DE1962355A1 - Anthraquinone dyes - Google Patents

Description

Pttent-AbteUunf My / IM

The present invention relates to anthraquinone dyes the general formula

NHCO-

(D

where R stands for a substituent, ρ the numbers 0-6, m is the number 5 and η is the number 1 or 2, as well as their division and use as pigments.

Suitable substituents R are, for example: halogen atoms such as fluorine, chlorine or bromine, nitro groups, amino groups, Alky! Amino groups with 1-18 carbon atoms, cycloalkylamino groups, Ary! Amino groups, alkyl carbony! Groups with 1-18 C atoms, Arylcarbony groups, for example substituted or unsubstituted Benzoyl or naphthoy! Amino groups, hydroxyl groups, Alkoxy groups, especially those with 1-3 carbon atoms, alkyl or optionally substituted phenyl mercapto groups, Alkyl or optionally substituted phenylsulfonyl groups, Carboxy group », carbalkoxy groups, optionally substituted Carbamoy groups, Acy groups, optionally substituted Suliamoyl groups or optionally substituted phenylsulfony ! amino groups.

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Preferred dyes are those of the formula

(H)

wherein RjR ^ are hydrogen or a substituent with the proviso that one or two of the radicals R ₁ -R. for a rest

-JMiO - // ^ ^m

stand and where R, m and ρ have the meaning given above.

Preferred among the dyes of the formula (II) are those in which two of the radicals R-i-R * represent the radical

are, but especially those in whichR ₁ and R "for the

-NHCO- <

and R, R ,, R., m and ρ have the meaning given in formula (II) and those in which R ₁ and R represent the remainder

stand, while R ₂ , R ^ R as well as m undj? have the meaning given in formula (II).

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Further preferred dyes are those of the formula (II) in which R ₁ -R _{4 have} the meaning given and at least one of the radicals R or R ₁ -R _{4 represents} the group

-HHCO- ^

wherein Y represents a substituent and q represents the Numbers 0-5 stands.

Suitable substituents Y here are those given for R. Preferred substituents Y are halogen such as I, Cl, Br, NO «, alkyl groups with 1-4 carbon atoms, trifluoromethyl groups, carboxyl groups, optionally substituted carbamoy groups, Hydroxy groups, alkoxy groups with 1-4 carbon atoms and suliamoyl groups.

Preferred dyes in the context of the formula (I) are furthermore very generally those which are free from sulfonic acid groups.

The compounds according to the invention are produced According to processes known per se by acylation of aminoanthraquinones of the formula

(H)

where R stands for a substituent, ρ stands for the numbers 0-6 and η stands for 1 or 2, with at least η mol a reactive derivative of a carboxylic acid of the formula

(IV)

iU

where m stands for the number 5.

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In a preferred embodiment, 1 mol of an amine of the formula (III) is used with at least η mol of a carboxylic acid halide the formula

COX

(V)

where m has the meaning given and X is halogen, such as fluorine, chlorine or bromine,

at temperatures between 40 ° C and 220 ° C in an inert organic solvents such as benzene, toluene, xylene, chlorobenzene, Dichlorobenzene, trichlorobenzene, nitrobenzene, optionally in the presence of basic catalysts such as pyriaine, Morpholine, trimethylamine, collidine, picoline, lutidine, quinoline, Dimethylformamide with or without the addition of acid-binding agents such as soda, potash, sodium or potassium bicarbonate or quick lime until all the starting amine is used up.

Suitable aminoanthraquinones of the formula (III) are, for example, the following:

1-amino-anthraquinone, 2-amino-anthraquinone, 1,4-, 1 »5-, 1,6-, 1,7-, 1,8- or 2,6-diamino-anthraquinone, 1,4,5,8-tetraaminoanthraquinone, 4-Amino-i-methylamino-anthraquinone. 4-amino-1-butylamino-anthraquinone, 4-Amino-1-dodecyl_jaino-anthraquinone, 4-Amino-i-octadecylamino-anthraquinone, 4-Amino-1-eyelohexylamino-anthraquinone * 4-Amino-i-anilino-anthraquinone, 4-Amino-1- (4-chloro-anilino) -anthraquinone, 4-Amino-1- (2,4-dichloroanilino) -anthraquinone, 4-Amino-1- (4-niethoxy-anilino-anthraquinone, 4-, 5- »6- and 7-chloro-1-amino-anthraquinone, 6- or 7-fluoro-1-amino-anthraquinone, 5 »b- or 6,7-dichloro-i-aminoanthraquinone, 6,7-difluoro-1-amino-anthraquinone,

