DE4442291A1 - Di:chloro-tri:pheno:di:oxazine derivs. used for pigmenting plastics - Google Patents

Abstract

6,13-dichloro tripheno dioxazine derivs. of formula (I) are claimed. R1, R2 = H; or R1+R2 = single chain X linking the 8,9-, 9,10- or 10,11-positions; R3 = R4 = H; or R3+R4 = a single chain Y linking the 1,2-, 2,3- or 3,4-positions, with the proviso that R3 and R4 are not H if R1, R2 = H; X, Y = -NR5-(CO)m-NH-, -CR5=CH-CO-NH-, -O-CH2-CO-NH-, -CO-CH=CR5-NH-, -CO-NH-CO-NH-, -CO-NH-CR6=N-, -CR6=N=CO-NH-, -NR5-(CO)m-O- or -NH-CR5=N-; R5,R6 = H, 1-4 C alkyl or phenyl; m = 1 or 2; if R3,R4 and R7 are in the 1,2,3- or 3,4,2-positions or R3,R4 and R7 in the 8,9,10 or 10,11,9-positions, then R7 = H or 1-2C alkoxy, otherwise R7 = H. Also claimed are plastics compsns. (II) contg. (I).

Description

The invention relates to the triphendioxazine compounds of the general Formula I

the cores designated A being, independently of one another, linear, in the 2,3 and 9,10 position, or angular, in the 1,2 and 8,9 or in the 3,4 and 10,11 position, anneals rings with the residual members of the formulas -NR₁- (CO) _m -NH-, -CR₁ = CH-CO-NH-, -O-CH₂-CO-NH-, -CO-CH = CR₁-NH-, -CO -NH-CO-NH-, -CO-NH-CR₂ = N-, -CR₂ = N-CO-NH-, -NR₁- (CO) _m -O- or -NH-CR₁ = N-,
R₁ is hydrogen, C _1-4 alkyl or phenyl,
R₂ is hydrogen, C _1-4 alkyl or phenyl
and m is 1 or 2,
wherein the angular molecules in the 3- and 10-position, respectively in the 2- and 9-position each carry a C _1-2 alkoxy group.

Among the alkyl and alkoxy radicals mentioned are those with 1 or 2 Carbon atoms are preferred.

The preparation of these compounds is characterized in that 1 mol of 2,3,5,6 Tetrachloro-1,4-benzoquinone with 2 moles of a compound of general formula II

where n is 1, 2 or 3,
condensed. If the heterocycles fused to the rings A are different, different compounds of the formula II must be used and measures for an asymmetric condensation must be taken.

The compounds of the formula II are known (see, for example, DE-OS 28 55 883) or leave in analogy to known, described methods, or to another, the To make a professional familiar method without difficulty.

In preferred pigments of the formula I, the formula parts correspond

preferably the formulas a to o.

where the bond denoted by * leads to the nitrogen atom and
R₁ is hydrogen, C _1-4 alkyl or phenyl, preferably hydrogen, methyl or ethyl and
R₂ is hydrogen, C _1-4 alkyl or phenyl, preferably hydrogen, methyl or ethyl
mean.

Most preferred compounds of formula I are those in which both rings A the formula parts a) or j) correspond. The pigments of the formula I according to the invention are ideal for dyeing plastic compounds, including solvent-free and solvent-containing masses of plastics or synthetic resins are understood (in paints on an oily or aqueous basis, in varnishes of various kinds, for Spin dyeing of viscose or cellulose acetate, for pigmenting polyethylene, Polystyrene, polyvinyl chloride, rubber and artificial leather). You can also print inks for graphic arts, pulp dyeing, coating of Textiles or for pigment printing.

The resulting dyeings are characterized by their excellent heat, light and Weather fastness, chemical resistance, color strength and the very good applicator properties, eg. B. Flockulationheit, crystallization and Dispersing fastness and especially by their migrating, efflorescence, overcoating and Solvent fastness.

By the aftertreatment of the crude pigments in organic solvents increased Temperatures, z. B. 110 ° -200 ° C, the pigment properties can often be further improved become. As organic solvents (in which the pigments themselves are not dissolved will come). Chlorobenzene (mixture), nitrobenzene, dimethylformamide, Dirnethylacetamid, glacial acetic acid, ethylene glycol or quinoline into consideration. These Post-treatment is preferably combined with a grinding or kneading operation.

In the following examples, parts are parts by weight and percentages Weight. The temperatures are given in degrees centigrade. A volume part corresponds to the volume of a part by weight of water.  

example 1

In 250 parts by volume of ethanol, 22 parts of 6-methoxy-5-arnino-benzimidazolone- (2), 15 Parts of chloranil (2,3,5,6-tetrachlorobenzoquinone) and 10 parts of anhydrous sodium acetate entered. The mixture is heated to boiling with stirring, allowed to cool, filtered the crystallized intermediate, washed with ethanol, then with water and it dries.

