DE1912899B - - Google Patents

Description

The new dyes free of acidic groups improve the general formula

A-N = N

in which A is the radical of a diazotizable amine, the radicals R ₁ and R _{2 are} alkyl groups and X is a hydrogen atom, an alkyl or alkoxy group. The dyes of the formula (I) can be prepared according to the invention by coupling the diazo derivative of a diazotizable, aromatic or heterocyclic amine A - NH ₂ with a coupling agent of the general formula in an acidic medium

in which the radicals R ₁ , R ₂ and X have the same meanings as above.

The diazotizable amines A - NH ₂ can be derived from the most varied of classes, such as: benzene, benzene-azo-benzene, naphthalene, naphthalenazo-benzene, thiazole, benzothiazole, thiadiazole, thiophene. In the case of heterocyclic amines, the amino function can be located either on the heterocycle or on the benzene ring. The diazotization is effected by methods known per se, for example by means of sodium nitrite or with nitrosylsulfuric acid.

The coupling agents of the formula (II) are new products. For example, they can be manufactured by the action of a cinnamoyl chloride in an inert solvent or diluent on amines of the general formula

(III)

in the presence of an acid absorbent. Such compounds in which the radicals R ₁ and R _{2 are} identical can furthermore be obtained by using the compounds of the formula

-CH = CH-COHN

subjected to an alkylation treatment.

With a view to use as dyes, it is advantageous that the dyes obtained are in a finely divided state. It is for this reason that the dyes according to the invention preferably predispersed and presented in paste or powder form. This form can be achieved by kneading the dyes in the paste state with dispersants, if appropriate in the presence of filler; this kneading

ίο can be followed by drying and color rubbing if necessary.

The dyes treated in this way can then be used in a long or short bath for coloring Padding or printing.

As the dispersant which can be used, there can be mentioned, for example, the products which result from the condensation of naphthalenesulfonic acids with formaldehyde, in particular the dinaphthyl methane disulfonates. sulfonated succinic acid esters, alkaline salts of the sulfuric acid esters of fatty alcohols, for example sodium lauryl sulfate, the lignosulfonates, soaps, alkaline salts of sulfuric acid esters of fatty acid monoglycerides or the condensation products obtained from cresols with formaldehyde and naphtholsulfonic acids are, the condensation products .von 4,4'-Dihydroxydiphenylsulfon with formaldehyde and alkaline bisulfites.

The coloring of polyester fibers can waiting of carrier materials at temperatures in the range of 80 to 125 ⁰ C or without a carrier under pressure between about 100 and 140 ⁰ C are effected in the opposite ".

One can just as polyester fibers with the aqueous dispersions of the novel dyes padding or printing, then fix the impregnation obtained between 140 and 23O ⁰ C, for example with the aid of steam, air, or by contact with a heated surface. The temperature range between 180 and 200 ^° C. is particularly favorable because the dyes spread quickly in the polyester fibers and do not sublime even if the action of these elevated temperatures lasts longer. This makes it possible to avoid contamination of the dyeing devices.

Cellulose 2 '/ ₂ acetate is preferably dyed by exhausting the color between 65 and 85.degree. C. and cellulose triacetate and polyamide fibers at temperatures of up to 115.degree. The most favorable pH range is between 2 and 9, and particularly 4 to 8 One can triacetate, and polyamide fibers such as polyester fibers, padding or printing with aqueous suspensions of the novel dyes and fix the impregnations obtained 140-210 ⁰ C.

The usual thickeners, for example, are used in padding or printing modified or unmodified, natural products such as alginates, crystallized resin, or Gum, carob, adragant resin, carboxymethyl cellulose, hydroxyethyl cellulose, starch or synthetic Products such as polyacrylamides or polyvinyl alcohols.

The shades obtained in this way are remarkably colourfast to heat setting, Sublimation, pleating, combustion gases, over-dyeing, dry cleaning, chlorine and damp loads, for example with water, washing and sweat. The retention of natural fibers, im particular of wool and cotton and the

1

drawability are good. The lightfastness is remarkable even in the case of light shades, so that the new dyes are very suitable for producing fashion shades. The dyes withstand the cook-out and the reduction at temperatures from 80 to 220 ⁰ C. This stability is not changed with respect to the bath even by the presence of dyeing accelerators.

The new dyes are used, among other things, for coloring polyolefin fibers, nitrile acrylic polymer and mixed polymer fibers and fibers based on polyvinyl derivatives can be used.

Certain dyes of the formula (I) are suitable for coloring in bulk paints, oils and synthetic materials Resins and spun synthetic fibers from their solutions in organic solvents.

Compared to the neighboring dyes in the formula

the paint mill. The dye dyes polyethylene glycol terephthalate fibers and triacetate cellulose greenish blue.

