NOWACK PATRIC (DE)
DREIER ROMEO (CH)
| WO2014016072A1 | 2014-01-30 | |||
| WO2009013122A2 | 2009-01-29 |
| GB1275603A | 1972-05-24 | |||
| US20140041134A1 | 2014-02-13 | |||
| US4678476A | 1987-07-07 | |||
| FR2008404A1 | 1970-01-23 | |||
| CN101955691A | 2011-01-26 |
| What is claimed is: 1 . A dye of formula (1 ). wherein Ri is bromo, nitro, cyano, methyl, methoxy or trifluoromethyl; R2 is hydrogen, chloro, bromo or trifluoromethyl; R3 is hydrogen, chloro, bromo, methoxy, trifluoromethyl, nitro or cyano; and R4 is methyl, ethyl, n-propyl, 2-methoxyethyl, methoxycarbonylmethyl or 2-methoxycarbonylethyl; with the proviso that R-i is cyano in case R2 denotes chloro or bromo and Ri is cyano or nitro in case R2 denotes trifluoromethyl. 2. A dye of formula (1 ) according to claim 1 , wherein Ri is cyano. 3. A dye of formula (1 ) according to claim 1 or 2, wherein R2 is chloro. 4. A dye of formula (1 ) according to any one of claims 1 - 3, wherein R3 is hydrogen. 5. A dye of formula (1 ) according to any one of claims 1 - 4, wherein R4 is methyl, ethyl, methoxycarbonylmethyl or 2-methoxycarbonylethyl. 6. A process for the preparation of a dye of formula (1 ) as claimed in claim 1 , which comprises diazotising a compound of formula and coupling the diazonium compound so obtained to a coupling component of formula wherein R-i , R2, R3 and R4 have the meanings given for formula (1 ) in claim 1 . 7. A dye mixture comprising at least one dye of formula (1 ) according to claim 1 and at least one further dye selected from the group consisting of C.I. Disperse Blue 60, C.I. Disperse Blue 79:1 , C.I. Disperse Blue 72:2, C.I. Disperse Blue 148, C.I. Disperse Blue 149, C.I. Disperse Blue 165, C.I. Disperse Blue 165:1 , C.I. Disperse Blue 207, C.I. Disperse Blue 284, C.I. Disperse Blue 295, C.I. Disperse Blue 316, C.I. Disperse Blue 337, C.I. Disperse Blue 354, C.I. Disperse Blue 366, C.I. Disperse Blue 367, C.I. Disperse Blue 368, C.I. Disperse Blue 376, C.I. Disperse Blue 378, C.I. Disperse Blue 380, C.I. Disperse Green 9, C.I. Disperse Violet 107, the compounds of formulas (101 ) - (179) described in WO 2014/016072, the compounds of formulas (101 ) - (106) described in WO 2009/013122 and the compounds of formulas II-2, II-3, II-4 and III-1 - III-8 described in CN 101955691 . 8. A process for dyeing or printing semi-synthetic or synthetic hydrophobic fibre material, in particular textile material, which comprises applying to or incorporating into the cited material at least one dye of formula (1 ) according to claim 1 or a dye mixture according to claim 7. 9. A process according to claim 8, wherein the hydrophobic material, preferably textile material, contains polyester fibres. 10. The material dyed or printed according to either claim 8 or claim 9. |
The present invention relates to disperse dyes having an acetylamino-substituted aniline coupling component, to a process for the preparation of such dyes and to their use in the dyeing or printing of semi-synthetic and, especially, synthetic hydrophobic fibre materials, more especially textile materials.
Disperse azo dyes derived from a nitroaniline diazo component and an acetylaminoaniline coupling component have been known for a long time, for example from FR 2008404, and are used in the dyeing of hydrophobic fibre materials. It has been found, however, that the dyeings or prints obtained using the dyes known at present do not in all cases meet current requirements, especially with regard to their fastness properties in respect of light, washing and perspiration. Particularly in the field of blue dyes there is a need for new dyes that give dyeings in brilliant shades having good fastness properties in respect of light, washing and perspiration.
It has now been found, surprisingly, that the dyes according to the invention meet the criteria mentioned above to a great extent.
The present invention accordingly relates to disperse dyes that yield dyeings having very good fastness to light, to washing and to perspiration and, in addition, exhibit good build-up both in the exhaust and thermosol processes and in textile printing.
