DD299733A7 - PROCESS FOR PREPARING BLACK TIN PIGMENTS - Google Patents

Abstract

Perylenetetracarboxylic acid or its dianhydride is obtained in aliphatic polyhydric alcohols which may be partially etherified and / or esterified with -methoxy-n-propionylamine, N-carbamidino-3-methyl-pyrazolone, dicyandiamide, ethylenediamine, b-hydroxyethylamine, n-butylamine. Butylamine, guanidine or guanylurea condensed at elevated temperatures without catalyst. The black pigments obtained have special IR reflection behavior.

Description

Characteristic of the known state of the art It is known from DT-OS 2,451,782 that perylenetetracarboxylic acid-N, N'-bis-ethoxypropyl imide is an orange pigment. In

of the 1 (M, 1 BKFAFKDHF the .L.'MY-butyrylaminopropylinnid of perylenetetracarboxylic acid is described as a black pigment.

In DT-AS 2,451,780, the Ν, Ν'-bis-v-hydroxypropylimide and the N, N'-bis-n-propylimld and in the DT-AS 2,451,783

the N, N'-bis-.beta.-phenylethyl imide of perylenetetracarboxylic acid presented as black pigments. A reference to the

Properties and synthesis of the N.N'-bis-v-methoxy derivative is not described. DT-AS 1,569,754 describes the reaction of aminoguanidine and its derivatives with perylenetetracarboxylic acid in

aliphatic and aromatic chlorinated hydrocarbons, in pyridine and quinoline. The DT-AS 1,569,755 and the

DT-AS 1.955.455 describe perylenetetracarboxylic acid condensation in aliphatic and aromatic chlorinated hydrocarbons,

in pyridine and quinoline.

The pigments of DT-OS 2,451,782 are all not black. The synthesis according to DT-OS 2,616,486 is very complicated and

time-consuming, the yield is poor. The DT-AS 2.451.780 supplies relatively low-color, the DT-AS 2.451.783 a very transparent, black-green pigment.

The synthesis processes described in DT-AS 1,569,754, DT-AS 1,569,755 and DT-AS 1.955.455 proceed substantially

slower than the one to describe here.

Object of the invention

The aim of the invention is the discovery of new camouflage pigments which have an extremely low remission in the visible range between 380 nm and 680 μm and a particularly high remission between 740 nm and 1280 nm, consequently appear black and impose very high demands on their light, weather , Solvent and migration fastness, as well as a simple manufacturing process.

Essence of the invention Technical problem to be solved On "-" * e of the invention is to provide novel perylenetetracarboxylic acid N, N'-bisimidpigmente, the new Synthesis points can be obtained and the above aim of the invention should be fair. Features of the invention The invention is characterized by the synthesis of the perylenetetracarboxylic acid N, N'-bisimide pigments of the general

Formula:

in the X = -CE ₀ -CH-CH

¹ ,

Oh'

-CH ₂ CH ₂ OH -CH ₂ CH ₂ -NH ₂

NH-CN

NH-C

ΊίΗ

NH-CO-NH

and R = -H, -Cl, -NO ₂

should be that have excellent properties as black camouflage pigments. The amino or amidino compounds which can be used here are therefore the following:

β-hydroxy-n-propylamine n-butylamine

monoethanolamine

ethylenediamine

dicyandiamide

Aminoguanidine "

guanylurea

guanidine

N-carbamidino-3-methylpyrazolone N-carbamidino-3-methyl-4-nitropyrazolone N-carbamidino-d-methyl-1-chloropyrazolone

The preparation of the perylenetetracarboxylic acid N.N'-blsimldplgmente successi in a simple manner by perylenetetracarboxylic acid or its dianhydride in the reaction medium is stirred together with the reacted amine or amidine derivative at room temperature and heated to 180 to 24O ⁰ C. Used as reaction medium:

ethylene glycol methylpolyglycol Äthylpolyglykol diethylene glycol triethylene propylene glycol dipropylene butyl polyglycol butyl glycol Glycol diacetate

Butanediol-1,3-butanediol-1,4

phenylglycol Xylenylglykol

Glycerine,

octanol dodecyl benzyl alcohol benzyl

In these reaction media, the condensation reactions proceed rapidly and almost quantitatively, if the temperatures are maintained between 160 and 25O ⁰ C for up to 150min. The beginning reaction is indicated by a strong increase in viscosity.