The table below gives additional examples of dyes according to the invention. The one used to manufacture Bases used can be diazotized by customary industrial processes, for example with sodium nitrite or nitrosylsulfuric acid according to their basicity. The cinnamoylamino group the formula

/ V- CH = CH - CONH -

is indicated below by the abbreviation Nz. The specified shades were obtained on polyethylene glycol terephthalate fibers.

Table 1

NH-acyl

such as the N-benzoylated derivatives (French patent specification 1 428 383), have the invention manufacturable dyes have a significantly improved fastness compared to sublimation, which could not be foreseen was.

The following examples in which parts are parts by weight unless otherwise specified explain the invention without restricting the scope of the invention.

example 1

408 parts of freshly distilled N, N - dimethyl - meta - phenylenediamine (boiling point = 112 ° C. at 0.7 Torr), then 450 parts of freshly distilled Ν, Ν-diethylaniline and finally 500 parts of cinnamoyl chloride are added to 900 parts of xylene . The temperature rises immediately to 115 ° C. The mixture is kept under gentle reflux for 2 hours and then allowed to cool. Pouring the thickened mass into 4500 parts of 6O ⁰ C hot water, wherein the mixture is stirred vigorously, filtered, teigt in 2000 parts of warm water again and acidified slightly until the purple reaction of congo red paper, filtered and dried. 785 parts of Ν, Ν-dimethyl-N'-cinnamoyl-meta-phenylenediamine, melting point 182 to 183 ° C. are obtained.

Example 2

20.8 parts of 2-amino-3,5-dinitro-benzonitrile are slurried in 50 parts of sulfuric acid of 66 ⁰ Be. In the cooled to 0 ⁰ C mixture of 100 parts of nitrosylsulfuric acid is poured, keeping the temperature between 0 and 5 ° C (prepared from 6.9 parts of sodium nitrite). After a few hours of stirring, while maintaining the temperature, 50 parts of acetic acid, then 26 parts of NN-dimethyl-N'-cinnamoylmeta-phenylenediamine, dissolved in 100 parts of acetic acid, are added. The viscous mass is poured into an ice-water mixture, filtered, pasted again if necessary and a dispersant, for example a condensation product of cresolformaldehyde-naphtholsulfonic acid, is added to the paste and processed

example dye "Tint 3 [4-nitro-2-cyano-6-chloro blue benzene] - <l azo 1> - [4-dimethylamino- 2-Nz-benzene] 4th [2,4-Dinitrobenzene] - Purple red <1 azo l> - [4-diethyl amino-2-Nz-benzene] 5 [4-nitro-2-cyanobenzene] - Purple red <1 azo l> - [4N-ethyl- N-methylamino- 2-Nz-benzene] 6th [2,4-Dinitro-6-chlorobenzene] - violet <1 azo l> - [4-dimethyl- blue amino-2-Nz-benzene] 7th [4-nitro-2-methylsulfonyl- Purple red benzene] - <l azo 1> - [4-dimethylamino- 2-Nz-benzene] 8th [4-nitro-2,6-dichlorobenzene] - Bordo red <1 azo l> - [4-dimethyl- amino-2-Nz-benzene] 9 [2,4-dinitro-6-methyl- Greenish sulfonylbenzene] - <l azo 1> - blue [4-dimethylamino- 2-Nz-benzene] 10 [4-nitro-2-methoxy- Bluish carbonylbenzene] - Red <1 azo l> - [4-dimethyl- amino-2-Nz-benzene] 11th [4-cyanobenzene] - <l azo 1> - Scarlet fever [4-dipropylamino- Red - 2-Nz-benzene] 12th [2-cyanobenzene] - <l azo 1> - orange [4-diethylamino- Red ' 2-Nz-benzene] 13th [4-chloromethylsulfonyl- Scarlet fever benzene] - <l azo 1> - Red [4-dimethylamino- 2-Nz-benzene] 14th [2,4-Dinitro-6-chlorobenzene] - blue <1 azo l> - [5-methoxy- 4-dimethylamino 2-Nz-benzene]

