DE3230433A1 - The use of metal complex dyes for dyeing plastic materials - Google Patents

Abstract

The invention relates to the use of disazomethine dyes of the formula I <IMAGE> in which the ring A may carry one or two, and the rings B and D may each carry one, two or three substituents from the series comprising cyano, halogen, nitro, C1-2-alkyl, C1-4-alkoxy, benzoylamino, chlorine-, bromine-, methyl-, benzoyl-, C1-2-alkoxy- or nitro-substituted benzoylamino, C2-3-acylamino, carboxyl, C1-4-alkoxycarbonyl, amino- carbonyl, mono- or di(C1-4-alkyl)aminocarbonyl, phenylaminocarbonyl, phenylsulphonylamino or N-C1-4-alkyl-N-phenylaminocarbonyl, and Me is nickel or copper, for mass dyeing of plastics.n

Description

THE USE OF METAL COMPLEX DYES TO COLOR PLASTIC

MATERIALS It has been found that the disazomethine dyes of the general formula I wherein the nucleus A has one or two, the nuclei B and D each have one, two or three substituents from the series cyano, halogen, nitro, C12-alkyl, C14-alkoxy, benzoylamino, once or twice by chlorine, bromine, methyl, Benzoyl, C1 2 -alkoxy or nitro-substituted benzoylamino, C2 3-acylamino, carboxyl, C1 4-alkoxycarbonyl, aminocarbonyl, mono- or di 4-alkyl) -aminocarbonyl, phenylaminocarbonyl, phenylsulfonylamino or N-C1 4-alkyl-N -phenylaminocarbonyl and Me means nickel or copper, excellent for mass coloring plastics, especially linear, aromatic polyesters and synthetic polyamides.

The dyes (or also dye mixtures) of the formula 1 a used, where R1 and / or R1 are hydrogen, methyl, nitro, chlorine or carboxyl, R2 and R21 are hydrogen or phenylsulfonylamino, R3 and R3 are hydrogen, methyl, methoxy or ethoxy and Me is nickel or copper, especially nickel.

Particularly preferred are the dyes of the formula I a in which R1 Hydrogen, chlorine, methyl, nitro or carboxyl, especially hydrogen or carboxyl and R ;, R2, R2, R3 and R3 are hydrogen, as well as those in which R1 and R1 = CH3 and R2, R2, R3 and R3 represent hydrogen.

In addition to the preferred use of the dyes of the formula I for mass dyeing of synthetic polyamides and especially high molecular weight, linear, aromatic Polyesters, these dyes can also be used for dyeing e.g. polyethylene, polypropylene, Polyvinyl chloride and polyacrylonitrile can be used in bulk.

The dyes of the formula I are known or can be prepared analogously to known processes [see e.g. Pfeiffer, Liebig's Annalen Vol. 503, (1933), pp. 84-130] easy to manufacture.

Among linear, saturated aromatic polyesters are in particular those to be understood by polycondensation of terephthalic acid and optionally Isophthalic acid, can be produced with ethylene glycol and / or cyclohexanediol. before all of them include the high-molecular, linear ones used in the textile industry Understand polyester materials.

Bulk dyeing is carried out by customary methods. In general the dyes or mixtures thereof after the necessary cleaning and grinding in the form of dye concentrates, the so-called "masterbatches", the polyester spinning mass added. The masterbatch is preferably produced by mixing one (if necessary low-melting) linear, saturated, aromatic polyester or copolyester with the finely ground dye.

Mixing can also be done, for example, by freezing with dry ice and Milling the polyester to a powder, mixing with the dye and optionally Processing of the mixture into granules in an extruder.

This mixture, be it in powder form or in the form of granules, either mixed with undyed polyester granulate and spun or in melted form State added to the spinning polyester mass.

The dye concentrates generally contain 15 to 60 percent by weight Dye and 85 to 40 percent by weight (low melting point) polyester.

After mixing the dye concentrate with the high molecular weight Polyester, this is further processed in a known way, e.g. to granules, Chips, films, foils or, preferably, fibers or threads that in turn reprocessed into yarns, cords, ropes, woven, knitted or "non-wovens" will.

The granules or chips are then processed in a further operation processed into films, foils, fibers or threads.

The dyes can also be condensed into the polyester material will. This means that you can use the dyes, e.g. the bis-ethylene glycol terephthalate polycondensation compound Add in the amounts necessary for the desired depth of color and the polycondensation perform in their presence.

In any case, the dyes must be in bulk when dyeing in bulk To be completely soluble, this is the only way to make the dyed material into fibers and to spin thin threads. Pigments, which by definition are insoluble, cannot be used for dyeing textile pulp. According to the invention The dyes used have excellent properties in the specified materials Solubility.

The dyeings obtained meet high fastness requirements, in particular to be mentioned are the light, migration, gas fume, ozone and sublimation fastness as well the wet fastness properties. The stability of the dyes mentioned is of the greatest importance compared to those occurring in the manufacture or processing of the polyester (Heat) exposure.

In the following examples the parts mean parts by weight which Temperatures are given in degrees Celsius.

Example 1 1000 parts of a commercially available polyester made from terephthalic acid and ethylene glycol are ground in a pin mill to a powder whose Polyester particles have a diameter between 300 and 600 μm. At room temperature This polyester powder is made in a closed mixer with 150 parts of the fine ground, unsubstituted dye of the formula I, in which Me is nickel, well mixed and then in an extruder at 250 ° throughout to form one Processed cable, which is then cut into granules.

