DE2130991A1 - Process for the production of water-insoluble azo dyes - Google Patents

Description

MTENTANWÄITI

DR. -ING. H. FiNCKe 9

DIPL-ING. H. BOHR ^l '

DtPL-ING 3. STAEGER % 2 JUNE 1971

MÖNCHEN 5 MOLLERSTR. 31

Folder 22594 Case: D * 2288l

PRIORITY: June 22nd, 1970 - Great Britain

Imperial Chemical Industries Limited Great Britain

Process for the production of water-insoluble

Azo dyes

The invention relates to water-insoluble azo dyes,

which is used for dyeing synthetic fabrics

109853/1723

especially good from aromatic polyesters
suitable

According to the invention, acidic water-solubilizing agents Group-free, water-insoluble azo dyes of the formula

created,

where H is an alkyl or aryl radical, that too

May contain substituents, represents and the

Benzene rings X and T contain further substituents

can·

The alkyl radicals B are preferably lower alkyl »
radicals, for example methyl, ethyl, n-propyl and n-butyl bath radicals, for example chlorine and broa atoms as substituents. Hydroxy groups, lower alkoxy groups such as
Methoxy and ithoxy groups, I-lower alkoxy lower alkoxy groups such as ß-methoxyethoxy groups, cyano groups,
Acyloxy groups such as lower alkylcarbonyloxy groups,
for example acetoxy and benzoyloxy groups may contain. The aryl radical R is preferably the phenyl radical,

109853/172 3

the ζ - Β _β can contain chlorine and bromine atoms, lower alkyl groups such as methyl groups, lower alkoxy groups such as methoxy groups, and acyloxy groups such as acetoxy and benzoyl groups as substituents

For the purposes of the invention, the terms "lower alkyl" and "lower alkoxy" alkyl and alkoxy radicals, respectively each with 1 to 4 carbon atoms

As examples of the other substituents in the benzene ring X one can mention the following: chlorine and bromate, cyano, nitro, trifluoromethyl groups, lower alkyl groups such as methyl groups, lower alkoxy groups such as methoxy groups, lower alkylsulfonyl groups such as methylsulfonyl groups, Carbon lower alkoxy groups such as carbomethoxy groups, carbonamide groups and H-lower alkyl and Ν, ΙΓ-di-lower alkyl derivatives thereof, sulfonamide groups and F-lower alkyl and Ιϊ, Η-di-lower alkyl derivatives thereof, and Acylamino groups such as acetylamino groups

The following can be mentioned as examples of the other substituents in the benzene ring Y: chlorine and bromine atoms, Acylamino groups such as acetylamino and benzoylamino groups, Lower alkylsulfonyl groups such as ethylsulfonyl groups, and sulfonamide groups as well as H-lower alkyl and H, H-di-lower alkyl derivatives thereof.

1 09853/1 723

According to a further feature of the invention is a Process for the preparation of the azo dyes proposed according to the invention, which consists in that an amine of the formula

Formula I.

diazotized and the diazo compound obtained with a coupling component of the formula

Formula II

where E, X and 7 have the meanings given above, is coupled.

The method according to the invention can be expediently by using sodium nitrite to make a solution or dispersion of the amine in an inorganic Acid or the amine to Hitrosylschulf elic acid is added and the resulting suspension or solution of the diazo compound to form a solution of the coupling component in aqueous alkali, which optionally contains a water-soluble organic liquid, is added. Of the

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The pH of the mixture obtained can optionally be adjusted so that the coupling is facilitated whereupon the dye obtained can be isolated in a conventional manner.

