DE2850706C3 - Cationic monoazo dyes, processes for their preparation and processes for dyeing and printing - Google Patents

Abstract

Cationic azo dyestuffs of the formula <IMAGE> wherein: R denotes hydrogen or methyl, R1 and R2 denote hydrogen or C1- C4-alkyl, R3 denotes C1-C4-alkyl, R4 denotes C1-C4-alkyl which is optionally substituted by OH, C2-C4- alkenyl or benzyl or phenylethyl which is optionally substituted by C1-C4- alkyl or halogen, and An<(-)> denotes an anion, are prepared. Processes for dyeing and printing materials which contain acid groups and consist completely or predominantly of polymerised unsaturated nitriles, of acid-modified polyesters or of acid-modified polyamides, and processes for dyeing or printing leather, paper, tannin- treated cotton, writing liquids, printing pastes, silk, cellulose acetate and fibres containing lignin are also disclosed.

Description

20th

and R ₃ Ci-Ci-alkyl,

Rt optionally substituted by OH Ci-Ci-alkyl, C ₂ -Ci-alkenyl or optionally by Ci-Ct-alkyl! or halogen-substituted benzyl or phenylethyl and

An (-) mean an anion.

2. Cationic azo dyes according to claim 1, characterized in that

and R3 represents methyl or ethyl and R _{4 represents} methyl, ethyl, hydroxyethyl, hydroxypropyl, allyl or benzyl.

3. Process for the preparation of cationic azo dyes of claim 1, characterized in that that one amines of the formula

30th

O ₃ N

NH,

diazotized and with ammonium compounds of the formula

50

CH ₇ -CH ₂ -NR, An ^e

R ₄

On ⁶

or with amines of the formula

CH ₂ -CH ₂ -N

coupled and in the latter case then with compounds of the formulas

R ₄ —An '

-CH-R ₄

CH

quaternized, where the radicals R, Ri, R ₂ , R ₃ and R ₄ and An (-) have the meaning given in claim 1. An 'is a radical which can be split off as an anion An'-' and R ' _{4 is} hydrogen, an alkyl radical whose number of carbon atoms is 2 less than that of R ₄ , or phenyl which is optionally substituted _{by C 1 -C 4 -alkyl or halogen.}

4. Process for dyeing and printing acidic group-containing materials that are completely or predominantly from polymerized unsaturated nitriles, such as acrylonitrile or vinylidenecyanide, consist of acid-modified polyesters or acid-modified polyamides, characterized in that the dyes according to Claim 1 are used.

5. Process for dyeing or printing leather. Paper, tanned cotton, writing fluids, Printing pastes, silk, cellulose acetate and lignin-containing fibers, characterized in that dyes according to claim 1 are used.

The invention relates to cationic azo dyes that are free from sulfonic acid and carboxylic acid and Are carboxylic acid groups, of the formula

O ₂ N- <f

R ₂

₂ - CiI ₂ -N-Rj

To ^e

(I)

R hydrogen or methyl,

Ri is hydrogen or Ci-C ₄ -alkyl,

gene of the formula

and R ₃ Ci-Q-alkyl,

R ₄ optionally substituted by OH-substituted C] -C ₄ -alkyl, C ₂ -C ₄ -alkenyl or optionally substituted by Ci-C ₄ -alkyl or halogen, benzyl or phenylethyl and

An (-) mean an anion.

The invention also relates to processes for the preparation of the dyes (1) and their use for dyeing and printing the natural and synthetic materials mentioned in the claims.

Azo dyes of the formula (I) in which R ;, R ₂ and R _{1 are} methyl or ethyl and R _{4 are} methyl, ethyl, hydroxyethyl, hydroxypropyl, allyl or benzyl are preferred.

