DE1272270B - Use of N, N'-dimethyl-3, 4, 9, 10-perylenetetracarboxylic diimide as pigment - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Irt. CL:

German class:

Number:
File number:
Registration date:
Display day:

D06p

C09d; C08g;
C09b

8m-12

22 g-10/01; 39 b-22/01;

8m-13

P 12 72 270.2-43 (B 61102)

February 2, 1961

July 11, 1968

It is known that N, N'-dimethyl-3,4,9,10-perylenetetracarboxylic acid diimide is used as a vat dye (C.I. Vat Red 23, Color Index, 2nd Edition, 1956, Vol. 2, p. 2466, C.I. No. 71130). It colors as from the literature, for example from the book by H. A. Lubs, “The Chemistry of Synthetic Dyes and Pigments ", p. 482 (New York, 1955), or is known from the German Auslegeschrift 1 031 449, Textile goods made of cotton in rather dull red tones. The lightfastness properties of cotton dyeings lie between the values 6 and 7 of the eight-point wool scale, depending on the color depth.

The invention now relates to the use of NjN'-dimethyl-S ^ ÄlO-perylenetetracarboxylic acid diimide as a pigment, except for the dyeing of high-melting, high-molecular polymers in bulk. For this use, the NjN'-dimethyl-S ^ ÄlO-perylenetetracarboxylic acid diimide as a marron-colored, strongly colored, pure, extremely light, weather, chemical and solvent-resistant Pigment ideally suited. The new pigment gives pigment-colored masses and mixtures of good brilliance and high color fastness.

It is advantageous to use Ν, Ν'-dimethyl-3,4,9,10-perylenetetracarboxylic acid diimide at a primary particle size of between 0.05 and 5 μ, preferably particularly well suited for pigment properties between 0.3 and 2 μ or between 0.05 and 0.5 μ, or with an even smaller mean primary particle size advantageously in the form of preparations with up to 20%, preferably up to 10%, calculated based on the weight of the dye, on partially or completely oil-soluble emulsifiers or on insoluble ones solid or other protective colloids, optionally mixed with up to 2%, calculated on the weight of the dye, of water-soluble dispersants.

The pigment dye can be used, for. B. for coloring flush pastes, printing inks, glue colors, Binder paints or varnishes of all kinds, such as physically and oxidatively drying varnishes, acid, amine and Use peroxide-curing paints or polyurethane paints, especially car paints. One can new pigment but also the dyeing of synthetic, semi-synthetic or masses natural macromolecular substances such as polyvinyl chloride, polystyrene, phenoplasts, aminoplasts and use rubber. Also for dyeing natural, regenerated or artificial fibers, such as glass, silicate, asbestos, wood, cellulose, acetyl cellulose, polyacrylonitrile, polyurethane and poly

Use of N, N'-dimethyl

3,4,9,10-perylenetetracarboxylic acid diimide as

pigment

Applicant:

Aniline & Soda Factory in Baden

Aktiengesellschaft, 6700 Ludwigshafen

Named as inventor:

Dr. Ewald Daubach, 6700 Ludwigshafen;

Dr. Bruno Hirsekorn, 6800 Mannheim;

Dr. Hanns Wüst, 6702 Bad Dürkheim;

Hans-Werner Schröder,

Dipl.-Chem. Heinrich Sixtus,

6700 Ludwigshafen;

Hans Langenfelder, 6800 Mannheim

Claimed priority:

Belgium of March 30, 1960 (467 767)

vinyl chloride fibers or their mixtures, the new pigment is suitable. Also it comes for coloring Powders, e.g. B. organic or inorganic pigments, rock flour, cements, gypsum, starch and wood flour into consideration. With the pigment according to the invention, prints, varnishes, paints, Coverings, coatings, shaped structures such as foils, threads, plates, blocks, granulates and Sticks with brilliant color and excellent durability.

