, benzotriazole, pyrazole,
anthraquinone, naphtholic acid imide, chromone, phthalimide or diphenylene oxide series,
R2 is an unsubstituted or substituted aryl radical or an unsubstituted or substituted aralkyi
radical and
R3 is an unsubstituted or substituted aryl radical or an unsubstituted or substituted aralkyi
radical,

with the proviso that when one of the substituents R2 and R3 is an unsubstituted or substituted aryl radical, the other is an unsubstituted or substituted aralkyi radical.
Of the substituents R1, the radicals of a diazo component of the benzene, naphthalene and
thiophene seR1es are preferred.
Especially prefenred as R1 is the radical of a diazo component of the benzene seR1es.
The aryl radicals denoted by R2 and R3 may be mono- or poly-substituted, especially mono-to tR1-substituted, e.g. by C1-C4a!kyl, CrC4alkoxy or halogen.
Preferably, the aryl radicals denoted by R2 and R3 are unsubstituted or substituted by methyl, methoxy, chloR1ne or fluoR1ne.
The aryl radicals denoted by R2 and R3 are especially substituted by methyl in the ortho-position and, more especially, the meta-position to the amino group.
The radicals R2 and R3 are very especially unsubstituted.
A preferred aryl radical for R2 and R3 is phenyl.
C1-C4Alkyl as a substituent of R2 and/or R3 is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
C1-C4Alkoxy as a substituent of R2 and/or R3 is e.g. methoxy, ethoxy, propoxy or butoxy.
A prefen-ed aralkyi radical for R2 and R3 is -C1-C4aIkyl-phenyl.
The phenyl radical in -C1-C4alkyl-phenyl can itself be mono- or poly-substituted by the substituents indicated above for "aryl radicals".
The bR1dging member-C1-C4alkyl- in -C1-C4alkyl-phenyl may be unsubstituted or substituted by hydroxy.
Preferably the bR1dging member-C1-C4alkyl- in -C1-C4alkyl-phenyl is unsubstituted.

Preferably, the phenyl radical in -C1-C4alkyl-phenyl does not itself carry substituents. Halogen as a substituent of R2 and/or R3 is bromine, fluoR1ne or especially chloR1ne. The azo dyes of the following formulae are important:





The present invention relates also to dye mixtures compR1sing at least two structurally different azo dyes of formula (1).
Preference is given to dye mixtures compR1sing two stmcturally different azo dyes of formula (1).
Special preference is given to dye mixtures compR1sing the azo dyes of formulae (2) and (3), (4) and (5), (6) and (7), and (8) and (9).
The amount of the individual dyes in the dye mixtures according to the invention may vary within wide limits from e.g. 95:5 to 5:95 parts by weight, especially from 70:30 to 30:70 parts by weight, more especially from 55:45 to 45:55 parts by weight, of the individual dyes in a dye mixture compR1sing two azo dyes according to the invention.
Very special preference is given to dye mixtures compR1sing the following structurally different azo dyes of formula (1):
A. azo dyes of fomiulae (2), (3), (4) and (5), and
B. azo dyes of formulae (6), (7), (8) and (9).
The amounts of the azo dyes in dye mixture A. may likewise vary within wide limits, preference being given to dye mixtures in which the sum of the azo dyes of formulae (2) and (3) and the sum of the azo dyes of formulae (4) and (5) vaR1es in a ratio by weight between 95:5 and 5:95, especially between 70:30 and 30:70, more especially between 55:45 and 45:55. the definitions and preferences given above for the dye mixture compR1sing two azo dyes according to the invention applying also to the ratio of the azo dyes of fonnulae (2) and (3). and (4) and (5).

The amounts of the azo dyes in dye mixture B. may likewise vary within wide limits, preference being given to dye mixtures in which the sum of the azo dyes of formulae (6) and (7) and the sum of the azo dyes of formulae (8) and (9) vaR1es in a ratio by weight between 95:5 and 5:95, especially between 70:30 and 30:70, more especially between 55:45 and 45:55, the definitions and preferences given above for the dye mixture compR1sing two azo dyes according to the invention applying also to the ratio of the azo dyes of formulae (6) and (7), and (8) and (9).