The organic and inorganic anions customary for cationic dyes are used as anions Anions into consideration

Inorganic anions are, for example, chloride, bromide, iodide, hydroxyl, hydrogen sulfate, sulfate, aminosulfate, Nitrate, dihydrogen phosphate, hydrogen phosphate, phosphate, carbonate, methosulfate, ethosulfate, Cyanate or IsocyanaL

Organic anions are, for example, formate, acetate, chloroacetate, hydroxyacetate, cyanoacetate, phenoxyacetate, propionate, S-chlorpropoir- · !, 2-hydroxypionate, 2-hydroxypropionate, 3- (j3-hydroxyethoxy) propionate, laurate, oleate, glycolate, thio ^ ykolai, citrate, glycerate, itaconate, acrylate, methacrylate, crotonate, oxalate, malonate, succinate, glutarate, adipate, tartrate, fumarate, maleate, ethanesulphonate, Aminoäthansulfonat, Methylaminoäthansulfonat, Acylaminoäthylsulfonat, Hydroxyäthansulfonat, benzenesulfonate, Ci-Ci ₂ alkyl benzene sulfonate, Benzoate, 2-hydroxybenzoate or 4-hydroxybenzoate

Colorless anions are preferred. For dyeing from an aqueous medium, those anions are preferred which do not affect the water solubility of the dye too much. For coloring from organic Solvents, those anions are preferred that increase the solubility of the dye in organic solvents promote, e.g. B. laurate, oleate, dodecylbenzenesulfonate or acetylamino-ethyl-sulfonate.

The anion is generally given by the manufacturing process. Preferably the dyes are located as chlorides. Hydrogen sulfates, sulfates, methosulfates or acetates. The anions can be known in Way to be exchanged for other anions.

The dyes of the formula (I) are obtained in a manner known per se by the diazotization of amines formula

(U)

and coupling either with anirnöniumvefbiridun-

CH ₁ -CH-,

»I.

-N - R ₃ An = R ₄ OP)

or with amines of the formula

Ri

R ₁

20th

CH ₁ -CH ₁ -N QV)

R ₃

and in the latter case subsequent quaternization with compounds of the formula

R ₄ —An '

or

CH ₂ ch-r;

(V)

(VI)

In the formulas III-V, RR ₄ and An '-' have the meaning given in formula I, An 'denotes a substituent which can be split off as an anion, and R ₄ ' is hydrogen, an alkyl radical whose number of carbon atoms is 2 less than that of R ₄ , or phenyl optionally substituted by Ci-C ₄ -alkyl or halogen.

The quaternization with the Veibinduhg ^ n VI takes place in The presence of compounds which give an anion An <~> under the quaternization conditions take place.

Manufactures of this type are known from DE-OS 23 09 528 and DE-OS 25 48 879, for example.

The new dyes are suitable for dyeing, printing and bulk dyeing of acidic groups containing materials, especially of products that are completely or predominantly polymerized unsaturated nitriles, such as acrylonitrile and vinylidenecyanide, or from acid-modified polyesters or from acid modified polyamides exist. The fibers are described, for example, in U.S. Patents 3,018,272. 3166531, 3039990 and 3454351. she are also suitable for the other known uses of cationic dyes, such as dyeing and printing on cellulose acetate, tanned cotton and paper, for the production of ballpoint pen pastes and stamp inks and for use in rubber printing.

Dyeing is carried out in a known manner from neutral or weakly acid liquor at 40-10Q ⁰ C or under pressure at about 100 ⁰ C, it can be done with the addition of usual aids, such, for example in the presence of retarders or emulsifiers,

When using for printing the specified Conventional auxiliaries, such as wetting agents and thickeners, are added to the printing inks. The dyeings and prints on the former

Materials, especially those based on polyacrylonitrile, are characterized by their high level of fastness and good affinity to the fiber, especially through very good light, wet, rub, pecature, sublimation and perspiration fastnesses. she are also excellent for dyeing in mixtures with other cationic dyes.

Some of these advantageous properties of the new dyes surprisingly surpass them of known, obvious dyes. So have the new dyes compared to the German ones Offenlegungsschriften 20 24 184, 20 41690 and 20 59 947 known dyes, which are different from 2,4-dinitro-6-bromobenzoI derive improved lightfastness. The dye, according to the German interpretation 15 44 563, example 8, from the columns 19/20 - Consec. No. 10 - described components, i.e. by coupling of diazotized! 2,6-dibromo-4-nitrobenzene with N-ethyl-N - (/? - dimethyIaminoäthyl) -m-toluidine in sulfuric acid solution is the inferior to the next comparable new dye in its affinity for polyacrylonitrile fibers at higher pH values.