26 parts of this intermediate are concentrated in 150 vol. H₂SO₄ conc. registered and stirred for 12 hours at room temperature. It is then poured out on ice, filtered pigment obtained, it is acid-free with water and dried, eg. B. at 600 in Vacuum. It is also possible to dilute the condensation mixture to 80%, the resulting Filter off the pigment and with 300 parts of 80% H₂SO₄, then with 150 parts of 50% H₂SO₄ and wash acid-free with 2000 parts of water. The moist press cake is then in 250 Divide dimethylacetamide and the remaining water at 100-150 ° distilled off. After cooling to 120 °, the pigment is filtered, with 200 parts of cold Dimethylacetamide and then washed with 100 parts of isopropanol and at 600 im Vacuum dried.

The resulting pigment corresponds to the formula

it colors Violet-colored plastics with excellent migration and solvent resistance.

aftercare

In a kneader heated to 75-78 °, 20 parts of the prepared according to Example 1 Pigments, with 23 parts of ethylene glycol and 160 parts of NaCl at 0.6 bar for 2 Kneaded for hours. It is then suspended in 1500 parts of water and allowed to stand for 2 hours Heated to 80 °. It is then filtered hot and with 4000 parts of hot water washed salt-free. The pigment is dried at 80 ° in vacuo.

Example 2

In 300 parts by volume of ethanol, 24 parts of 4-methyl-5,8-dimethoxy-6-amino-quinolone (2), 12 parts of chloranil and 8.5 parts of anhydrous sodium acetate added, with stirring and reflux cooled for 6 hours, cooled to room temperature, the formed Precipitate filtered off, with ethanol, then with water and again with ethanol washed. The ethanol-wet intermediate is in 300 vol. Parts stirred o-dichlorobenzene to a finely divided suspension, boiled with stirring for 8 hours, wherein the distilled ethanol / dichlorobenzene mixture replaced by o-dichlorobenzene becomes. It is allowed to cool to 100 °, filtered, the residue is washed first with hot o- Dichlorobenzene, then with hot ethanol, then with hot and finally with cold water and dry it.

This gives the pigment of the formula

the plastics in blue shades with excellent migration and solvent fastness colored.  

aftercare

10 parts of the pigment prepared according to Example 2 are in the presence of 30 parts NaCl and 150 parts of acetone in a ball mill of 0.5 l capacity with 1 kg 4 mm diameter steel balls ground for 72 hours. The obtained Ground material is separated from the balls with a sieve, filtered and with 2000 parts Washed salt-free water. The pigment is dried at 80 ° in vacuo.

In analogy to the information in Examples 1 and 2, the pigments of the formula I, wherein rings A correspond to the following formulas a to m.

Ex. Ring A 3 a 4 b 5 c 6 d 7 e 8th f 9 G 10 H 11 i 12 j 13 k 14 l 15 m

The groups a-m are as follows:

Application example 1

4 parts of the pigment according to Example 1 are with
96 parts of a mixture
50 parts of a 60% solution of coconut-aldehyde-melamine resin solution in butanol,
10 parts of xylene and
10 parts of ethylene glycol monoethyl ether
Milled for 24 hours in a ball mill. The resulting dispersion is sprayed onto aluminum sheet, allowed to air dry for 30 minutes and then baked at 120 ° C. for 30 minutes. This gives a brilliant reddish violet film with very good migration fastness and good light and weather resistance.

Application Example 2

Example for the production of a 0.1% colored PVC film (blend of colored pigment to white pigment 1: 5):
16.5 parts of a plasticizer mixture, consisting of equal parts of dioctyl phthalate and dibutyl phthalate, with
0.05 parts of pigment according to Example 1 and
0.25 parts titanium dioxide mixed. Then be
33.5 parts of polyvinyl chloride added. The mixture is rolled for 10 minutes on a two-roll mill with friction, wherein the forming coat is cut with a spatula continuously and rolled up. The one roller is kept at a temperature of 40 °, the other at a temperature of 140 °.

Then the mixture is stripped off as a coat and 5 minutes at 160 ° between pressed two polished metal plates.

So you get a reddish purple colored PVC film of high brilliance and very good Migration and light fastness.

Claims (3)

1. The triphendioxazine compounds of the general formula I the cores designated A being, independently of one another, linear, in 2, 3 and 9, 10 position, or angular, in 1, 2 and 8, 9 or in 3, 4 and 10, 11 position, anneals rings with the residues of the formulas NR₁- (CO) _m -NH-, -CR₁ = CH-CO-NH-, -O-CH₂-CO-NH-, -NR₁- (CO) _m -O-, -CO -CH = CR₁-NH-, -CO-NH-CO-NH-, -CO-NH-CR₂ = N-, -CR₂ = N-CO-NH- or -NH-CR₁ = N-,
R₁ is hydrogen, C _1-4 alkyl or phenyl,
R₂ is hydrogen, C _1-4 alkyl or phenyl
and m is 1 or 2,
wherein the angular molecules in the 3- and 10-position, respectively in the 2- and 9-position each carry a C _1-2 alkoxy group. 2. A process for preparing the triphendioxazine compounds of the formula I, according to claim 1, characterized in that one mole of 2,3,5,6-tetrachloro-1,4-benzoquinone with 2 moles of a compound of general formula II where n is 1, 2 or 3,
condensed. 3. Use of the compounds of the formula I according to claim 1 as pigments, for dyeing plastic compounds.