DE3501199A1 - Azo pigment dyes - Google Patents

Abstract

Pigment dye mixtures having particularly good dispersibility, prepared by coupling a compound of the formula H3C-CO-CH2-CO-NH-R2-NH-CO-CH2-CO-CH3 with 8 to 20 mol per cent of diazotised anthranilic acid C1-4-alkyl ester and 80 to 92 mol per cent of diazotised aminoterephthalic acid di-C1-4-alkyl ester.

Description

Case 150-4871

AZO - PIGMENT DYES

350119jB

It has been found that mixtures of azo pigments of the Formula I a, I b and I c

R ₁ O-CO

COOR,

VVp- ^COoR i

Il

H ₃ C - CO - CH - CO - NH

Il

R ₂ - NH - CO - CH - CO - CH ₃

(I.

-CO

COOR ₁

Il

H ₃ C -CO-CH-CO-NH COOR ₁

Il

N - NH - CO - CH - CO - CH.

(I b),

COOR ₁

Il

H ₃ C

- CO - CH - CO - NH R ₂ - NH

COOR ₁

Il

N CO-CH- CO -CH ₃

(I.

INSPECTED

- 5 - Case 150-4871

wherein the Ri independently of one another Ci_4-Alky1reste and

the f * 2 independently of one another each have a 1,4-phenyl radical, the up to can carry to two substituents, namely up to two methyl, methoxy, chlorine or bromine and / or one trifluoromethyl or nitro, each a 4,4'-biphenylene radical, which is in the 3 and 3'-position by chlorine, bromine, methyl and / or Methoxy is substituted, or a 1,4- or 1,5-naphthylene radical mean,

where in the mixture of the dyes of these three formulas 8 to 20 mol percent Benzoic acid ester residues and 92 to 80 mole percent terephthalic acid ester residues are present, excellent for dyeing plastic masses, and are particularly suitable for spin-dyeing polypropylene fibers. The mixtures according to the invention have, in addition to the very good general Fastness properties, especially light fastness, excellent dispersibility, which makes it possible to use them for spin-dyeing because the staple fibers have a high tensile strength. Especially in this capacity they are the individual components of the mixtures according to the invention think. The high color strength of the new pigment mixtures should also be mentioned.

Particularly preferred are the pigment dye mixtures in which in the Formulas I a, I b and I c

^R l Ci_2 ~ alkyl radicals and R2 optionally has one or two substituents from

1,4-phenylene bearing series of chlorine, methyl and methoxy, 3,3'-dichloro-, -dimethoxy- or -dimethyl-4,4'-biphenylene or 1,5-naphthylene.

Particularly preferred are the pigment mixtures in which R ^ Ci_2-Alkylreste and R2 is unsubstituted 1,4-phenylene and the 8 to 12 mole percent benzoic acid ester residues and 92 to 88 mole percent terephthalic acid ester residues contain.

- () - Cast l'j (MH / l

The production of the new pigment mixtures is characterized by

that mnan 0.8 to 2 mol of a diazotized amine of the formula II a

COOR.

(H a) "2

and 9.2 to 8 moles of a diazotized amine of formula II b

R ₁ O - CO

(H b)

with 5 moles of a compound of the formula III qoOR

H ₃ C-CO-CH ₂ -CO-NH-R ₂ -Nh-CO-CH ₂ -CO-CH ₃ (III) couples.

The compounds of the formulas II a, II b and III are known. Diazotize and domes are carried out according to commonly used methods.

In the following examples, parts mean parts by weight and Percentages by weight. The temperatures are given in degrees Celsius.

example

a) 76.0 parts of 2-aminoterephthalic acid dimethyl ester and 6.1 parts of anthranilic acid methyl ester are concentrated with 10 parts of water and 10 parts by volume. Hydrochloric acid stirred for four hours. You cool in an ice / Water bath and by adding 125 parts of ice to 0 ° and the mixture is mixed with 105 parts by volume of 4N aqueous sodium nitrite solution. This solution is stirred for a further hour at 0 to 5 °, low Quantities of excess nitrite are destroyed with aminosulfonic acid and finally filtered clear.