example 1

26 g of 2,6-dibromo-4-nitro-aniline are stored at 30-35 ° C while stirring in small portions in a mixture of 40 ml of conc. Sulfuric acid and 14.5 ml of 41% Entered nitrosylsulfuric acid and stirred for a further 2 hours at this temperature

28.5 g of 2- (N-ethyl-N-phenyl-amino) -äthyI-trimethylammoniummethylsulfat and 1 g of sulfamic acid are dissolved in 100 ml of water. After adding ice, add the above diazonium salt solution is added at a maximum of 5 ° C. with stirring. Then add approx. 60 ml of 30% sodium hydroxide solution has a pH of approx. 0.2 discontinued After the coupling has ended, the mixture is diluted with 1 liter of water and the resultant is sucked off Dye off. The cation of the dye formed has the formula

O ₂ N

C ₂ H ₅

CH ₂ -CH ^ -N (CHj) ₃

When dried, the dye is a brown powder that dissolves in water with a brown color.

Example 2

If in Example 1 the coupling component is replaced by 30 g of 2- (N-ethyl-N-3'-methyl-phenyl-amino) -ethy! - trimethylammonium methyl sulfate, a dye is obtained whose cation has the formula

O ₂ N

C ₂ H ₅

CH ₂ -CH ₂ -N (CHj) ₃

corresponds and dyes the polyacrylic materials according to Example 2 in real brown tones.

If the coupling component is replaced in Example 1 by the compounds listed in the table below, this is how you get dyes that color polyacrylonitrile in the specified shades:

CHj

R. CH ₂ R. -CH ₂ -NR ₂
I. R, R; Hue on
Polyacrylonitrile H I.
CH, CH, -CHj-CH = CH ₂ yellow-brown Example no. Cl-I ₃ C ₄ H, -CH ₂ -C ₆ H ₅ Brown 3 H C ₂ H ₅ -CH ₂ -CH-CHj yellow-brown 4th OH 5 CHj C ₂ H ₅ -CH ₂ -CH ₂ -OH Brown 6th

Example 7

0.8 g of the dye obtained in Example 1 are dissolved in 3 l of water with the addition of 3 ml of 30% strength acetic acid. In this bath at 40-50 ⁰ G was added 100 g of polyacrylonitrile, the temperature of the dye bath is increased within about 40 minutes at 100 ⁰ G and dyed at that temperature for about 1 hour. The result is a yellow-brown dyeing with excellent fastness properties.

Example 8

A polyacrylonitrile fabric is printed with a printing paste, which is produced in the following manner became:

30 parts of the dye described in Example 1, 50 parts of thiodiethylene glycol, 30 parts of cyclohexanol and 30 parts Parts of 30% acetic acid are poured over with 330 parts of hot water and 500 parts of the resulting solution Share Kristaügurnrni (gum srabicum as a thickener) given. Finally, 30 parts of zinc nitrate solution are added.

The pressure obtained is dried, steamed for 30 minutes and then rinsed. You get one brown print with good fastness properties.

Example 9

Acid-modified Polyglykolterephthalatfasern be at 2O ⁰ C in a liquor ratio 1: introduced 40 in an aqueous bath containing, per liter, 3 g to 10 sodium sulfate, 0.1 to 1 g Oleyalkoholpolyglykoiäther (from 1 mole Oleylalkohöl + 50 moles of ethylene oxide), 0 to 15 g Dimethylbenzyldodecylarrirnöhiümchlorid and 0.15 g of the dye of Example 1 and was adjusted to pH 4 to 5 with acetic acid. The mixture is heated within 30 min. At 100 ⁰ G and the bathroom holds 60 minutes at this temperature. The fibers are then rinsed and dried. A brown coloration with very good authenticity properties is obtained.

Example 10

From 15 parts of the dye mentioned in Example 1, 15 parts of polyacrylonitrile and 70 parts of dimethylform - ". Mid a stock solution is prepared which is added to a conventional spinning solution of polyacrylonitrile and is spun in a known manner. A brown dyeing with very good fastness properties is obtained.

Claims (1)

Patent claims: 1, Cationic monoazo dyes of the form] Br O ₁ N wherein
R. Hydrogen or methyl, hydrogen or C ₁ -C ₄ -AlCyI, 15th