DE3413603A1 - Metal complex dyes and their use for dyeing plastic compositions - Google Patents

Abstract

Sulphonamide-substituted, metallated bisazomethine dyes are outstandingly suitable for dyeing compositions of linear, aromatic polyesters.

Description

A-

Case 150-4872

METAL COMPLEX DYES AND THEIR USE FOR COLORING PLASTIC COMPOUNDS

It has been found that the disazomethine dyes of the general Formula I.

wherein R ₁ and R ^ independently of one another carry hydrogen, unsubstituted or water-insolubilizing substituents

C-j_ ₄ ~ alkyl or phenyl,
the two R ₃ hydrogen, C ^ -alkyl, C _1-2 -AIkOXy or halogen, or, bonded in the 3- and 4-position, a group of the formula -CH = CH-CH = CH- and

Me mean nickel, cobalt, copper or zinc, excellent for mass coloring polyesters.

The dyes (or also dye mixtures) are preferably the above formula I used,

where R, and R _? , independently of one another hydrogen or C, _ ₄ ~ A1kyl, the two R ₃ is hydrogen, C ^ -alkyl, C _1-2 -alkoxy, chlorine or bromine, and Me is nickel cobalt, copper or zinc.

The compounds of the formula I a

Case 150-4872

(I a)

wherein R and R "independently of one another hydrogen, unsubstituted or C,. -alkyl or phenyl bearing substituents that do not make water solubility,

the two R.s are hydrogen, C, p-alkyl, C, ₂ -alkoxy or halogen, and Me is nickel, cobalt, copper or zinc, and the compounds of the formula I b,

(I b),

wherein R- is hydrogen, unsubstituted or insoluble in water C, «-alkyl or phenyl bearing making substituents,

R, - unsubstituted or non-water-solubilizing subs tuo

ducks-bearing C, _.- alkyl and Me nickel, cobalt, copper or zinc

mean, are new and therefore also a subject of the present invention per se.

The new compounds of the formulas I a or I b are prepared by metallizing a compound of the formulas II a or II b

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(Π a)

(II b)

with nickel, cobalt, copper or zinc.

The connections Ila and Hb are metallized in a general manner known manner [e.g. Pfeiffer, Liebig's Annalen, Vol. 503 (1933), P.84-130].

The compounds of the formulas Ila and Hb can be easily, in analogy on processes for the production of similar compounds (e.g. DE-OS 20 07 844).

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

Among linear, saturated aromatic polyesters are in particular to be understood as those produced by polycondensation of terephthalic acid and optionally isophthalic acid, with ethylene glycol and / or cyclohexanediol getting produced. In particular, these include the high molecular weight, linear polyester materials used in the textile industry to understand.

Bulk dyeing is carried out by customary methods. In general the dyes or mixtures thereof are after the necessary cleaning and grinding in the form of dye concentrates, the so-called "Masterbatches", added to the polyester pulp. The masterbatch is preferably prepared by mixing a (optionally low-melting) linear, saturated, aromatic polyester or copolyester with the finely ground dye.

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Mixing can also be done, for example, by freezing with dry ice and grinding the polyester to a powder, mixing with the dye and, if necessary, processing the mixture into granules in an extruder, be performed.

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

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

After the dye concentrate has been mixed with the high molecular weight polyester, it is further processed in a known manner, e.g. to granules, chips, films, foils or, preferably, to fibers or threads, which in turn are made into yarns, cords, ropes, woven, knitted or " Non-Wovens ^{N are} processed.

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. This means that the dyes, e.g. the bis-ethylene glycol terephthalate polycondensation compound, can be used in the colors required for the desired depth of color add the necessary amounts and carry out the polycondensation in their presence.

In any case, the dyes must be completely soluble in the mass during mass dyeing, this is the only way to make the dyed material possible To spin fibers and thin threads.

The dyes used according to the invention have excellent solubility in the specified materials.

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The dyeings meet high fastness requirements, particularly noteworthy are the light, to migration, gas Fume-, ozone and subli mierechthe it and the wet fastness properties. The stability of the dyes mentioned with respect to the (heat) stress that occurs during the production or processing of the polyesters is of the greatest importance.

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

Example 1_

24.4 parts of salicylaldehyde are dissolved in 500 parts of ethanol at room temperature, 24.9 parts of Ni (CH-COO) ₂ ^ H ₂ O are added, and 26.3 parts of 3,4-diaminobenzene-1-sulfonic acid phenylamide are slowly added at the boiling point offset. It is boiled under reflux for a further 5 hours, cooled to ambient temperature, the red-brown precipitate is filtered off, washed with ethanol and dried.

Analogously to the working instructions of this example, the dyes the table below, in which the substituents according to formula I are entered, are prepared.