- 7 - Case 150-4871

350119?

b) 55.2 parts of Ν, Ν-diacetoacetic acid para-phenylenedianiide are in Share water and 60 parts by volume of 30 percent sodium hydroxide solution Dissolved about 50 ° and the solution filtered.

c) The diazonium salt solution (according to a) is with 1000 parts of water and 600 parts of ice are added and the pH is adjusted to 4.0 with sodium acetate solution. Then the solution of the coupling component (according to b) flow in over the course of approx. 30 minutes. A lemon-yellow suspension is formed, which is 2 hours at 5 to 10 °, 1 hour at 40 ° to 45 "and 1 hour at 80 to 85". Thereupon the suspension filtered, the press cake washed salt-free, dried and ground. He colors plastics in very real, yellow tones.

By varying the molar proportions of dimethyl 2-aminoterephthalate (or other, C2_4 ~ alkyl ester) and anthranilic acid methyl (or a C2_4 ~ alkyl) ester within the limits given above is obtained Pigment mixtures with very similar properties. Is used in place of the Ν, Ν-diacetoacetic acid para-phenylenediamide the product essentially substituted by methyl, a strongly reddish-tinged pigment is obtained, para-phenylenediamide substituted by methoxy gives orange pigments and the chlorine-substituted product a greenish-yellow pigment.

In general, the pigment properties, in particular the light fastness and the dispersibility, of the mixtures according to the invention, by treating the raw dyes in a high-boiling solvent, in particular dimethylformamide or 1,2-dichlorobenzene, still to be improved.

- 8 - Case 150-4871

APPLICATION EXAMPLE

70 parts of commercially available polyethylene with a low molecular weight and 30 parts of the pigment mixture prepared according to the above example are processed into a dye concentrate in an extruder. This concentrate is then in a ratio of 1:50 with commercially available Polypropylene blended and spun into fibers in the usual way. Mixed with polyethylene in the same proportion, it can also become too Blown films are processed.

Claims (7)

SANDOZ-PATENT-GMBH 7850 Lörrach Case λ50-4871ft / AZO - PIGMENT DYES Patent claims 1. pigment dye mixture containing compounds of the formulas I a, I b and I c R ₁ O-CO COOR ₁ R ₁ OC COOR ₁ H ₃ C -CO- N N Il Il N N 'I - CO - NH - R ₀ - NH - CO - CH - CO - CH. (I a), COOR ₁ R ₁ O-CO Il NH ₃ C -CO-CH COOR ₁ Il N - CO - NH - R ₀ - NH - CO - CH - CO - CH, (I b). Case 150-4871 COOR ₁ COOR ₁ -CO-NH-R ₂ -NH-CO-Ch-CO - (I c), wherein the Ri independently of one another Ci_4-Alkylreste and R ₂ independently of one another each have a 1,4-phenylene radical which can carry up to two substituents, namely up to two methyl, methoxy, chlorine or bromine and / or a trifluoromethyl or nitro, and a 4,4'-biphenylene radical in each case 3 and 3'-position is substituted by chlorine, bromine, methyl and / or methoxy, or are each a 1,4- or 1,5-naphthylene radical, where in the mixture 8 to 20 mol percent of benzoic acid ester residues and 92 to Mol percent terephthalic acid ester residues are present. 2. A pigment dye mixture according to claim 1, wherein in the formula I a, I b and I c ^ l Ci_ ₂ -alkyl radicals and R ₂ optionally denotes 1,4-phenylene, 3,3'-dichloro-, -dimethoxy- or -dimethyl-4,4'-biphenylene or 1,5-naphthylene bearing one or two substituents from the series consisting of chlorine, methyl and methoxy . 3. Pigment dye mixture according to claim 1, wherein in the formulas I a, I b and I c Ri are Ci_ ₂ -alkyl radicals and R _{2 are} unsubstituted 1,4-phenylene. - 3 - Case 150-4871 4. A pigment dye mixture according to claim 1, 2 or 3, which is in a mixture 8 to 12 mole percent benzoic acid residues and 92 to 88 mole percent Contains terephthalic acid residues. 5. Production of the pigment dye mixture according to claim 1, characterized in that characterized in that 0.8 to 2 mol of a diazotized amine of the formula II a COOR ₁ a) and 9.2 to 8 moles of a diazotized amine of formula II b R ₁ O - CO NH ₉ ² (H b) COOR ₁ with 5 moles of a compound of formula III H3C-CO-CH2-CO-NH-R2-NH-CO-CH2-CO-CH3 (III) clutch. 6. Use of the pigment dye mixture according to claims 1, 2, 3 or 4 for coloring plastic masses. 7. Use of the pigment dye mixture according to claims 1, 2, 3 or 4, for spin-dyeing polypropylene fibers.