The pigment-colored mixtures, which are the effective coloring component, the brilliant, marron-colored and contain pigments according to the invention which are very lightfast and weather-resistant, can per se known processes are produced. For example, for the production of flush pastes, Printing inks, glue paints, plastic dispersions and spinning solutions, pigment doughs or other preparations be used. However, the pigment can also be stirred in, rolled in, kneaded in or Grinding in water, organic solvents, non-drying oils, drying oils, lacquers, plastics or rubber. Finally, it is also possible to dry the pigment Mixing with organic or inorganic compounds,

809 569/583

Granulates, fibers, powders and other pigments to be processed into mixtures of substances.

The use of N ^ '- Dmethyl-SA ^ 10-perylenetetracarboxylic acid diimide is of particular technical interest for coloring natural and / or synthetic resins, lacquers, fibers, plastics, rubber, binder paints, printing inks, Glue paints, dry paints and flush pastes.

The mean primary particle size of the crystals which is particularly well suited for use as a pigment of N, N'-dimethyl-3,4,9,10-perylenetetracarboxylic acid diimide is between 0.05 and 5 μ, preferably between 0.3 and 2 μ, or between 0.05 and 0.5 μ in Direction of their greatest extent. The other two dimensions are relatively small and usually do not exceed the value of 0.5 μ.

Dye particles with an average primary particle size of 0.3 to 2 μ can be obtained in different Win way, e.g. B. by pumping the dye at about 50 to 60 ° C and slow oxidation, appropriately with air. The vat usually contains about 0.5% dye, 2% aqueous Sodium hydroxide solution 40 ° Be and 0.5% sodium dithionite. For the production of finer primary particles, the largest dimension of which is approximately 0.05 to 0.5 μ, one can follow the usual methods for the preparation of N, N'-dimethyl-3,4,9, iq-tetracarboxylic acid diimide operate by, for example, following the procedure of the German patent specification 386 057 of May 6, 1919 Perylen-3,4,9,10-tetracarboxylic acid anhydride with methylamine or methyl chloride on perylene-S ^ AlO-tetracarboxylic acid diimide in the presence of sodium hydroxide in a pressure vessel or by for example by the process of German patent specification 276 357 N-methylnaphthalenedicarboximide fused with potassium hydroxide.

If necessary, the Ν, Ν'-dimethyl-3,4,9,10-perylenetetracarboxylic acid diimide can be used with an average primary particle size of approximately 0.05 to 0.5 μ can also be used in the form of preparations with up to 20%, preferably up to 10%, calculated on the weight of the dye in part or in full oil-soluble emulsifiers or insoluble solid or other protective colloids, if appropriate in a mixture with up to 2%, calculated on the weight of the dye, of a water-soluble one Dispersant. To do this, for example, the dye can be slurried in 80% sulfuric acid, stir the slurry for up to 48 hours at temperatures between 20 and 80 ° C and post it before cooling to about 20 to 50 ° C in water, in which the required Amount of one of the emulsifiers or dispersants mentioned below has distributed or dissolved. Man but can also be a suspension of the dye in the form of primary particles whose size is between about 0.05 and 0.5 μ in the direction of their greatest extent, before drying up to 20%, preferably up to 10%, calculated on the weight of the dye, of partially or completely oil-soluble Emulsifiers or insoluble solid or other protective colloids, optionally in a mixture with up to 2%, calculated on the weight of the dye, of a water-soluble dispersant.

In the form of dye particles smaller than those mentioned above with an average primary particle size between 0.05 and 0.5 μ in the direction of its greatest dimension, Ν, Ν'-dimethyl-3,4,9,10-perylenetetracarboxylic acid diimide is used advantageously in the form of preparations with up to 20%, preferably up to 10%, calculated on the weight of the dye on partially or completely oil-soluble emulsifiers or on insoluble solids or other protective colloids, optionally in a mixture of up to 2%, calculated on the weight ίο the dye, a water-soluble dispersant.