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ORf ^ N INSPECTED

4,5, ö-trichloro-1-araino-anthraquinone, 5, b-Dicftior-1,4-dimnino-anuhrachinon, 4-chloro-1,5-diamino-anthraquinone, 3-bromo-4-amino-l- (p-toluidino) -anthraquinone, 4- or 5-nitro-'lamind-anthraquinone S-nitro-l ^ -diamino-anthraquinone, 4- or S-amino-l-acetylamino-anthraquinone, 5-amino-l-propionylaminoanthraquinone , 5-amino-l-butyrylamino-anthraquinone, 5-amino-llaurylamino-ar.thraquinone, S-amino-l-palmitoylamino-anthraquinone, 5-amino-l-stearoylamino-anthraquinone, ^ -, 5- or 8-amino -lbenzoylamino-anthraquinone, S-amino-li ^ -dibenzoylamino-anthraquinone, 4-amino-1- (2-, 3- or ^ -chloro-benzoylaraino) -anthraquinone, ^ -Araino-li ^ -fluoro-benzoylaminoI-anthraquinone , 4-aminol- (2,4-difluoro-benzoylamino) -anthraquinone, k -amino- 1- (2, ¹ I-, 2,5- or 5 * ⁱ t-dichloro-benzoylamino) -anthraquinone, 4-amino -l- (2,4,5-tri-chloro-benzoylamino) -anthraquinone, ¹ I-AmInO-I- (2, 3, ^, 5-2,3 * 5 * 6- or 2,3, ² 1 , 6-tetrachlorobenzoylamino) anthraquinone, ¹ I-AmInO-I- (pentachlorobenzoylaminoj-anthraquinone, 4-amino-1- ( ¹ t-fluoro-2-chloro r-benzoylamino) anthraquinone, 4-amino-1- (2-fluoro-4-chlorobenzoylamino) -anthraquinone, 4- or 5-amino-1- (2-bromobenzoylamino) anthraquinone, 4- or 5-amino -l- (4-chloro-2-bromobenzoylamino) anthraquinone, 4- or 5-amino-1- (2-chloro-4-bromobenzoylamino) anthraquinone, 4- or 5-amino-1- (2,4-dibromo -benzoy ± amino) -anthraquinone, 4- or 5- ^ mino-1- (2-, 3- or 4-nitro-benzoylamino) -anthraquinone, 4- or 5-amino-1- (4- or 6-chloro -3-nitro-benzoylamino) -anthraquinone, 4- or 5-amino-1- (2,4- or 3,5-dinitro-benzoylamino) -anthraquinone, 4- or S-amino-i-phenyl-acetylamino-anthraohinoTi , 4- or 5-amino-1- (4-chloro-phenyiacetyl-amino) -anthraquinone, 4- or 5-amino-1- (4-nitro-phenylacetylamino) -anthraquinone, 4- or 5-amino-1- (2- or 3-methyl-benzoylamino) -anthraquinone, 4- or 5-amino-1- (3-trifluoromethyl-benzoylamino) -anthraquinone, 4- or 5-amino-1- (4-nitro-3-methyl- benzoylamino) anthraquinone, 4- or 5-amino-1- (4-methyl-benzoylamino) -anthraquinone, 4- or 5-amino-1- (4-trifluoromethyl-benzoylamino) -anthr aquinone, 4- or 5-amino-1- (4-methyl-phenylacetyiamino) -anthraquinone,