The dyes according to the invention correspond to formula
wherein
Ri is bromo, nitro, cyano, methyl, methoxy or trifluoromethyl;
R 2 is hydrogen, chloro, bromo or trifluoromethyl;
R 3 is hydrogen, chloro, bromo, methoxy, trifluoromethyl, nitro or cyano; and R 4 is methyl, ethyl, n-propyl, 2-methoxyethyl, methoxycarbonylmethyl or
2-methoxycarbonylethyl;
with the proviso that R-i is cyano in case R 2 denotes chloro or bromo and Ri is cyano or nitro in case R 2 denotes trifluoromethyl.
In formula (1 ) Ri is preferably cyano.
Further preferred are dyes of formula (1 ) wherein R 2 is chloro. Special preference is given to dyes of formula (1 ) wherein R 3 is hydrogen.
R 4 in formula (1 ) is preferably methyl, ethyl, methoxycarbonylmethyl or
2-methoxycarbonylethyl.
The invention also relates to a process for the preparation of a dye of formula (1 ) as defined above, which comprises diazotising a compound of formula
R, and coupling the diazonium compound so obtained to a coupling component of formula wherein R-i, R 2 , R3 and R 4 have the meanings given for formula (1 ) above.
The diazo components of formula (2) as well as the coupling components of formula (3) are known or can be prepared in a manner known per se. Some are commercially available.
The diazotisation 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, for example using nitrosylsulfuric acid. In the diazotisation, an additional acid may be present in the reaction medium, for example phosphoric acid, sulfuric acid, acetic acid, propionic acid or hydrochloric acid or a mixture of such acids, for example a mixture of propionic acid and acetic acid. The diazotisation is advantageously carried out at temperatures of from -10 to 30°C, for example from -10°C to room temperature.
The coupling of the diazotised compound to the coupling component of formula (3) 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 hydrochloric acid, acetic acid, propionic acid, sulfuric acid and phosphoric acid.
The present invention further relates to a dye mixture comprising at least one dye of formula (1 ) as defined above and at least one further dye selected from the group consisting of C.I. Disperse Blue 60, C.I. Disperse Blue 79:1 , C.I. Disperse Blue 72:2, C.I. Disperse Blue 148, C.I. Disperse Blue 149, C.I. Disperse Blue 165, C.I. Disperse Blue 165:1 , C.I. Disperse Blue 207, C.I. Disperse Blue 284, C.I. Disperse Blue 295, C.I. Disperse Blue 316, C.I. Disperse Blue 337, C.I. Disperse Blue 354, C.I. Disperse Blue 366, C.I. Disperse Blue 367, C.I.
Disperse Blue 368, C.I. Disperse Blue 376, C.I. Disperse Blue 378, C.I. Disperse Blue 380, C.I. Disperse Green 9, C.I. Disperse Violet 107, the compounds of formulas (101 ) - (179) described in WO 2014/016072, the compounds of formulas (101 ) - (106) described in WO 2009/013122 and the compounds of formulas II-2, II-3, II-4 and 111-1 - III-8 described in CN 101955691 . The dye mixtures according to the invention can be prepared, for example, by simply mixing the individual dyes.
The amount of the individual dyes in the dye mixtures according to the invention can vary within a wide range.
The dye mixtures according to the invention advantageously contain at least 20 % by weight, preferably at least 30 % by weight and especially at least 40 % by weight, of one or more dyes of formula (1 ). The dyes and dye mixtures according to the invention can be used in the dyeing or printing of semi-synthetic and, especially, synthetic hydrophobic fibre materials, more especially textile materials. Textile materials composed of blends that contain such semi-synthetic and/or synthetic hydrophobic fibre materials can likewise be dyed or printed using the dyes or dye mixtures according to the invention.
Semi-synthetic fibre materials that come into consideration are especially cellulose 2½ 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 1 ,4-bis(hydroxymethyl)cyclohexane; of polycarbonates, for example those of a,a-dimethyl-4,4-dihydroxy-diphenylmethane and phosgene, and of fibres based on polyvinyl chloride and on polyamide.
The application of the dyes and dye mixtures according to the invention to the fibre materials is effected in accordance with known dyeing procedures. 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 2½ acetate is dyed preferably at from 65 to 85°C and cellulose triacetate at temperatures of from 65 to 1 15°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 like screen printing or ink-jet printing.
The said fibre materials can be in a variety of processing forms, e.g. in the form of fibres, yarns or non-wovens, in the form of woven fabrics 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 that purpose, the dye is ground so that its particle size is on average from 0.1 to 10 microns. The grinding can be carried out in the presence of dispersants. For example, the dried dye is ground with a dispersant or is kneaded in paste form with a dispersant and then dried in vacuo or by atomisation. The preparations so obtained can be used, after the addition of water, to prepare print 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, carboxymethylcellulose, hydroxyethylcellulose, starch or synthetic products, for example polyacrylamides, polyacrylic acid or copolymers thereof, or polyvinyl alcohols.