Such very particularly fine primary particles can be obtained in various ways, for example by adding N, N'-dimethyl-3,4,9,10-perylenetetracarboxylic acid diimide at ordinary temperature Dissolve in at least 90% sulfuric acid and stir the solution into water, in which one expediently previously distributed the required amount of one of the emulsifiers or dispersants mentioned below ao or has solved. But you can also slurry the dye in the form of primary particles, whose size is below 0.05 μ in the direction of its greatest extent, before drying up to 20%, preferably up to 10%, calculated on the weight of the dye, of partially or completely oil-soluble emulsifiers or insoluble solid or other protective colloids, if appropriate in a mixture with up to 2%, calculated on the weight of the dye, of a water-soluble dispersant admit.

Partly or completely oil-soluble emulsifiers are e.g. B. alcohols, such as dodecyl alcohol, sperm oil alcohol, Stearyl alcohol and oleyl alcohol; or substituted phenols and natphthalols such as dodecylphenol and octylnaphthol. But also amines, such as oleylamine, stearylamine and coconut fatty amine; Carboxylic acids, such as Stearic acid, lauric acid, abietic acid or other resin acids or their salts; Carboxylic acid esters, such as Triethanolamine monostearate; Carboxamides such as oleic acid ethanolamide; or the Oxäthylierungs- resp. Oxpropylation products of the compounds mentioned, such as the adduct of 4 moles of ethylene oxide of oleic acid, the adduct of 8 moles of ethylene oxide with heptylnophthol or the adduct of 5 moles of ethylene oxide in sperm oil alcohol; as well as other common emulsifying agents such as Petroleum sulfonates or dialkyl sulfosuccinates, and mixtures thereof, come as partial or complete Oil-soluble emulsifiers into consideration. As insoluble solid protective colloids are z. B. aluminum hydroxide hydrate and silica gel mentioned, and as other protective colloids, for example, silicones or silicic acid esters, such as tetraundecanol silicic acid ester, Ethyl silicone oil and other more or less strongly crosslinked plastics, e.g. B. polycondensation products, such as alkyd resins, or polymerization products such as styrene-divinylbenzene or styrene-butadiene copolymers, mentioned.

All of the aforementioned partially or completely oil-soluble emulsifiers, insoluble solid protective colloids or other protective colloids can also in mixtures with one another and optionally together with water-insoluble, volatile solvents, such as white spirit, benzene, xylene, cyclohexane or their mixtures can be used.

Examples of water-soluble dispersants are alkyl sulfonates, such as the sodium salt of Octadecane-1-sulfonic acid; Alkylarylsulfonates, like that

Sodium salt of dodecylbenzenesulfonic acid; Addition products of ethylene oxide to alcohols, like that Addition product of 20 moles of ethylene oxide with sperm oil alcohol; Addition products of ethylene oxide to phenols, such as the adduct of 20 moles of ethylene oxide with dodecylphenol; Addition products of ethylene oxide on amines, such as the adduct of 10 moles of ethylene oxide on oleylamine; Addition products of ethylene oxide to carboxylic acids, such as the adduct of 40Mol ethylene oxide with ricinoleic acid; or others Ethylene oxide addition products, such as the sodium salt of the sulfuric acid ester of the addition product of 4 moles of ethylene oxide in sperm oil fatty acid monoethanolamide into consideration. Furthermore his also that Reaction product of naphthalene-2-sulfonic acid with formaldehyde and its alkali metal salts, such as Sodium or potassium salt, and protective colloids such as polyvinylpyrrolidone or copolymers of the Maleic acid, fumaric acid, itaconic acid and their acid derivatives with capable of copolymerization Vinyl and acrylic compounds or acrylamide-methacrylamide copolymers, named as water-soluble dispersants. The aforementioned water-soluble dispersants can also be used in Mixtures are used with each other.