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4- or 5-amino-l- (4-tert-butyl-benzoylamino) -anthraquinone, 4- or 5-amino-l- (4-phenyl-benzoylamino) -anthraquinone, 4- or 5-amino-l- ( 3-earboxy-benzoylamino) -anthraquinone, 4- or 5-aminol- (3- or 4-carbamoyl-benzoylainino) -anthraquinone, 4- or 5-aminol- (4-methylcarbamoyl-benzoylamino) -anthraquinone, 4- or 5 -Aminol- (4-n-butylcarbamoyl-benzoylamino) -anthraehinone, 4- or 5-amino-1- (4-phenylcarbamoyl-benzoylamino) -anthraquinone, 4 ° i} §ino-l- / ~ 4- (2- chlorophenylcarbamoyl) benzoylamino_7-anthraquinone, 4- or 5-aminol- / ~ 4- (sulfolan-3-yl-phenylcarbamoyl) -benzoylamino 7-anthraquinone, 4- or 5-amino-1- (2-hydroxy-benzoylamino ) anthraquinone, 4- or 5-amino-1- (2-methoxy-benzoylamino) -anthraquinone, 4- or 5-aminol- (4-chloro-2-hydroxy-benzoylamino) -anthraquinone, 4- or 5-aminol - (2-chloro-4-hydroxy-bsnzoylamino) -anthraquinone, 4- or 5-aminol- (4-methoxy-benzoylamino) -anthraquinone, 4- or 5-amino-1- (3-sulfamoyl-benzoylamino) -anthraquinone , 4- or 5-amino-1- (2-chloro-3-sulfamoyl-benzoylamino) -anth rachinone, 4-amino-1- (naphthoyl-1- or -2-.amino) -anthraquinone, 8-amino-1- (2-, 3- or 4-chloro-benzoylamino) -anthraquinone, 8-amino-l - (2,4-, 2,5- or 3,4-dichlorobenzoylamino) -anthraquinone, 8-amino-1- (4-nitro ~ benzoylamino) -anthraquinone, 8-amino-1- (4-nitro-benzoylamino) anthraquinone, 8-aminol (3- or 4-methylbenzoylamino) anthraquinone, 8-amino-1- (3- or 4-trifluoromethylbenzoylamino) anthraquinone, 8-amino-1- (4-methoxybenzoylamino) anthraquinone , 5j8-dichloro-4-.ami.no- 1-benzoylamino) anthraquinone, 5 * 8-dichloro-4-amino- (2-, 3- or 4-chloro- or 2,4-dichloro- or 4- methyl-benzoylamino) -anthraquinone, 4- or 5-amino-1-hydroxy-anthraquinone, 4,8-diamino-1-hydroxy-anthraquinone, 4,5,8-triamino-1-hydroxy-anthraquinone, 8-chloro 5-araino-1,4-dihydroxyanthraquinone, Se-Dlchlor-1,4-diamino-anthraquinone, 8-nitro-4 "amino-1,5-dihydroxy-anthraquinone, 4,8-dialino-1,5-dihydroxy-anthraquinone , 5-nitro-4-amino-l, 8-d ^ hydroxy-anthraquinone, 4,5-diamino-1,8-dihydroxyanthraquinone, e-amino-l ^^ - trihydroxy-anthraquinone, 4-Amino-1-methoxy- or iso-propoxy-anthraquinone, 1-amino-4-hydroxy-2-phenoxy-anthraquinone, e-chloro - ^ - amino-1-hydroxy- or-methoxyanthraquinone, 2,6-dibromo -l, 5-diam ± no- ¹ t, 8-dihydroxy-anthraquinone, the compound that is used in the bromination of 4,8-diamino-1,5-dihydroxy- or 4,5-diamino-1,8- dihydroxy-an thrachinone in, for example, sulfuric acid, and which contains about one atom of bromine per mole of 4,8-diamino-1,5-dihydroxy- or 4 _f 5-diamino-1,8-dihydroxy-anthracite,

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l-Amino-anthraquinone-2-carboxylic acid ₁ l-Amino-anthraquinone-2-carbon-. acid amide, l-amino-anthraquinone-i-carboxylic acid methyl ester, propyl ester or butyl ester, l-amino-2-acetyl-anthraquinone ^^ - Amino-1- (p-toluenesulf araido) -2- (phenyl-sulfonyl J-anthraquinone, 1-amino-6-methylmercapto-anthraquinone, l-amino-6-phenylmercapto-anthraquinone, l-amino-6-methylsulfonyl-anthraquinone and l-amino-6- (4-chloro-phenylsulfonyl) -anthraquinone.

Suitable carboxylic acid derivatives are bapw. the halides, in particular the fluorides, chlorides and bromides or the esters, in particular the methyl esters or ethyl esters of carboxylic acids of the formula (IV)

such as pentachlorobenzoic acid.

The dyes of the formula I obtained are suitable for dyeing a wide variety of materials, for example as vat dyes to 'dyeing cellulose fibers, but especially as pigments. Thanks to their excellent lightfastness and good migrationfastness, they can be used for a wide variety of pigment applications will.

