DE1943057A1 - Insoluble monoazoic dyes - Google Patents

Abstract

WATER-INSOLUBLE AZO-DYES FOR HYDROPHOBIC SYNTHETIC FIBRES. M2A. Are of formula:- (where X1 are nitro, cyano-(di)alkylsulphonyl; X2 is Cl, Br, nitro, cyano, or alkylsulphonyl; X3 is Cl, Br or (pref.) H; Y and H, alkyl, alkoxy or acylamine; Z is alkyl, alkoxy or (pref.) H; R1 is C3-10 alkenyl (pref. C3-4) and R2 is opt. substd. alkyl). Preparation comprises coupling a compound of formula:- with a compound of formula:-.

Description

Water-insoluble monoazo dyes (addendum to the patent ..... - Pat.Anm.Az .: ....... Ref. 2875) Subject of the main patent, which itself in the addendum to the patent ...... (Pat.Anm.Az .: ....... Ref. 2875) . Az. P 18 07 763.9) are valuable, water-insoluble monoazo dyes of the general formula in which X1 is nitro, cyano, alkylsulfonyl or dialkylaminosulfonyl, X2 is chlorine, bromine, nitro, cyano or alkylaulfonyl, X3 is chlorine or bromine, Y is hydrogen, alkyl, alkoxy or acylamino, R1 is alkenyl with 3-10 carbon atoms, preferably 3-4 carbon atoms and R2 denotes optionally further substituted alkyl.

In a further development of this subject of the invention has now been found that such water-insoluble monoazo dyes of the above formula, the in the 6-position of the benzene core originating from the coupling component another contain selected substituents, also have excellent properties.

The present invention accordingly relates to water-insoluble monoazo dyes of the general formula in which X1, X2, X3, Y, R1 and R2 have the same meaning as in the main patent and Z denotes alkyl or alkoxy.

The new dyes are prepared in the usual way by coupling diazotized amines of the general formula with tertiary amines of the general formula where X1, X2, X3, Y, Z, R1 and R2 have the above meaning.

As diazo components used in the present process the same ones that are listed in the main patent come into question, e.g. 2-chloro-4-nitro-6-bromaniline, 2,6-dibromo-4-nitro-nitraniline, 2-chloro- or 2-bromo-4-nitro-6-cyananiline, 2-chloro- or 2-bromo-4-nitro-6-methylsulfonylaniline, 2-chloro- or 2-bromo-4,6-dinitraniline and the corresponding 4-cyano-, 4-alkylsulfonyl- and 4-dialkylaminosulfonyl-aniline.

The coupling components used in the present process are, for example the following are used: N-alkyl-N-allyl-2-methyl-5-methoxy-aniline, N-alkyl-N-methallyl-2-methyl-5-methoxy-aniline, N-alkyl-N- (buten-2-yl) -2-methyl-5-methoxy-aniline, N-alkyl-N-allyl-2-methoxy-5-acetylaminoaniline, N-alkyl-N-methallyl-2-methoxy-5-acetylamino-aniline, N-alkyl-N- (buten-2-yl) -2-methoxy-5-acetylamino-aniline, N-alkyl-N-allyl-2-ethoxy-5-acetylamino-aniline, N-alkyl-N-methallyl-2-ethoxy-5-acetylamino-aniline, N-alkyl-N- (buten-2-yl) -2-ethoxy-5-acetylamino-aniline. As alkyl groups in the sense According to the above definition, preference is given to methyl, ethyl and butyl, i.e. those with 1-4 carbon atoms understood.

Particularly valuable dyes are obtained with coupling components, whose alkyl group is a ß-substituted ethyl group, such as phenethyl, hydroxyethyl, Alkoxyethyl, such as ethoxyethyl, acyloxyethyl, such as acetyloxyethyl or propionyloxyethyl, Cyanoethyl, alkoxycarbonylethyl, such as methoxycarbonylethyl, alkylsulfonylethyl, such as Methylsulfonylethyl or nitroethyl.

With the new dyes, synthetic, hydrophobic materials, such as linear polyester, acetyl cellulose, polyamide and polycarbonate, in excellent Color and print wise.

Among structures made of synthetic hydrophobic materials are, for example Foils, films or textiles such as fibers, threads, flakes, woven and knitted fabrics to understand.

Textile goods made from polyesters, such as polyethylene glycol terephthalate, or those based on terephthalic acid and p-dimethylolcyclohexane can be used with dye the dyes according to known methods. The dyeing temperatures for the in dyes present in aqueous dispersion are at 95-1000C at normal pressure, preferably at 100 ° C or under increased pressure at 104-1400 ° C.

When using temperatures around 1000C it is recommended to use the dye bath Add swelling agent (carrier). As swelling agents, e.g. aromatic hydrocarbons, such as diphenyl, aromatic halogen compounds such as chlorobenzenes, aromatic carboxylic acids, such as benzoic acid and salicylic acid, phenols such as o- and p-phenylphenols, esters such as Terephthalic acid esters, can be used.

Instead of dyeing from the bath, you can also use hot air fixation Make the dyes at temperatures of 200-2300C. Printing can be carried out in this way be that the printed goods in the presence of a carrier at temperatures between about 80-1100C or in the absence of a carrier at about 110-1400C or steamed is also treated according to the so-called thermosetting process at around 1702300C.