continuation

example dye Color tint 15th [2-cyano-4-nitrobenzene] - violet <1 azo l> - [5-methyl- blue 4-dimethylamino 2-Nz-benzene] 16 rjZ-Nilro ^ -methylsulfonyl- Bluish benzene] - <l azo 1> - Red [4-dimethylamino- 2-Nz-bcnzol] 17th ^ -ChloM-nitrobcnzol] -: Bluish <l azo l> - [4-dimethyl- Red amino-2-Nz-bcnzol] 18th [4-nitrobenzene] - <l azo 1> - Scarlet fever [S-mcthyM-dimethyl- Red amino-2-Nz-benzoI] 19th [4-thiocyanate benzene] - orange <1 azo l> - [4-dimethyl- Red amino-2-Nz-benzene] 20th [4-ethoxycarbonylbenzene] - orange <1 azo l> - [4-dimethyl- amino-2-Nz-bcnzol] 21 [4-Acctylbenzol] - <1 azo 1> - orange [4-dimethylamino- 2-Nz-bcnzol] 22nd [4-dimethylaminosulfonyl- orange bcnzol] - <l azo 1> - [4-dimethylamino- 2-Nz-bcnzol] 23 [4-cyclohexylamino- orange carbonylbenzene] - <1 azo l> - [4-dimethyl- amino-2-Nz-bcnzol] 24 [^ -Nilro ^ -chlorobenzene] - Red <1 azo l> - [4-dimethyl- amino-2-Nz-benzene] 25th [2-nitro-4-trilluomethyl Red bcnzol] - <l azo 1> - [4-dimethylamino- 2-Nz-bcnzol] 26th [2,4-Dinilro-6-bromobenzene] blue <1 azo l> - [5-ethoxy- 4-dimethylamino 2-Nz-bcnzol] 27 [2-cyano-4-chlorobenzene] - Scarlet fever <1 azo l> - [4-dimethyl- Red amino-2-Nz-bcnzol] 28 [2-chloro-4-nitrobenzene] - Purple red <1 azo l> - [4-dibutyl- amino-2-Nz-bcnzol]

example Amines Color tint at
Polyester fibers 5 31 5-nitro-2-amino Ruby red 1,3,4-thiodiazole 32 2-amino-3-nitro-5-acetyl- Blue green thiophene 33 2-amino-6-nitrobenzo- Ruby red IO thiazole 34 2-amine o-6-cya η topzo- Bluish thiazole Red 35 2-amino-4,6-dinitrobenzo- Blue green thiazole ' ⁵ 36 2-amino-4-nitro-6-methyl- violet sulfonylbenzothiazole blue 37 2-amino-6-chloromethyl- Ruby red sulfonylbenzothiazole 20th 38 2-amino-6-thiocyanate Ruby red benzothiazole 39 3-phenyl-5-amino- Ruby red 1,2,4-thiodiazole 40 4-aminoazobenzene Red 41 4-amino-2-methoxyazo- Bluish benzene Red 42 4-amino-3-chloroazobenzene Bluish Red 30th 43 4'-nitro-2-methyl-4-amino- Red azobenzene 44 1 - PhenyIazo-4-amino- Red naphthalene

By coupling the diazo derivatives of the amines designated below with N ₁ , Ν, -dimethyl-N ₃ -CiIHIaInOyI-1,3-phenylcndiamine, further dyes of the formula (1) are obtained.

Table 2

example Amines Color tint at
Polyester fibers 29
30th 4-methylsulfonyl-
l-naphlhylamine
2-amino-5-nitrothiazole Brownish red
Reddish
blue

Example 45

A polyethylene glycol terephthalate fabric is impregnated by padding with a bath containing 9.0 parts of dye from Example 2, 0.5 parts of polyglycol ether of oleyl alcohol per 1000 parts by volume, Contains 1.5 parts polyacrylamide and the amount of water necessary to make up to 1000 parts. After drying, the fabric undergoes a heat setting for 1 minute at 200 ° C., then a reduction treatment subjected to sodium dithionite. A greenish-blue shade is obtained.

Example 46

A fabric of polyethylene glycol terephthalate is printed with a printing paste that is per 1000 parts 20 parts of the dye from Example 3, 150 parts of the sodium salt of sulfonated castor oil · Contains 600 parts of thickener and 230 parts of water. After drying the fabric is heat-set for 1 minute at 200 ° C. and then subjected to a reduction treatment. A blue shade with good general fastness properties is obtained.

Example 47

At 60 to 70 ° C., 100 parts of cellulose triacetate fabric are introduced into a dyebath of 3000 parts by volume a, this 1 part of the dye of Example 18 and 15 parts of o-phenylphenol. Man bring the bath to a boil over half an hour and put the dye under boil for 1 hour away. After the final treatment, a scarlet dye with good general fastness properties is obtained.

Claims (2)

Patent claims: 1. A process for the preparation of water-insoluble mono- and disazo dyes, characterized in that the diazo derivative of a diazotizable amine of the formula A - NH ₂ , in which A is the radical of a diazotizable amine, in an acidic medium with a coupling agent of the formula • 5 CO-CH = CH ^ f \ wherein the radicals R ₁ and R _{2 are} alkyl groups and X is hydrogen or an alkyl or alkoxy group to form compounds the general formula A —N == NH
CO-CH = CH ^ f wherein A, X, R ₁ and R _{2 have} the same meaning as above, couples. 2. Use of the dyes which can be prepared according to claim 1 for dyeing hydrophobic ones Fibers. 109530/336