The novel dyes of the formula (I) are obtained in a form suitable for pigments form or can be converted to conversion into a form suitable for pigments form by per se known after-treatment in fine distribution, ZUIr ₁ example by dissolving or swelling in strong inorganic acids such as sulfuric acid and discharging on ice. Fine division can also be achieved by grinding with or without grinding aids such as inorganic salts or sand, if appropriate in the presence of solvents such as toluene, xylene, dichlorobenzene or N-methylpyrrolidone. The color strength and transparency of the pigment can be influenced by varying the post-treatment.

The pigments according to the invention can be used to produce very real pigmented systems, such as mixtures with others Substances, preparations, paints, printing inks, colored paper and colored macromolecular substances are used. When mixed with other substances, for example, those with inorganic white pigments such as titanium dioxide (rutile) or to be understood with cement. Preparation are for example

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Plush pastes with organic liquids or doughs and fine doughs with water, dispersants and optionally preservatives. The term paint stands, for example, for physically or oxidatively drying paints, stoving paints, Reaction paints, two-component paints, emulsion paints for weatherproof coatings and glue paints. Under inks are to understand those for paper, textile and metal printing. The macromolecular Substances can be of natural origin such as rubber, obtained through chemical modification such as acetyl cilulose, Cellulose butyrate or viscose or produced synthetically, such as polymers, polyaddition products and polycondensates. Called be plastic masses such as polyvinyl chloride, polyvinyl acetate, polyvinyl propionate, polyolefins, for example polyethylene or Polypropylene, polyester for example polyethylene erephthalate, Polyamides, super polyamides, polymers and copolymers of acrylic esters, methacrylic esters, acrylonitrile, acrylamide, butadiene, Styrene, as well as polyurethanes and polycarbonates. The substances pigmented with the claimed products can be in any form are present.

The eriinduEpegefliäß compounds have excellent pigment properties and are not only excellent water-fast, oil-proof, acid-fast, lime-proof, alkali-proof, solvent-proof, overpainting, spray-coating, sublimation-proof, heat-resistant, vulcanization-resistant, but also very productive, easy to distribute in plastic materials and are extremely fast to light and weather.
The parts given in the examples are parts by weight.

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ORIGINAL INSPECTED

1 egg ; _Λ ν -jcc Example 1;

a) To a solution of 26.2 parts of pentachlorophenol-benzoyl chloride in 600 parts of nitrobenzene to wear at 100 ⁰ C a good 10.0 parts of ground 1,4-diamino-anthraquinone. The mixture is heated to 210 ° C. over the course of one hour, while stirring, and the mixture is stirred at this temperature for a further four hours. The precipitate is filtered at 17O ⁰ C, washed with nitrobenzene of 170 ⁰ C after washed after cooling to 60 ⁰ C with methanol nitrobenzene-free and dried at 50 ⁰ C in a circulating air oven. 27> O parts of l ^ -Di-Cpentachlor-benzoylaminoi-anthraquinone are obtained in the form of orange-red bar-shaped prisms which dissolve red in concentrated sulfuric acid.

b) 8 parts of l ^ -Di-Cpentachlor-benzoylaminoJ-anthraquinone, which were finely divided by grinding in a vibrating mill with 2 parts of xylene and 160 parts of sodium chloride and washing out of the common salt components, are coated with a baking varnish made of 25 parts of coconut oil alkyd resin (40 % Coconut oil), 10 parts of melamine resin, 50 parts of toluene and 7 parts of glycol monomethyl ether on an automatic Hoover-Muller grinding machine. The mixture is applied to the substrate to be painted, the paint is cured by baking at 13 ° C. and red, opaque paints are obtained that are very fast to overpainting and have excellent fastness to light and weather. Pigmented stoving enamels with the same fastness properties are obtained if 15-25 parts of the specified alkyd resin or an alkyd resin based on cottonseed oil, castor oil or synthetic fatty acids are used and, instead of the specified amount of melamine resin, 10-15 parts of the mentioned melamine resin or a condensation product of formaldehyde with urea or with Benzoguanamine uses.

Instead of the specified amount of pigment, 1 to 10 parts of a mixture of titanium dioxide (rutile type) are rubbed with that in Example Ib The pigment specified in the ratio 0.5-50: 1 in the paint specified in Example Ib is obtained with the same further processing Coatings with the same fastness properties and with increasing Titanium dioxide content after white shifted red color.