The diazotisation of the compound of formula (50) is carR1ed out in a manner known perse, for example with sodium nitR1te in an acidic, e.g. hydrochloR1c-acid-containing or sulfuR1c-acid-containing, aqueous medium. The diazotisation may, however, also be canied out using other diazotisation agents, e.g. using nitrosylsulfuR1c acid. In the diazotisation, an additional acid may be present in the reaction medium, e.g. phosphoR1c acid, sulfuR1c acid, acetic acid, propionic acid or hydrochloR1c acid or a mixture of such acids, e.g. a mixture of propionic acid and acetic acid. The diazotisation is advantageously canied out at temperatures of from -10 to 30°C, for example from -10°C to room temperature.

The coupling of the diazotised compound of formula (50) to the coupling component of formula (51) is likewise effected in known manner, for example in an acidic, aqueous or aqueous-organic medium, advantageously at temperatures of from -10 to 30°C, especially below 10°C. Examples of acids used are hydrochloR1c acid, acetic acid, propionic acid, sulfuR1c acid and phosphoR1c acid.
The compounds of formula (50) are known or can be prepared in a manner known perse. The coupling components of formula (51) are known or can be prepared in a manner known perse.

wherein R1, R2 and R3 are as defined above for formula (1) and R4 has the same meanings as R3 independently of R3 and n and m are the numbers 1, 2 or 3. The above coupling component mixture can be prepared, for example, as follows: a compound of formula


From the resulting coupling component mixture, the individual coupling component(s) of formula (51) or formulae (51a) and (51b) can be obtained by subsequent chromatographic separation.
The dye mixtures compR1sing four structurally different azo dyes of formula (1) can be prepared, for example, by simply mixing together two of the two-component dye mixtures descR1bed above, e.g. a mixture compR1sing the azo dyes of formulae (2) and (3) and a mixture compR1sing the azo dyes of formulae (4) and (5).
The azo dyes and dye mixtures according to the invention can be used in the dyeing and pR1nting of semi-synthetic and, especially, synthetic hydrophobic fibre mateR1als, more especially textile mateR1als. Textile mateR1als composed of blends that contain such semisynthetic and/or synthetic hydrophobic textile mateR1als can likewise be dyed or pR1nted using the azo dyes or dye mixtures according to the invention.
Semi-synthetic textile mateR1als that come into consideration are especially cellulose 2% acetate and cellulose tR1acetate.

Synthetic hydrophobic textile mateR1als consist especially of linear, aromatic polyesters, for example those of terephthalic acid and glycols, especially ethylene glycol, or condensation products of terephthalic acid and 1,4-bis(hydroxymethyl)cyclohexane; of polycarbonates, e.g. those of a,a-dimethyl-4,4-dihydroxy-diphenylmethane and phosgene, and of fibres based on polyvinyl chloR1de and on polyamide.
The application of the azo dyes and dye mixtures according to the invention to the textile mateR1als is effected in accordance with known dyeing procedures. For example, polyester fibre mateR1als 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 (earners) at temperatures of from 80 to 140°C. Cellulose 214 acetate is dyed preferably at about from 65 to 85**C and cellulose tR1acetate at temperatures of up to 115**C.
The azo 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 mateR1als only slightly (very good reservation), so that they can also be used satisfactoR1ly in the dyeing of polyester/wool and polyester/cellulosic fibre blend fabR1cs.
The azo dyes and dye mixtures according to the invention are suitable for dyeing in accordance with the thermosol process, in the exhaust and continuous process and for pR1nting processes. The exhaust process is preferred. The liquor ratio is dependent upon the nature of the apparatus, the substrate and the form of make-up. It may, however, be selected within a wide range, e.g. from 1:4 to 1:100, but is preferably from 1:6 to 1:25.
The said textile mateR1al can be in a vaR1ety of processing forms, e.g. in the form of fibres, yams or non-wovens, in the form of woven fabR1cs or knitted fabR1cs.
It is advantageous to convert the azo dyes and dye mixtures according to the invention into a dye preparation pR1or to use. For this purpose, the azo dyes are ground so that their particle size is on average from 0.1 to 10 microns. The gR1nding can be cam'ed out in the presence of dispersants. For example, the dR1ed azo dye is ground with a dispersant or is kneaded in paste form with a dispersant and then dR1ed in vacuo or by atomisation. The preparations so obtained can be used, after the addition of water, to prepare pR1nting pastes and dyebaths.