The pigments obtainable in the reaction mixture according to the invention are not always identical to those obtainable in quinoline or trichloro or nitrobenzene pigments. The pigments obtainable by the method according to the invention can often be used without further formation according to special processes for coloring the desired camouflage sets

 The following examples are intended to explain the process:

example 1 FIG. 1 shows a camouflage pigment based on perylenetetracarboxylic acid-N, N'-bis-1-methoxy-n-propyl-imide DE-AS 2.451.281 shown

100 parts of diethylene glycol are mixed with 30 parts perylenetetracarboxylic dianhydride and

Stirring 10 parts of ethylenediamine, then heated to 11O ⁰ C, the stirred mixture thickens and turns black. Now slowly heated to 200 ⁰ C and left for 30 min. It is cooled to about 150 ⁰ C, then diluted with dimethylformamide to twice the volume and filtered off at about 5O ⁰ C. The filter cake is reslurried in hot dimethylformamide, then filtered off and washed with water. This gives 37.5 parts of perylenetetracarboxylic acid N, N'-bis (ßaminoäthyOimid as deep black powder.

Example 3

Working according to Example 1, but using diethylene glycol and 12.8 parts of 1-N-carbamidino-3-methylpyrazolone- (5), we obtain 43.6 parts perylenetetracarboxylic acid N, N'-bis (1'-N "- carbamidino-3'-methylpyrazolone (5 ') imide as a violet-black powder.>

Example 4 However, benzyl alcohol is used according to example 1 and 12.8 parts of dicyandiamide are added to give 36.2 parts Perylenetetracarboxylic acid -N.N'-bis-la-cyanamino-α-iminol-methylimide as violet-black powder. Example 5 If, according to Example 1, phenylglycol is used and 20.4 parts of aminoguanidine carbonate are added, 43 parts of the product are obtained

corresponding bisimides as a black-violet powder.

Examples Except using ethylene glycol as in Example 1 and slowly heated to 18O ⁰ C, the result is an equally good pigment such as

according to Example 1, but only 31.8 parts of the black pigment.

Example 7

If, however, according to Example 1 diglycol and 14.1 parts of guanylurea, we obtain 39.2 Teilö of a violet-black pigment, which is the perylenetetracarboxylic acid-N, N'-bis (a-imido-a-ureido) methylimide.

Example 8 If, however, triglycol is used according to example 1 and 19.6 parts of guanidinium bicarbonate are used, 40.2 parts of one are obtained

black-violet pigments.

Example 9 If, however, according to Example 1, n-octyl alcohol, we obtain after 120 min at 165 ⁰ C, a black pigment the same

Quality.

Claims (1)

A process for the preparation of black Tarnp segments, characterized in that perylenetetracarboxylic acid or its dianhydride to Ν, Ν'-bisimides of the following general formula: OH CHgCHgCHg-CHO -CHgCHgOH CH2CHGNHg NH - CN NHg NH - Cv NHg NH-CO-NHg X - Ν _ν ) = ⁱ \ A =: ' NX in the X = -CH ₂ -CH-CH ₃ - N and R = -H, -CI, -NO 2 should be, being used as the reaction medium alcohols of chain length C ₆ to C ₁₂ , di- and trialcohols and their semi-or Volläther or esters and araliphatic alcohols or their esters and at temperatures between 8O ⁰ C and 28O ⁰ C, preferably 16O ⁰ C and 23O ⁰ C, are reacted over a period of 30 to 150 min. For this 8 pages drawings Field of application of the invention The invention relates to a process for the preparation of black camouflaged pigments of the perylenetetracarboxylic diimide series. These pigments can be used for dyeing and printing on plastics, such as polyvinyl chloride, aminoplasts, cellulose derivatives, alkyd resins, polyethylenes, rubbers and silicones, of lacquers based on cellulose derivatives, post-chlorinated PVC or polyethylene or rubber, Vkyd, Epoxyd, Phthalates, polyesters or natural resins, polyurethanes, silicones, latices, amine resins and mouse paints of paper, polyacrylonitrile and printing inks, whereby the special use in camouflage sets to imitate the remission behavior of leaf green in various green to olive, more rarely sandy to earthy or gray Nuances can be made according to the specific tolerance curves. .