Example 1: In 157 g of nitrosylsulfuric acid (made from 150 g Sulfuric acid 660 Be and 7 g sodium nitrite) are 26.2 g 2-bromo-4'6-dinitro-aniline at 15-200C entered and stirred at 200C for 3 hours.

28.7 g of N-allyl-N-cyanoethyl-2-ethoxy-5-acetylamino-aniline are in the equivalent amount of dilute aqueous hydrochloric acid dissolved and 1 g of urea, 375 g of ice and the Dvazo solution described above are added. The reaction mixture is diluted with ice water, stirred briefly, filtered off with suction and the residue thoroughly washed with water.

After drying, 49 g of a blue dye powder are obtained, which in finely dispersed form dyes polyester in a navy blue shade.

The following table lists further dyes according to the invention which dye polyester fibers in the specified shades with similarly good properties: General formula: Example X1 X2 X3 YZ R1 R2 shade 2 NO2 NO2 Cl NHCOCH3 OCH3 allyl CH2CH2CN blue 3 "" Br "OC2H5" CH2CH2COOCH3 "4""Br NHCOC2H5 OCH3 methallyl C2H5 5" CN Br OC2H5 CH3 butene-6 "2-yl violet CN Br NHCOCH3 OC2H5 Allyl "bla 7" CN Br "OCH3" CH2CH2OCOCH3 "8" SO2CH3 Cl "OC2H5" CH2CH2SO2CH3 violet 9 "" Br NHCOC2H5 "" CH2CH2CN "10 CN CN Br" II AlCOCH3 OCH3 CN CN Br3 "NH2CH2 violet 11 CN CN Br" II CH2CH2OH bordo 12 CH3SO2 Br Br "OC2H5""" 13 "CN Cl""""violet 14 (CH3) 2NSO2 Cl Cl OCH3 CH3" CH2CH2C6H5 red-brown 15 "NO2 Br NHCOCH3" lt CH2CH2OH bordo 16 NO2 Br Br "OCH2. CH2 17 "Cl Cl" OC2H5 Methallyl CH2CH2CN "Example 18: In a dye liquor whose pH is adjusted to 5-6 with acetic acid and 5-10 g of a swelling agent such as o-phenylphenol and 0.5 to 1 liter of water g of finely dispersed dye of Example 1, 25 g of yarn made of polyethylene glycol terephthalate are introduced at 50-600C, the dye bath within 30M heated to boiling temperature in minutes and held at this temperature for 90 minutes. The material colored in this way is treated reductively for 20-30 minutes at 60-70 ° C. with 4 ml / l sodium hydroxide solution (380 Be) and 2 g / l dithionite. It is then rinsed warm, acidified with acetic acid and rinsed again.

This gives a clear blue coloration with very good fastness properties.

Example 19: With a padding liquor that contains 2-3 g of one per liter of water Ethylene oxide addition product as a dispersant, 20 g of a thickener based on polyacrylic acid and containing 2 g of finely dispersed dye of Example 1, a fabric made of polyethylene glycol terephthalate is padded at 40 ° C, dried and thermosolated with hot air at 200-2300C for 60 seconds, after a reductive Post-treatment with 4 ml / l sodium hydroxide solution (380 sec) and 2 g / l dithionite for 20 minutes at 60-700C the material is rinsed, acidified and rinsed again.

This gives a clear blue coloration with very good fastness properties.

Example 20: A polyester fabric is printed on a roller printing machine printed with a printing paste of the following composition: 50 g of 10% dye paste, which contains the dye of Example 4 in finely dispersed form, 250 g starch tragacanth thickening, 250 g crystal rubber thickening (1: 3) and 450 g water or thickening. After printing and drying, the fabric is either thermosolated at 190-210 ° C. for 30-60 seconds or steamed for 10-20 minutes at 1-2 atm. Both methods will produce blue prints obtained from very good fastness properties.

Claims (5)

Claim (1che 9 Water-insoluble monoazo dyes of the general formula in which X1 is nitro, cyano, alkylsulfonyl or dialkylaminosulfonyl, X2 is chlorine, bromine, nitro, cyano or alkylsulfonyl, X3 is chlorine or bromine, Y is hydrogen, alkyl, alkoxy or acylamino, Z is alkyl or alkoxy, R1 is alkenyl with 3-10 carbon atoms and R2 is optionally further substituted alkyl. 2. Water-insoluble monoazo dyes of those specified in claim 1 general formula in which X1 is nitro, cyano, methylsulfonyl, or dimethylaminosulfonyl, X2 chlorine, bromine, nitro, cyano or methylsulfonyl, X3 chlorine or bromine, Y alkoxy with 1-4 carbon atoms, acetylamino or propionylamino, Z methyl, methoxy or xthoxy, R1 Allyl, methallyl or buten-2-yl and R2 ethyl, cyanoethyl, methylsulfonylethyl, acetoxyethyl, Mean methoxycarbonylethyl or hydroxyethyl. 3. Process for the preparation of water-insoluble monoazo dyes of the general formula given in Claim 1, characterized in that diazotized amines of the general formula are used with tertiary amines of the general formula wherein X1, X2, X31 Y, Z, R1 and R2 have the meanings given in claim 1, couples. 4. Process for dyeing and printing synthetic hydrophobic Materials, characterized in that a dye of the type specified in claim 1 is used general formula used. 5. With a dye of the general formula given in claim 1 colored or printed synthetic hydrophobic materials.