The N ^ '- dimethyl-SA ^ iO-perylenetetracarboxylic acid diimide usually results in the form of finely divided primary particles and transparent ones in the form of coarse primary particles covering paintwork. But it is possible to use one that is present in finely divided form To agglomerate pigment in such a way that full-tone coatings can be obtained with it, for example by swelling in 81 to 82% sulfuric acid at 20 to 70 ° C and precipitation in Presence of the abovementioned partially or completely oil-soluble emulsifiers, such as dodecyl alcohol or oleic acid ethanolamide.

Although the good dyeing properties are known from German Auslegeschrift 1 055 156 which are the N, N'-dimethyl-3,4,9,10-perylenetetracarboxylic acid diimide when it is used for dyeing textile goods from the vat, it was not foreseeable that the dye would also make a valuable pigment. The requirements regarding the authenticity properties to be placed on a vat dye and on a pigment are so different that An insoluble anthraquinone dye is usually whole when it is used as a vat dye behaves differently than when used as a pigment.

The fact that the N, N'-dimethyl-3,4,9,10-perylenetetracarboxylic acid diimide excellent as marron-colored, strongly colored, pure, exceptionally light-, weather-, chemical- and solvent-resistant Pigment is suitable and pigment-colored masses and mixtures of good brilliance and high color fastness is particularly surprising, not least because than the professional world from the literature, z. B. from the German Auslegeschrift 1 055 156 or from the French patent specification 1154 385 of July 5, 1956 had to deduce that the subject in question Dye is unusable as a pigment.

The dye used according to the invention is a pigment of high color strength and good all-round fastness properties. Not only does it stand out as a pigment with excellent lightfastness, the reaches the value 8 measured according to the eight-point wool scale even in very strong white lightening; the N, N'-dimethyl-3,4,9,10-perylenetetracarboxylic acid diimide Rather, it produces a pigment with very good fastness to solvents and plasticizers, which at the same time is also well sprayed over and painted over. This pigment continues to stand out its excellent temperature resistance and excellent weather resistance. Due to these properties, the pigment is not

ίο solely for coloring paints, in particular of stoving enamels, very suitable, but it can also be used generally for exterior paints, for example on the basis of binder paints, can be used very well.

The parts and percentages given in the examples are weight units.

example 1

In a baking varnish made from 40 parts of coconut oil alkyd

ao resin (40% coconut oil), 12 parts of urea-formaldehyde resin, 40 parts of xylene and 8 parts of n-butanol 4 to 8 parts of the pigment obtainable according to paragraphs 3 and 4 using a funnel mill or rubbed in a ball mill. With the varnish obtained in this way, marron-colored varnishes can be produced, which have a high gloss after baking, are transparent and have excellent weather and weather conditions are overpainted.

The pigment used according to paragraph 1 is obtained in the following way:

2000 parts of an aqueous slurry of 100 parts of 3,4,9,10-perylenetetracarboximide with an average primary particle size of about 0.1μ in the direction of its greatest dimension are stirred in a pressure vessel with 250 parts of a 50% aqueous sodium hydroxide solution. 150 parts of methyl chloride are then pressed onto this mixture, the mixture is slowly heated to 100 ° C. and kept at this temperature for a few hours (as a rule, 4 to 8 hours are sufficient). After the reaction mixture has cooled, the deposited dye is filtered off with suction and washed free of salt with warm water.
The filter material is then mixed with 5 parts of dodecyl alcohol and 0.5 parts of the adduct of 20 moles of ethylene oxide with sperm oil alcohol and so much water is added (about 400 to 500 parts) that a well-flowing dye paste is formed. The dough obtained in this way is homogenized using a conventional grinding device for wet grinding, e.g. B. a powerful stirring device or a so-called disintegrator or a corundum disk mill, and then dries it to a paste with slow stirring and indirect heating, for example with steam. This paste is then, expediently in a drying cabinet, further dried at 60 to 80 ° C and the dry material in a gentle manner, for. B. ground with the help of a so-called disintegrator or a cross beater mill.