The dyes and dye mixtures according to the invention impart to the mentioned materials, especially to polyester materials, level colour shades having very good in-use fastness properties, such as, especially, good fastness to light, to thermofixing, to pleating, to chlorine and to wetting, such as fastness to water, to perspiration and to washing; the finished dyeings are also distinguished by very good fastness to rubbing. Special mention should be made of the good fastness properties of the resulting dyeings in respect of light, perspiration and, especially, washing.
The dyes and dye mixtures according to the invention can also be used satisfactorily in the preparation of mixed shades together with other dyes.
The dyes and dye mixtures according to the invention are also very suitable for dyeing hydrophobic fibre materials from supercritical C0 2 .
The present invention relates also 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 textile materials, wherein a dye according to the invention is applied to the said materials or is incorporated into those materials. The said hydrophobic fibre materials are preferably textile polyester materials. Further substrates that can be treated by the process according to the invention as well as preferred process conditions can be found above in the detailed description of the use of the dyes according to the invention. The invention relates also to hydrophobic fibre materials, especially polyester textile materials, dyed or printed by the said process.
The dyes according to the invention are also suitable for modern reproduction processes, for example thermotransfer printing.
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.
RT = room temperature
I. Preparation Examples Example 1.1
A. Diazotation
20 g of cone, sulfuric acid are placed in a laboratory reaction apparatus. After addition of 5 g ice the solution is cooled to RT. At this temperature, 6.01 g of 2-bromo-4-nitro-6-cyanoaniline are added. After being stirred for 30 min at RT and cooling down to 10 °C, 8.2 g of 40 % nitrosylsulfuric acid are added dropwise. The reaction mixture is stirred for a further 60 min at 10 °C. Afterwards, the excess nitrite is destroyed by addition of sulfamic acid.
B. Coupling
7.83 g of finely powdered N-3-nitrobenzyl-N-ethyl-3-acetylaminoaniline prepared according to the method described in Example 1 a of FR 2008404 are suspended in 10 ml ethanol and mixed with 20 g of ice.
Under stirring the solution of the diazonium salt obtained in step A is added dropwise within 60 min. The reaction mixture is stirred at RT over night. After filtration, washing and drying