The following can be mentioned as specific examples of the amines of the formula I: o-ffitraniline, 2,4- and 2,6-dinitraniline, 2,4,6-trinitraniline, 2,4-dinitro-5-chloro or -bromo- or -cyanoaniline, 2,4-dinitro-6-chloro- or -bromo- or -cyanoaniline, 2-nitro-4-carboxamide- or -sulfonamid- or carbomethoxy- or -cyanoaniline, 4- or 5-methoxy-2-nitroaniline and 4- or 5- * methyl-2-nitroaniline

The coupling components of the formula II can by reacting an amine of the formula -HH ^ -H with a Acid of the formula

* "COOH COOH

or the corresponding anhydride, wherein R and X the o.a. have meanings, are produced «

As specific examples of these coupling components can stan mention the following: H-ethyl homophthalimide (H-ethylisoquinoline-1,3-diol), N-methylhomophthalimide,

H-phenyl homophthalimide, N- (4-methoxyphenyl) homophthalimide,

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H- (r-Hethoxypropyl) homophthalimid, IT- (ß-Hydroxyäthyl) homophthalimid, N ~ iLthyl-6- or -7-nitrohomophthalimide and H-ethyl-6- or -7-acetylaminoh.omophthalimid.

The azo dyes according to the invention are suitable either individually or in the form of mixtures for the Dyeing of synthetic textiles, e.g. cellulose acetate and cellulose triacetate textiles, polyamide textiles like ζ · Β · Textile fabrics made of polyhexamethylene adipamide, and preferably fabrics made from aromatic polyesters, e.g. Polyalkylene terephthalate. Such textiles can be in the form of threads, yarns, woven or knitted fabrics.

Such fabrics can be conveniently with the dyeing dyes according to the invention as defined above in that the textile fabric is immersed in a dye bath composed of an aqueous dispersion of one or more of the Dyes and preferably a nonionic, cationic and / or anionic surface-active Contains agent, whereupon the dyebath for a corresponding time at a suitable temperature gets warmed up. In the case of cellulose acetate secondary fabrics the dyeing process is preferred

- "7 -

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, at a between 60 and 85 ° C temperature lying durchgeführtj with cellulose triacetate or polyamide textile materials, the dyeing is preferably at 95 to 100 ⁰ C; are textiles of aromatic polyesters, the dyeing may be preferably in the presence of a carrier, either at 90 to 100 ° C, ζ · Β · diphenyl or o ~ hydroxydiphenyl performed or above 100 ⁰ C, preferably effected at 120 to 140 ⁰ C at atmospheric pressure .

But you can also proceed in such a way that an aqueous dispersion of the azo dyes on the textile is applied by a block or pressure process, after which the textile fabric is heated or with steam is treated. In such methods, the aqueous dispersion preferably contains the monoazo dye a thickener such as tragacanth, gum arabic or sodium alginate

At the end of the dyeing process, the dyed textile fabric is preferably rinsed with water or briefly with it Treated soapy water before drying. In the case of textile fabrics made from aromatic polyesters the dyed fabric is preferably treated with an alkaline aqueous sodium hydrosulfite solution subjected before it is treated with soapy water to remove weakly adhering dye from

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- 8 ~
remove from the surface of the fabric.

They have excellent affinity and dyes Build-up potential with regard to synthetic textiles, in particular 'textiles made from aromatic polyesters, so that deep color tones can be achieved. The dyeings obtained have good fastness against light, hateful treatments and above all «» dry heat treatments, how they are carried out e.g. at high temperatures during pleating «

If desired, the inventive Azo dyes when applied to synthetic fabrics together with other disperse dyes can be used as e.g. in British patents 806 271, 835 819, 840 903, 847 175 »852 396, 852 493, 859 899, 865 328, 872 204, 894 012, 908 656, 909 843, 910 306, 9U 856, 919 424, 944 513, 944 722, 953 887, 959 816, 960 235 and 961 412 are described.

The invention is explained in more detail below purely by way of example using exemplary embodiments, with parts being by weight.

example 1

5.5 parts of a 14% aqueous sodium nitrite

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solution are a suspension of 1.38 parts of o-nitroaniline in a mixture of 20 parts of water and 4 ropes of lee-concentrated aqueous hydrochloric acid added with stirring at 0 to 5 ° C within 30 minutes, and the resulting mixture is 3 hours Stirred at this temperature. The mixture is filtered. The filtrate is used to remove excess Nitrous acid treated with sulfamic acid and then a solution of 2.1 ropes of N-ithyl homophthalimide in 150 ropes of water with 0.4 ropes of sodium hydroxide and 15 ropes of sodium acetate at a temperature between 0 and 5 ° C. The mixture is stirred for 30 minutes, and the precipitated dye is filtered off, washed with water and dried.