Example 2

A mixture of 70 parts of polyvinyl chloride, 30 parts of di-isooctyl phthalate and 1 part of titanium dioxide (Rutile) is given together with 0.5 parts of paragraph 3 pigment with the help of an approximate 160 ° C heated mixing mill colored in the usual way. You get an intensely marron

colored polyvinyl chloride, which is excellent for the production of shaped structures, such as films or Profiles, is suitable. The dyeing is characterized by excellent light and plasticizer fastness the end.

The pigment used in accordance with paragraph 1 is produced as follows:

100 parts (calculated on dry weight) of the according to example 1, paragraph 3, or according to the method of German patent specification 276 956 or according to the method of German patent specification 386 057 as moist Filter readily available dye N, N'-dimethyl-3,4,9,10-perylenetetracarboxylic acid diimide are dried at 100 ° C and ground. Now the dry goods are entered with stirring in 2000 parts 80% sulfuric acid and after distributing during Stirred at 60 to 70 ° C. for 25 hours. After cooling to 40 ° C., the sulfuric acid slurry is left of the dye in a thin stream into a mixture of 20,000 parts of water of approximately 50 ° C, 10 parts of oleic acid ethanolamide and 50 parts of white spirit pour in while stirring vigorously. That Well is then suctioned off, washed acid-free with 20 to 30 ° C warm water, in a vacuum Dried at 60 to 80 ° C and carefully ground. This gives a pigment in the form of a soft grain Powder, which is particularly suitable for coloring structures made of plasticized polyvinyl chloride, but also for coloring paints made on a natural or synthetic basis in transparent maroon tones.

Example 3

4 to 8 parts are added to a stoving enamel prepared according to the information in Example 1, Paragraph 1 of the pigment obtained according to Example 2, paragraph 3, using a ball mill or a funnel mill rubbed in. With the lacquer obtained in this way, similar transparent marron-colored lacquers can be produced produce as with the paint described in Example 1, paragraph 1.

Coatings with greater opacity are obtained if, during the preparation of the stoving varnish, a pigment goes out according to the information in Example 2, paragraph 3, but using 81 to 82% sulfuric acid is obtained instead of 80% sulfuric acid during the swelling.

Example 4 5 <>

A nitrocellulose solution consisting of 19 parts of nitrocellulose (ester-soluble 2: 1, butanol-moist), 5 parts Dibutyl phthalate, 3 parts of butylbenzyl phthalate, 4 parts of a condensation product from cyclohexanone and methylcyclohexanone, 30 parts of butyl acetate, 10 parts of ethyl acetate and 29 parts of toluene, is mixed with 2 parts of the pigment obtainable in accordance with paragraph 4 using a ball mill or a funnel mill rubbed. The yellow paintwork produced with this nitrocellulose spray paint shows excellent light and overspray fastness. Even a heavily lightened paintwork that is on one part of the marron-colored pigment contains 100 parts titanium dioxide (rutile), is still characterized by excellent lightfastness, the value of which (measured according to the eight-point wool scale) 8 is.

Coatings with a low covering power are obtained if one takes care of the preparation of the nitrocellulose spray paint from 2 parts of the pigment obtainable according to Example 1, paragraphs 3 and 4, starts.

The pigment used according to paragraph 1 is obtained in the following way:

A 0.5% aqueous slurry of 100 parts (calculated on dry weight) of the dye N, N'-dimethyl-3,4,9,10-perylenetetracarboxylic acid diimide obtained as moist filter material according to Example 1, paragraph 3, becomes aqueous with 400 parts Sodium hydroxide solution 40 ° Be and 10 parts of the sodium salt of the condensation product of naphthalene-2-sulfonic acid and formaldehyde mixed. 100 parts of sodium dithionite are then added to the mixture and the dye is vat by heating the mixture to 50 to 60 ° C. for 60 minutes. If necessary, you have to add more sodium dithionite to the vat during this time. The dye is then oxidized again for a few hours (approximately 3 to 10 hours) while air is passed through the 6O ⁰ C warm vat, it is suctioned off, washed salt-free with water and dried. This gives a pigment in the form of a grain-soft powder which can be used to color paints in highly opaque marron-colored tones.