I I .75 g (83 %) of the dye of formula (101 ) are obtained.
(101 ) The dyes (102) - (1252) listed in Table 1 are prepared analogously to the process described in Example 1.1 .
Table 1 :
^max = wavelength of the absorption maximum)
Compound Ri R 2 R 3 R 4
101 CN Br m-N0 2 -C 2 H 5 573
102 CN Br m-N0 2 -CHs
103 CN Br m-N0 2 n-C 3 H 7
104 CN Br m-N0 2 -CH 2 CH 2 OCHs
105 CN Br m-N0 2 -CH 2 CO-OCH 3
106 CN Br m-CFs -CH 2 CH 2 CO-OCH 3
107 CN Br m-CFs -CHs
108 CN Br m-CFs -C 2 H 5
109 CN Br m-CFs n-C 3 H 7
1 10 CN Br m-CFs -CH 2 CH 2 OCHs
1 1 1 CN Br m-CFs -CH 2 CO-OCH 3
1 12 CN Br m-CFs -CH 2 CH 2 CO-OCH 3
1 13 CN Br p-OCHs -CHs
1 14 CN Br p-OCHs -C 2 H 5
1 15 CN Br p-OCHs n-C 3 H 7
1 16 CN Br p-OCHs -CH 2 CH 2 OCHs
1 17 CN Br p-OCHs -CH 2 CO-OCH 3
1 18 CN Br p-OCHs -CH 2 CH 2 CO-OCH 3
1 19 CN Br p-CN -CHs
120 CN Br p-CN -C 2 H 5
121 CN Br p-CN n-C 3 H 7
122 CN Br p-CN -CH 2 CH 2 OCH 3 288 CN H H -C 2 H 5 545
289 CN H H n-C 3 H 7
290 CN H H -CH 2 CH 2 OCH 3
291 CN H H -CH 2 CO-OCH 3
292 CN H H -CH 2 CH 2 CO-OCH 3
293 N0 2 CF 3 m-N0 2 -CH 3
294 N0 2 CF 3 m-N0 2 -C 2 H 5
295 N0 2 CF 3 m-N0 2 n-C 3 H 7
296 N0 2 CF 3 m-N0 2 -CH 2 CH 2 OCH 3
297 N0 2 CF 3 m-N0 2 -CH 2 CO-OCH 3
298 N0 2 CF 3 m-CF 3 -CH 2 CH 2 CO-OCH 3
299 N0 2 CF 3 m-CF 3 -CH 3
300 N0 2 CF 3 m-CF 3 -C 2 H 5
301 N0 2 CF 3 m-CF 3 n-C 3 H 7
302 N0 2 CF 3 m-CF 3 -CH 2 CH 2 OCH 3
303 N0 2 CF 3 m-CF 3 -CH 2 CO-OCH 3
304 N0 2 CF 3 m-CF 3 -CH 2 CH 2 CO-OCH 3
305 N0 2 CF 3 p-OCH 3 -CH 3
306 N0 2 CF 3 p-OCH 3 -C 2 H 5
307 N0 2 CF 3 p-OCH 3 n-C 3 H 7
308 N0 2 CF 3 p-OCH 3 -CH 2 CH 2 OCH 3
309 N0 2 CF 3 p-OCH 3 -CH 2 CO-OCH 3
310 N0 2 CF 3 p-OCH 3 -CH 2 CH 2 CO-OCH 3
31 1 N0 2 CF 3 p-CN -CH 3
312 N0 2 CF 3 p-CN -C 2 H 5
313 N0 2 CF 3 p-CN n-C 3 H 7
314 N0 2 CF 3 p-CN -CH 2 CH 2 OCH 3
315 N0 2 CF 3 p-CN -CH 2 CO-OCH 3
316 N0 2 CF 3 p-CN -CH 2 CH 2 CO-OCH 3
317 N0 2 CF 3 p-CI -CH 3
318 N0 2 CF 3 p-CI -C 2 H 5
319 N0 2 CF 3 p-CI n-C 3 H 7
320 N0 2 CF 3 p-CI -CH 2 CH 2 OCH 3 321 N0 2 CF 3 p-CI -CH 2 CO-OCH 3
322 N0 2 CF 3 p-CI -CH 2 CH 2 CO-OCH 3
323 N0 2 CF 3 p-Br -CH 3
324 N0 2 CF 3 p-Br -C 2 H 5
325 N0 2 CF 3 p-Br n-C 3 H 7
326 N0 2 CF 3 p-Br -CH 2 CH 2 OCH 3
327 N0 2 CF 3 p-Br -CH 2 CO-OCH 3
328 N0 2 CF 3 p-Br -CH 2 CH 2 CO-OCH 3
329 N0 2 CF 3 p-N0 2 -CH 3
330 N0 2 CF 3 p-N0 2 -C 2 H 5
331 N0 2 CF 3 p-N0 2 n-C 3 H 7
332 N0 2 CF 3 p-N0 2 -CH 2 CH 2 OCH 3
333 N0 2 CF 3 p-N0 2 -CH 2 CO-OCH 3
334 N0 2 CF 3 p-N0 2 -CH 2 CH 2 CO-OCH 3
335 N0 2 CF 3 H -CH 3
336 N0 2 CF 3 H -C 2 H 5
337 N0 2 CF 3 H n-C 3 H 7
338 N0 2 CF 3 H -CH 2 CH 2 OCH 3
339 N0 2 CF 3 H -CH 2 CO-OCH 3
340 N0 2 CF 3 H -CH 2 CH 2 CO-OCH 3
341 N0 2 H m-N0 2 -CH 3
342 N0 2 H m-N0 2 -C 2 H 5
343 N0 2 H m-N0 2 n-C 3 H 7