An aqueous dispersion of this dye gives yellow on fabrics made from aromatic polyesters Colorations with excellent fastness properties.

The table below shows further examples of sispersion azo dyes according to the invention listed, which are obtained by the fact that the amines indicated in the 2nd column of the table are diazotized and the diazo compounds obtained each with the in the 3 * column of the table

- 10 -

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specified coupling components are coupled, working analogously to Example 1 · In The 4 × column of the table shows the color shades that are used when dyeing aromatic polyester textiles can be obtained with the respective dyes

- 11 -

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example

Coupling component

hue

β 2 4-methoacy-2-nitr aniline 3 5-methoxy-2-nitroaniline 4th 4-methyl-2-nitroaniline I. 5 2,4-dinitraniline W. 6th 4-Chlo2v2-aitraniline O
co 7th 6-cyano-2,4-dinitraniline CX)
cn 8th 2-kitraniline co 9 - «3
K> 10 It CaJ 11th It 12th η 13th η 14th η 15th It 16

tf-lthyl homophthalimide

K- (r -Me thoacypropyl) homoplithalimide N-plaenyl homophthalimide K-ethyl-G-nitrohomoplithalimide

N-methylnomophthalimide

K-n-butyl homophthalimide

K- (ß-Hydroxyethyl) homophthalimide

N-Cβ-cyanoethy-homophthalimide N- (B-acetoxyethyl) homoplithalimide K- (β-Benzoyloxyattiyl) homophthalimide

orange

yellow

η η η

Orange yellow

M R

Il

OO CD CD CD

example

AmIn coupling component

hue

17 18

20 21 22 23 24

25 26

27 28

29

2-nitroaniline

6-bromo-2,4-dinitraniline

4-trifluoromethyl-2-nitranilln

4-methylsulfonyl-2-nitroaniline

4-CaΓbometlloxy-2-nitΓaniline

4- (N _$ N-dimethylcarbonamide) -2-nitroaniline

4- (N, N-33imethylsulfonamide) -2-nitroaniline

N- (B-methoxyethyl) homoplithalimide N- ß-Cß'-methoxyethoxy ^ äthyl homophthalimid If- (p-chlorophenyl) homophthalimide N- (o-tolyl) homophthalimide H- (p-ardsidine) homophthalimide IT- (p-benzoyloxyplienyl) homophthalimide

K- (p-Ace toxyphenyl) homophthalimide

K-ethyl homophthalimide

CD CD CD

30th 31 32 O co 33 OO 34 · 35 NJ ω 36

Example amine coupling component shade

4 ~ Acetylamino-2-nitroaniline N-Ethylhomophthalimide Orange

2-Nitraniline Er-Ethyl-6-acetylaBinohoiaophthalimid Red-yellow

ⁿ N-ethyl-6-bronshomophthaliiaid orange

^M II-ethyl-6-cyanhomophthalide "

ⁿ K-ethyl-6- (H, N-diethylsulfonamide) homo- -a

phthalimide "^

ⁿ R-ethyl-6-methylsulfonylhoiaophthalide ^M.

"N-Ätiiyl-7-acetylaminohomoph'to.alimid"

ο co co

Claims (1)

Claim Process for the production of water-insoluble, acidic, water-solubilizing groups Azo dyes of the formula wherein H is an alkyl or aryl radical that also has substituents may contain, represents and the benzene rings X and Y may contain further substituents, characterized in that an amine of the formula diazotized and the diazo compound obtained with a coupling component of the formula (y where E, 2 and Y have the above meanings, is patted. _109853/1723