For pR1nting, the customary thickeners will be used, e.g, modified or unmodified natural products, for example alginates, BR1tish gum, gum arable, crystal gum, locust bean flour, tragacanth, carboxymethylceliulose, hydroxyethylcellulose, starch or synthetic products, for example polyacrylamides, polyacrylic acid or copolymers thereof, or polyvinyl alcohols.
The azo dyes and dye mixtures according to the invention impart to the mentioned mateR1als, especially to polyester mateR1al, level colour shades having very good in-use fastness properties, such as, especially, good fastness to light, more especially very good high temperature light fastness, fastness to thermofixing, to pleating, to chloR1ne and to wetting, such as fastness to water, perspiration and washing; the finished dyeings are also distinguished by good fastness to rubbing.
The azo dyes and dye mixtures according to the invention can also be used satisfactoR1ly in the preparation of mixed shades together with other dyes.
The azo dyes and dye mixtures according to the invention can be used especially as a suitable component in a tR1chromatic dyeing or pR1nting technique.
In the process for tR1chromatic dyeing of semi-synthetic or'synthetic hydrophobic fibre mateR1als there is used at least one red-dyeing azo dye of formula
(1),
wherein R1 is the radical of a diazo component of the benzene, naphthalene, diphenyl, azobenzene, thiophene, benzothiazole, benzisothiazole, thiadiazole, indazole, benzotR1azole, pyrazole. anthraquinone, naphtholic acid imide, chromone, phthalimide or diphenylene oxide seR1es, R2 is an unsubstituted or substituted aryl radical or an unsubstituted or substituted aralkyi radical and R3 is an unsubstituted or substituted aryl

radical or an unsubstituted or substituted aralkyi radical, with the proviso that when one of the substituents R2 and R3 is an unsubstituted or substituted aryl radical, the other is an unsubstituted or substituted aralkyi radical,
optionally in combination with further red dyes, e.g. C.l. Disperse Red 086, C.l. Disperse Red 279, Dianix Rot HF-LS (Dystar) or Palanil Rot FFB (BASF),



The dyes of formulae (10) to (18) are known or can be prepared analogously to known compounds in accordance with procedures known perse.

The definitions and preferences given above apply also to the red-dyeing azo dye of formula (1).
TR1chromatic dyeing is the additive colour mixing of suitably selected yellow- or orange-dyeing, red-dyeing and blue-dyeing dyes with which any desired shade of the visible colour spectrum can be achieved by an appropR1ate choice of the relative proportions of the dye components.
In a preferred embodiment of the tR1chromatic process according to the invention, a dye mixture compR1sing the red-dyeing azo dyes of formulae (2), (3), (4) and (5) together with the blue-dyeing dyes of formulae (10) and (11) and the yellow-dyeing dye of formula (12) is used.
In a further preferred embodiment of the tR1chomatic process according to the invention, a dye mixture compR1sing the red-dyeing azo dyes of formulae (6), (7). (8) and (9) together with the blue-dyeing dyes of formulae (10) and (11) and the yellow-dyeing dye of formula (12) is used.

wherein R1 is the radical of a diazo component of the benzene, naphthalene, diphenyl, azobenzene, thiophene, benzothiazole, benzisothiazole, thiadiazole, indazole, benzo-tR1azole, pyrazole, anthraquinone, naphtholic acid imide, chromone, phthalimide or diphenyl-ene oxide seR1es. R2 is an unsubstituted or substituted aryl radical or an unsubstituted or substituted aralkyi radical and R3 is an unsubstituted or substituted aryl radical or an unsubstituted or substituted aralkyi radical, with the proviso that when one of the substituents R2