In the main flow of a screw spinning machine, commercially available linear, aromatic polyester (polyethylene terephthalate) heated to 270-275 ° and means a dosing device with the dye concentrate melted in the bypass flow, which was prepared as described above, added. The dosing device sets the polyester stream 4 parts of dye concentrate per 48 parts of polyethylene terephthalate to. The mixture is then at 270-275 ° with a take-off speed of 200 Meters per minute, the fibers are spun in a stretching machine 900 stretched in a ratio of 1: 4 and in a ring twisting machine in the usual way twisted. A very real dyed brown-orange yarn is obtained in this way.

The unsubstituted dye of the formula used in the above example I can be prepared as follows: 22.4 parts of salicylaldehyde are in 200 parts Ethanol dissolved at boiling temperature with a solution of 24.9 parts of Ni (CH3C00) 2.4H20 and 27.2 parts of sodium acetate in 100 parts of water are added, under reflux for one hour cooked and slowly at boiling temperature with a solution of 10.8 parts of ortho-phenylenediamine added in 80 parts of ethanol. The mixture is refluxed for a further 5 hours and cooled to ambient temperature, the red-brown precipitate is filtered off and washed with a little ethanol and dry it. For cleaning, 20 parts of the obtained The dye was boiled in 200 parts of dimethylformamide for 1 hour, and the suspension was filtered cold and washed with dimethylformamide, ethanol and water and the dye in vacuo dried.

The other dyes can also be used in accordance with the procedure in Example 1 of formula I can be used. In this way fibers or yarns with a greenish-yellow tinge are obtained to dark red-brown nuances. For example, the nickel-containing dyes give the Formula I a, where R1 = nitro and the other substituents are hydrogen, colorations dark red-brown shade, R1 = carboxyl and the other substituents hydrogen, gives red-brown shades of color, R1 and R1 = methyl, the other substituents Hydrogen, gives coloration of a brown-orange shade, R1 = methyl, the other substituents Hydrogen, gives coloration of a brown-orange shade, R1 = chlorine, the other substituents Hydrogen, gives coloration of brown-orange nuances, R2 and R2 = phenylsulfonylamino, the other substituents are hydrogen, give colorations of a golden-yellow shade, R3 and R3 = methoxy, the other substituents are hydrogen, gives yellow-brown colorations Nuance.

With the dyes of the formula I a, in which Me is copper and R1 = Chlorine or methyl and the other substituents are hydrogen, colors greenish yellow shade.

Example 2 1360 parts of ethylene glycol and 1700 parts of dimethyl terephthalate together with 0.55 parts of manganese acetate are stirred for 3 1/2 hours for approx. 1800 heated and the methanol formed is distilled off.

The mass is then suitable for polycondensation in a vacuum Vessel transferred with a mixture of 80 parts of ethylene glycol, 0.45 parts Antimony trioxide, 2.0 parts of trinonylphenyl phosphite and 17 parts of the unsubstituted Dye of the formula 1, wherein Me is nickel, added and with stirring at a successively increasing vacuum up to 1 Torr. heated to 275 ° until, while distilling off of ethylene glycol, the intrinsic viscosity has reached a value of q = 0.70.

The dyed polyester thus obtained is now in strand form for cooling pressed in water, granulated, the granules dried in vacuo at 140 ° for 16 hours and finally spun, drawn and, analogously to the information in Example 1 twisted. A brown-orange yarn with excellent properties is obtained in this way.

In accordance with the above rule, the others in example 1 mentioned dyes are used.

Claims (7)

THE USE OF METAL COMPLEX DYES FOR COLORING PLASTIC MATERIALS Patent Claims 1. The use of the disazomethine dyes of the general formula I wherein the nucleus A has one or two, the nuclei B and D each have one, two or three substituents from the series cyano, halogen, nitro, C1-2-alkyl, C14-alkoxy, benzoylamino, through chlorine, bromine, methyl, benzoyl, C1 2-alkoxy or nitro-substituted benzoylamino, C2 3-acylamino, carboxyl, C1 4-alkoxycarbonyl, aminocarbonyl, mono- or di- (C1-4-alkyl) -amino-carbonyl, phenylaminocarbonyl, phenylsulfonylamino or N-C1 4 -Alkyl-N-phenylaminocarbonyl and Me mean nickel or copper for mass coloring plastics. 2. The use of a dye or a mixture of dyes of the formula I a wherein R1 and / or R; Hydrogen, methyl, nitro, chlorine or carboxyl, R2 and R21 denote hydrogen or phenylsulfonylamino, R3 and R3 denote hydrogen, methyl, methoxy or ethoxy and Me denotes nickel or copper, in particular nickel. 3. The use of a dye of the formula I a, according to claim 2, where R1 is hydrogen, chlorine, methyl, nitro or carboxyl, especially hydrogen or carboxyl and Rl, R2, R2, R3 and hydrogen, as well as those in which R1 and Rj = CH3 and R2, R2, R3 and R3 are hydrogen. 4. The use of the compounds according to claim 1 for dyeing synthetic polyamides in bulk. 5. The use of the compounds according to claim 1 for dyeing linear aromatic polyesters in bulk. 6. Dye concentrates containing 15 to 60 percent by weight of one or more contain several dyes of the formula I according to claim 1 in dissolved form. 7. Plastic compounds containing one or more dyes of the formula I contained in dissolved form.