344 N0 2 H m-N0 2 -CH 2 CH 2 OCH 3
345 N0 2 H m-N0 2 -CH 2 CO-OCH 3
346 N0 2 H m-CF 3 -CH 2 CH 2 CO-OCH 3
347 N0 2 H m-CF 3 -CH 3
348 N0 2 H m-CF 3 -C 2 H 5
349 N0 2 H m-CF 3 n-C 3 H 7
350 N0 2 H m-CF 3 -CH 2 CH 2 OCH 3
351 N0 2 H m-CF 3 -CH 2 CO-OCH 3
352 N0 2 H m-CF 3 -CH 2 CH 2 CO-OCH 3
353 N0 2 H p-OCH 3 -CH 3 387 N0 2 H H -CH 2 CO-OCH 3
388 N0 2 H H -CH 2 CH 2 CO-OCH 3
389 CH 3 H m-N0 2 -CH 3
390 CH 3 H m-N0 2 -C 2 H 5
391 CH 3 H m-N0 2 n-C 3 H 7
392 CH 3 H m-N0 2 -CH 2 CH 2 OCH 3
393 CH 3 H m-N0 2 -CH 2 CO-OCH 3
394 CH 3 H m-CF 3 -CH 2 CH 2 CO-OCH 3
395 CH 3 H m-CF 3 -CH 3
396 CH 3 H m-CF 3 -C 2 H 5
397 CH 3 H m-CF 3 n-C 3 H 7
398 CH 3 H m-CF 3 -CH 2 CH 2 OCH 3
399 CH 3 H m-CF 3 -CH 2 CO-OCH 3
400 CH 3 H m-CF 3 -CH 2 CH 2 CO-OCH 3
401 CH 3 H p-OCH 3 -CH 3
402 CH 3 H p-OCH 3 -C 2 H 5
403 CH 3 H p-OCH 3 n-C 3 H 7
404 CH 3 H p-OCH 3 -CH 2 CH 2 OCH 3
405 CH 3 H p-OCH 3 -CH 2 CO-OCH 3
406 CH 3 H p-OCH 3 -CH 2 CH 2 CO-OCH 3
407 CH 3 H p-CN -CH 3
408 CH 3 H p-CN -C 2 H 5
409 CH 3 H p-CN n-C 3 H 7
410 CH 3 H p-CN -CH 2 CH 2 OCH 3
41 1 CH 3 H p-CN -CH 2 CO-OCH 3
412 CH 3 H p-CN -CH 2 CH 2 CO-OCH 3
413 CH 3 H p-CI -CH 3
414 CH 3 H p-CI -C 2 H 5
415 CH 3 H p-CI n-C 3 H 7
416 CH 3 H p-CI -CH 2 CH 2 OCH 3
417 CH 3 H p-CI -CH 2 CO-OCH 3
418 CH 3 H p-CI -CH 2 CH 2 CO-OCH 3
419 CH 3 H p-Br -CH 3 486 CF 3 H m-N0 2 -C 2 H 5
487 CF 3 H m-N0 2 n-C 3 H 7
488 CF 3 H m-N0 2 -CH 2 CH 2 OCH 3
489 CF 3 H m-N0 2 -CH 2 CO-OCH 3
490 CF 3 H m-CF 3 -CH 2 CH 2 CO-OCH 3
491 CF 3 H m-CF 3 -CH 3
492 CF 3 H m-CF 3 -C 2 H 5
493 CF 3 H m-CF 3 n-C 3 H 7
494 CF 3 H m-CF 3 -CH 2 CH 2 OCH 3
495 CF 3 H m-CF 3 -CH 2 CO-OCH 3
496 CF 3 H m-CF 3 -CH 2 CH 2 CO-OCH 3
497 CF 3 H p-OCH 3 -CH 3
498 CF 3 H p-OCH 3 -C 2 H 5
499 CF 3 H p-OCH 3 n-C 3 H 7
500 CF 3 H p-OCH 3 -CH 2 CH 2 OCH 3
501 CF 3 H p-OCH 3 -CH 2 CO-OCH 3
502 CF 3 H p-OCH 3 -CH 2 CH 2 CO-OCH 3
503 CF 3 H p-CN -CH 3
504 CF 3 H p-CN -C 2 H 5
505 CF 3 H p-CN n-C 3 H 7
506 CF 3 H p-CN -CH 2 CH 2 OCH 3
507 CF 3 H p-CN -CH 2 CO-OCH 3
508 CF 3 H p-CN -CH 2 CH 2 CO-OCH 3
509 CF 3 H p-CI -CH 3
510 CF 3 H p-CI -C 2 H 5
51 1 CF 3 H p-CI n-C 3 H 7
512 CF 3 H p-CI -CH 2 CH 2 OCH 3
513 CF 3 H p-CI -CH 2 CO-OCH 3
514 CF 3 H p-CI -CH 2 CH 2 CO-OCH 3
515 CF 3 H p-Br -CH 3
516 CF 3 H p-Br -C 2 H 5
517 CF 3 H p-Br n-C 3 H 7
518 CF 3 H p-Br -CH 2 CH 2 OCH 3 II. Application Examples
11.1 : Dyeing of polyester
1 part by weight of the dye of formula (101 ) prepared in Example 1.1 is milled together with four parts of a commercially available dispersing agent and 15 parts of water. Using that 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.
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