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T a b e 1 le

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example
No. ^R l ^R 2 ^R 3 Me 2 -CH ₃ H H Ni 3 -CH ₃ ■ ^CH 3 H Ni 4th -C ₂ H ₅ H H Ni 5 - ^C 2 ^H 5 - ^C 2 ^H 5 H Ni 6th HC ₄ H ₉ H H Ni 7th - ^CH 3 - ^C 6 ^H 5 H Ni 8th H H H Ni 9 - ^CH 3 - ^CH 3 H CO 10 ■ ^C 2 ^H 5 H H Cu 11th ■ ^CH 3 " ^CH 3 H Zn 12th " ^CH 3 -H 4-OCH ₃ Ni 13th - ^CH 3 - ^CH 3 3-CH ₃ Ni 14th -C ₂ H ₅ -C ₂ H ₅ 4-Cl Ni 15th -CH ₃ -CH ₃ 3-CH = CH-CH = CH-4 Ni

The nuances of the disgusting dyes are yellow-brown to red-brown, those of the cobalt-containing dyes brown, those of the copper-containing dyes The dyes are brown and those of the zinc-containing dyes are yellow.

Case 150-4872

COLOR EXAMPLE 1

1000 parts of a commercially available polyester made from terephthalic acid and ethylene glycol are ground in a pin mill to form a powder, the polyester particles of which have a diameter between 300 and 600 μ . At room temperature, this polyester powder is mixed well in a closed mixer with 150 parts of the finely ground dye according to Example 1 and then processed in an extruder at 250 ° throughout to form a 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, by means of a metering device, the dye concentrate, which has been melted in the bypass flow and prepared as described above, is added. The metering device adds 4 parts of dye concentrate per 48 parts of polyethylene terephthalate to the polyester stream. The mix will then spun at 270-275 ° with a take-off speed of 200 meters per minute, the spun fibers in a stretching machine at 90 ° im Ratio 1: 4 drawn and in a ring twisting machine on the usual Twisted wisely. A very real dyed orange yarn is obtained in this way.

COLOR EXAMPLE 2

1360 parts of ethylene glycol and 1700 parts of dimethyl terephthalate will be together with 0.55 parts of manganese acetate while stirring for 3 1/2 hours for approx. Heated to 180 ° and the methanol formed was distilled off.

The mass is then transferred to a vessel suitable for polycondensation in vacuo, mixed with a mixture of 80 parts of ethylene glycol, 0.45 parts of antimony trioxide, 2.0 parts of trinonylphenyl phosphite and 17 parts of the dye according to Example 3 and gradually increasing with stirring Vacuum to 1 Torr, heated to 275 ° until, with removal of ethylene glycol by distillation, the intrinsic viscosity has reached a value of η = 0.70.

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The dyed polyester thus obtained is now in strand form for cooling pressed in water, granulated, the granules at 140 ° for 16 hours dried in vacuo and finally spun, drawn and twisted analogously to the information in dyeing example 1. This gives an orange yarn with excellent properties.

In accordance with the above regulations, the others in the table mentioned dyes are used.

Claims (4)

SANDOZ-PATENT-GMBH Case T50-4872 L ö r r a c h METAL COMPLEX DYES AND THEIR USE FOR COLORING PLASTIC COMPOUNDS Patent claims 1. The use of the compounds of the formula I. (I), R ₃ ο / = NN = v - ρ where R. and R _? independently of one another hydrogen, unsubstituted or carrying substituents which do not make water soluble C, ₄ -alkyl or phenyl, the two R- hydrogen, C, «-alkyl, C, ,, - alkoxy or halogen, or, bound in 3- and 4-position, a group of Formula -CH = CH-CH = CH- and Me mean nickel, cobalt, copper or zinc for coloring polyesters in bulk. «F Case 150-4872 2. The use of the compounds of the formula I according to claim 1, in which R 1 and R ₂ independently of one another are hydrogen or C _{1 -alkyl, the two R 3 are} hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, chlorine or Bromine and Me mean nickel, cobalt, copper or zinc for coloring polyesters in bulk. 3. The compounds of formula I. SO ₂ NR ₁ R ₂ N N (Ia), wherein R, and R- independently of one another hydrogen, unsubstituted or water-insolubilizing substituents carrying C, - alkyl or phenyl, the two R ^ hydrogen, C, ,, - alkyl, C-, "-alkoxy or halogen, and Me mean nickel, cobalt, copper or zinc. 4. The compounds of the formula I b> (Ib) wherein R _{5 is} hydrogen, unsubstituted or non-water-solubilizing substituents carrying C ^^ - alkyl or 3Α13603 Case 150-4872 ^R 6 Me Phenyl, unsubstituted. or non-water-solubilizing C 1-4 -alkyl and Mean nickel, cobalt, copper or zinc. Process for the preparation of compounds of the formula I a, according to Claim 3, characterized in that a compound of the formula II a (II a) metallized with nickel, cobalt, copper or zinc. Process for the preparation of compounds of the formula I b according to Claim 4, characterized in that a compound of the formula II b (II b) metallized with nickel, cobalt, copper or zinc. 3700 / HW / HB