and R3 is an unsubstituted or substituted aryl radical, the other is an unsubstituted or substituted aralkyi radical,
at least one blue-dyeing dye of formulae (10) to (13) and at least one yellow-dyeing dye of formulae (14) to (18).
The definitions and preferences given above apply also to the red-dyeing azo dye of formula (1).
The azo dyes and dye mixtures according to the invention are also very suitable for dyeing hydrophobic textile mateR1al from supercR1tical CO2.
The present invention relates also to the above-mentioned use of the azo dyes and dye mixtures according to the invention as well as to a process for the dyeing or pR1nting of semi-synthetic or synthetic hydrophobic fibre mateR1al, especially textile mateR1al, which process compR1ses applying the azo dyes or dye mixtures according to the invention to the said mateR1al or incorporating them into that mateR1al. The said hydrophobic fibre mateR1al is preferably textile polyester mateR1al. Further substrates that can be treated by the process according to the invention and also preferred process conditions can be found above in the detailed descR1ption of the use of the azo dyes and dye mixtures according to the invention. The invention relates also to hydrophobic fibre mateR1al, especially polyester textile mateR1al, dyed or pR1nted by the said process.
The azo dyes and dye mixtures according to the invention are also suitable for modem reproduction processes, e.g. thermotransfer pR1nting.
The following Examples serve to illustrate the invention. In the Examples, unless otherwise indicated, parts are parts by weight and percentages are percent by weight. The temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is the same as that between grams and cubic centimetres.
Example 1:
A. In a laboratory reaction apparatus,
with stining and with cooling at a temperature of from 20 to 30°C. 27.80 g of 2-amino-5-
nitro-benzonitR1le are introduced into 40.00 g of a 97% sulfuR1c acid and stirR1ng is canied out

for 30 minutes. A further 10.00 g of a 97% sulfuR1c acid are then added to the resulting suspension, with stirR1ng, and the reaction mass is stirred for a further 30 minutes and cooled to about from 5 to 15*C. 47.70 g of a 40% nitrosylsulfuR1c acid are then added dropwise and the resulting solution is then stirred for 2 hours at from 10 to 20°C.
B. In a laboratory reaction apparatus,
76.00 g of powdered 2,6-dichloro-3-cyano-4-methylpyR1dine are suspended in 250.00 ml of tR1ethylamine and the suspension is heated to from 50 to 55°C. At that temperature, 49.00 g of phenethylamine are added dropwise and the mixture is stinred at 60°C for 12 hours. The temperature is then increased to about from 80 to 90°C, and the tR1ethylamine is separated off by distillation for about 10 hours. 100.00 ml of aniline are then added dropwise to the resulting solution and the solution is stirred at 150°C for 12 hours. 450.00 ml of a 4N HCI are then added and the reaction mass is poured into 150.00 g of ice and stirred for about 3.5 hours, filtered with suction, washed with 6,00 litres of water and dR1ed.
C. In a laboratory reaction apparatus,
63.30 g of the coupling component mixture prepared under B. are introduced into a mixture
of 250.00 ml of a 2N HCI and 200.00 ml of water. The resulting suspension is stirred for
1 hour, then filtered with suction and washed with water and the resulting filter cake is
introduced into 200.00 ml of a 80% acetic acid.
100.00 ml of ethyl alcohol are added to the resulting suspension; the mixture is cooled to
about 0°C and the diazo solution prepared under A. is added dropwise in the course of
30 minutes at a temperature of The resulting very viscous reaction mass is diluted with 150.00 ml of water and stinted for
3 hours at from 5 to 10°C.
The precipitated reaction product is then filtered off with suction, washed with water and
dR1ed.
76.60 g of a dye mixture consisting of the azo dyes of formulae


are obtained, which dyes polyester in red shades.
If required, the individual azo dyes of formulae (8) and (9) can be isolated by subsequent chromatographic separation.
Analogously to Example 1 it is possible to prepare the azo dyes listed in Tables 1 and 2, which likewise dye polyester in orange to reddish-violet shades:







Example 2;
Using a liquor ratio of 1:20, 100 g of polyester fabR1c are immersed at room temperature in a
liquor containing
0.07 g of a dye mixture compR1sing the azo dyes of formulae (2), (3), (4) and (5) in a ratio of
1:1:1:1,
0.058 g of a dye mixture compR1sing the dyes of formulae (10) and (11) in a ratio of 1:1,
0.57 g of a dye of formula (12),
1 g/1 of ammonium sulfate and
0.5 g/l of a commercially available levelling agent,
the liquor having been adjusted to a pH of 4.5 to 5 with 80% fornnic acid. The liquor is then
heated first to 60°C at a heating rate of 3°C/minute and then to 130°C at a heating rate of
2°C/minute.
Dyeing is carR1ed out at 130°C for 60 minutes. The liquor is then cooled to 40^0 and the
dyed polyester fabR1c is washed with water and cleaned reductively for 20 minutes at 70 -
80°C in a bath containing 5 ml/I of 30% sodium hydroxide solution, 2 g/l of 85% sodium
dithionite solution and 1 g/l of a commercially available detergent. The finished dyeing is
then washed with water and dR1ed.
A tinctoR1ally strong violet dyeing having good allround properties, especially excellent high
temperature light fastness properties, is obtained.