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INSPECTED

10 1 9 j /: 3 5 5

Coatings with similar fastness properties are obtained when using physically drying fuel, zapon and nitro lacquers , of air-drying oil, synthetic resin and nitro combination paints, oven- and air-drying epoxy resin paints, if necessary in combination with urea, melamine, alkyd or phenolic resins.

If you use reaction varnishes based on unsaturated polyester resin or amine hard oxide epoxy resin lacquers with dipropylenetriamine as an amine component, one obtains red coatings with excellent weather resistance and bloom resistance.

Pigmentation of similar fastness is obtained when using other two-component lacquers based on aromatic or aliphatic Isocyanates and polyethers or polyesters containing hydroxyl groups, as well as with moisture-drying polyurea lacquers resulting in polyisocyanate lacquers.

c) 5 parts of a fine dough obtained by kneading 50 parts of 1, 4-di- (penta chloro-benzoylamino) anthraquinone with 15 parts of a Ary lpolyglykoläther emulsifier and 35 parts water with 10 parts barytes as a filler, 10 parts of titanium dioxide ( Rutile type) as a white pigment and 40 parts of an aqueous emulsion paint containing approx. 50 % polyvinyl acetate, mixed. The paint is spread and, after drying, red paints are very good fastness to lime and cement, and are also extremely fast to weather and light.

The fine dough obtained by kneading is equally suitable for pigmenting clear polyvinyl acetate emulsion paints for Emulsion paints that contain copolymers of styrene and maleic acids as binders, as well as emulsion paints Based on poly vinyl propionate, polymethacrylate or butadiene styrene and glue-based wallpaper paints with chalk.

Other non-ionic emulsifiers, such as the reaction products of nonylphenol with ethylene oxide or ionic wetting agents, such as the sodium salts of alkylaryl sulfonic acids, e.g. B. the DinaphfchyImethandisulfonsäure, sodium salts of substituted sulfofatt ^ hireesters and.

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H atrium al ze of paraffin sulfonic acids in combination with alkyl polyglycol ethers be used.

d) A mixture of t> 5 parts of polyvinyl chloride, 35 parts of diisooctyl phthalate, 2 parts of dibutyl tin mercaptide, 0.5 part Titanium dioxide and 0.5 part 1, Jl-di- (pentachlor-benzoylamino) -anthraquinone, that was burned in fine dispersion by grinding with sodium chloride in the presence of white spirit, is put on a Mixing mill colored at l65 ° C. You get an intense red colored mass used for the production of foils or moldings can serve. The dyeing is characterized by excellent light fastness and very good plasticizer fastness.

Red moldings of very good fastness to light and migration are obtained if C.2 parts of the specified, finely divided pigment are mixed with 100 parts of polyethylene, polypropylene or polystyrene granules and injected directly in an injection molding machine or in one at 220 ° to 280 ° C Extrusion press into colored rods or processed into colored skins on the mixing mill. The skins or rods are, if necessary, granulated and injected in an injection molding machine. Synthetic polyamides of caprolactam or of adipic acid and hexamethylenediamine or the condensates of terephthalic acid and dyed ivthylenglykol 300 ⁰ C, if appropriate under Stickstoffatnosphäre, - Similarly, at the 280th

If 1 part of the specified, finely divided pigment is mixed with 10 parts of titanium dioxide (rutile type) and 100 parts of a powdered copolymer based on acrylonitrile-butadiene-styrene and colored at 140 ° -18O ° C. on a roller mill, one obtains a red skin that is granulated and injected in a spatula pouring machine at 200-25O ° C. Red moldings are obtained with very good light and migration fastness and excellent heat resistance. In a similar manner, but at temperatures of l80 - 22O ⁰ C and without the addition of titanium dioxide plastics are colored based on cellulose acetate, cellulose butyrate and their mixed ¹ with similar fastnesses.

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Red, transparent granules of excellent lightfastness and heat resistance are obtained when 0.2 parts of the specified Pigment in finely divided form with 100 parts of a plastic based on polycarbonate in an extruder or in a kneading screw at 250-280 ° C and processed into granules.

e) 90 parts of a slightly branched polypropylene glycol with a molecular weight of 2500 and a hydroxyl number of 56, 0.25 part of endoethylene piperazxn, 0.3 part of tin (II) octoate,

1 part of a polyether siloxane, 3.5 parts of water, 12 parts of a grind of 10 parts of finely divided 1,4-di- (pentachlorobenzoylamino) -anthraquinone in 50 parts of the specified polypropylene glycol are mixed well and then mixed with 45 parts of tolylene diisocyanate (80 % 2nd , 4- and 20 % 2,6-isomer) mixed intimately and poured into a mold. The mixture becomes cloudy after 6 seconds and foam formation occurs. After 70 seconds, an intensely red-colored, soft polyurethane foam has formed, the pigmentation of which has excellent lightfastness.