Example 5

A mixture of 30 parts of barium sulfate (so-called blanc fixe), 5 parts of titanium dioxide (rutile), 3 parts of talc and 2 parts of calcium carbonate (chalk) together with 0.2 parts of ammonium polyacrylate and 0.3 part of a 25% aqueous ammonia solution suspended in 23 parts of water. This slurry is now rubbed in and stirred into a mixture of 36 parts of a customary polyvinyl propionate dispersion (with 50% solids content) and 0.5 part of a high polymer ammonium polyacrylate, which serves as a thickening agent. In the so prepared white binder you put 0.5 parts of a aqueous pigment dough, the preparation of which is explained in the third paragraph, with the aid of a stirrer a. The marron-colored marron-colored ones made with this binder color are outstandingly lightfast and wet-wipe-fast Paints are also well suited as exterior paints.

Instead of 36 parts of polyvinyl propionate dispersion, it is also possible to prepare the white binder the same amount of other conventional plastic dispersions, such as styrene-butadiene copolymers or polyvinyl acetate or the same amount of rubber latex.

The pigment dough used in accordance with paragraph 1 is produced as follows:

100 parts (calculated on dry weight) of that obtained as moist filter material according to Example 1, paragraph 3 Dye N.N'-Dimethyl-S ^ ÄlO-perylenetetracarboxylic acid diimide are with 20 parts of the addition product of 8 moles of ethylene oxide to heptylnaphthol mixed, stirred well and dried at 80 to 100 ° C. This mass is now under Adding a little water (about 15 to 25 parts is usually sufficient) in a kneader, such as it is brought onto the market by the Werner and Pfleiderer company until a sufficient number of items have been reached fine distribution (the average size of the aggregate

gate should not be more than 1 to 2 μ) kneaded and then mixed with water to form a dough of about 45 processed up to 50% dye content. In this form, the pigment is suitable for coloring plastic emulsions (Binder paints), which are used in particular for the execution of lightfast and weather-resistant exterior paints are intended, as well as for the coloring of paper, especially wallpaper, as well for other colors in which an aqueous solution forms the outer phase, and for production of rubber printing inks.

Claims (4)

Patent claims: 1. Use of N, N'-dimethyl-3,4,9,10-perylenetetracarboxylic acid diimide as a pigment, except for dyeing high-melting, high-molecular-weight polymers in bulk. 2. Use according to claim 1, characterized in that N, N'-dimethyl-3,4,9,10-perylenetetracarboxylic acid diimide used in a mean primary particle size between 0.05 and 5 μ in the direction of their greatest extent. 3. Use according to claim 1, characterized in that N, isr-dimethyl-3,4,9,1O- 10 perylenetetracarboxylic diimide with a mean primary particle size of less than 0.05 μ in Direction of their greatest expansion in the form of preparations with up to 20%, calculated on that Weight of the dye, of partially or fully oil-soluble emulsifiers or of insoluble ones solid or other protective colloids are used. 4. Use according to claim 1, characterized in that N, N'-dimethyl-3,4,9,10-perylenetetracarboxylic acid diimide in a mean primary particle size of less than 0.05 μ in the direction of their greatest extent in the form of Preparations with up to 20%, calculated on the weight of the dye, of partially or completely oil-soluble emulsifiers or insoluble solid or other protective colloids in Mixture with up to 2%, calculated on the weight of the dye, of water-soluble dispersants used. Considered publications:
French patent specification No. 1183 591,
234,534;
Swiss patent specification No. 101 763. When the application was announced, a coloring table with an explanation was displayed.