s
wherein
Ri is the radical of a diazo component of the benzene, naphthalene, diphenyl, azobenzene.
thiophene, benzothiazole, benzisothiazole, thiadiazole, indazole, benzotriazole, pyrazole,
anthraquinone, naphtholic acid imide, chromone, phthaiimide or diphenylene oxide series,
R2 is an unsubstituted or substituted aryl radical or an unsubstituted or substituted aralkyl
radical and
R3 is an unsubstituted or substituted aryl radical or an unsubstituted or substituted aralkyl
radical,
with the proviso that when one of the substituents R2 and R3 is an unsubstituted or
substituted aryl radical, the other is an unsubstituted or substituted aralkyl radical.
2. A dye mixture comprising at least two structurally different azo dyes of fonmula (1)
according to claim 1.
3. A dye mixture according to claim 2 comprising the azo dyes of formulae





8. A dye mixture according to claim 7 comprising the azo dyes of formulae


9. A dye mixture according to claim 7 comprising the azo dyes of formulae

10. A process for the preparation of an azo dye of formula (1) according to claim 1. wherein
a compound of formula


wherein Ri, R2 and R3 are as defined forfonnuia (1).
11. A process for the dyeing or printing of semi-synthetic or synthetic hydrophobic fibre material, wherein an azo dye of fonnuia (1) according to claim 1 or a dye mixture according to claim 2 is applied to the said material or is incorporated into that material.

wherein R1 is the radical of a diazo component of the benzene, naphthalene, diphenyl, azobenzene, thiophene, benzothiazole, benzisothiazole, thiadiazole, indazolie, benzo-triazole, pyrazole, anthraquinone, naphtholic acid imide, chromone, phthaiimide or diphenylene oxide series, R2 is an unsubstituted or substituted aryl radical or an unsub-stituted or substituted aralkyi radical and R3 is an unsubstituted or substituted aryl radical or an unsubstituted or substituted aralkyi radical, with the proviso that when one of the substituents R2 and R3 is an unsubstituted or substituted aryl radical, the other is an unsubstituted or substituted aralkyi radical, at least one blue-dyeing dye of formula




13. A process for the trichromatic dyeing or printing of semi-synthetic or synthetic hydrophobic fibre material, wherein a trichromatic mixture according to claim 12 is used.
14. Use of an azo dye of formula (1) according to claim 1 or of a dye mixture according to claim 2 in the dyeing or printing of semi-synthetic or synthetic hydrophobic fibre materials.
15. A semi-synthetic or synthetic hydrophobic fibre material dyed or printed with a dye of
formula (1) according to claim 1 or with a dye mixture according to claim 2.

16. An azo dye of formula substantially as herein descnbea ana exenipiuicu.
17. A dye mixture substantially as herein described and exemplified.
18. A process for the dyeing or printing of semi-synthetic or synthetic hydrophobic fibre material substantially as herein described and exemplified.


Documents:


Patent Number 224328
Indian Patent Application Number 1175/CHENP/2003
PG Journal Number 49/2008
Publication Date 05-Dec-2008
Grant Date 10-Oct-2008
Date of Filing 29-Jul-2003
Name of Patentee CIBA SPECIALTY CHEMICALS HOLDING INC
Applicant Address KLYBECKSTRASSE 141, CH-4057 BASEL,
Inventors:
# Inventor's Name Inventor's Address
1 PICHLER, Y VONNE RODLERWEG 25, CH-4203 GRELLINGEN,
2 LAUK, URS ALFRED-STRBELWEG 15, CH-8047 ZURICH,
PCT International Classification Number C09B29/42
PCT International Application Number PCT/EP02/00513
PCT International Filing date 2002-01-18
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 01810079.2 2001-01-26 EUROPEAN UNION