A red flexible polyurethane foam is even more lightfast Pigmentation is obtained if 90 parts of a weakly branched one are used Polyesters made from adipic acid, diethylene glycol and trimethylolpropane with a molecular weight of 2000 and a hydroxyl number of 60 mixed with the following components: 1.2 parts of dimethylbenzylamine, 2.5 parts of sodium castor oil sulfate,

2 parts of an oxyethylated, benzylated oxydiphenyl, 1.75 parts of water, 12 parts of a paste, prepared by grinding 10 parts into fine division; Brought l, 4-di- (pentachlorbenzoylamino) -anthraquinones in 50 parts of the above polyester and after mixing 40 parts of toluene diisocyanate (65 % 2,4- and 35 % 2,6-isomer) stirred in and the mixture in a Form pours and dilutes.

f) With a printing ink, produced by rubbing 35 parts finely divided 1,4- (di- (pentachlor-benzoylamino) -anthraquinones and 65 parts of linseed oil and the addition of 1 part of Siccativ (co-naphthenate, 50 pounds in white spirit) are red offset prints

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high brilliance and color strength and very good light and lacquer fastness obtain. Use of this printing ink in letterpress, collotype, stone or steel engraving leads to red prints that are more similar Fastnesses. If the pigment is used to color tinplate printing or low-viscosity gravure printing inks or printing inks, red prints of similar fastness properties are obtained.

g) A printing paste is prepared from 10 parts of one of the fine pigment pastes given in Example Ic, 100 parts of 3 # gum tragacanth, 100 parts of an aqueous 50% egg albumin solution and 25 parts of a nonionic wetting agent. A textile fiber fabric is printed, steamed at 100 ^° C. and a red print is obtained which is distinguished by excellent fastness properties, in particular light fastness. Instead of tragacanth and egg albumin, other binders which can be used for fixing to the fiber, for example those based on synthetic resin, British gum or cellulose glycolate, can be used in the printing approach.

h) A mixture of 100 parts light crepe, 2.6 parts sulfur,

1 part of stearic acid, 1 part of mercaptobenzothiazole, 0.2 part of hexamethylenetetramine, 5 parts of zinc oxide, 60 parts of chalk and

2 parts of titanium dioxide (anatase type) is put on a mixing roll mill at 50 ° C with 2 parts of 1M-Di-Cpentachlor-benzoylaminoJ-anthraquinone colored and then vulcanized for 12 minutes at 140 ° C. A red colored vulcanizate of very good lightfastness is obtained.

i) 100 parts of a 20 iigen aqueous paste of 1,5-di- (pentachlor-benzoylamino) -anthraquinone, prepared for example by dissolving the dye in 96 # sulfuric acid at -5 to +5 ⁰ C, pouring onto ice, filtering and Washed neutral with water, 22500 parts of an aqueous approximately 9 Äigen viscose solution are added in the stirrer. The colored mass is stirred for 15 minutes, then deaerated and subjected to a spinning and desulfurization process. Yellow-colored threads or films with very good lightfastness are obtained.

Red pigmented threads or films of similar authenticity are obtained by separating a solution colored with the 1,4-di- (pentachlorobenzoylamino> -anthraquinone which has been finely divided)

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of acetyl cellulose in acetone or a 15 - 25 # solution of Polyacrylonitrile in dimethylformamide using a dry spinning process undergoes.

k) 10,000 parts of a paper pulp, containing per 100 parts

4 parts of cellulose are treated in the Hollander for about 2 hours. During this time you give every quarter of an hour 4 parts resin glue, then 30 parts of a 16 / Sigen pigment dispersion, obtained by ball milling 4.8 parts of 1,4-di- (pentachlorobenzoylamino) anthraquinone with 4.8 parts Dinaphthylmethanedisulfonic acid and 22 parts of water, then

5 parts of aluminum sulfate. After completion on the paper machine a red colored paper of excellent lightfastness and solventfastness is obtained.

1) The red pigmented papers produced according to Example Ik with the 55% solution of a urine of f-formaldehyde resin soaked in n-butanol and baked at 140 ° C. Red laminate papers with very good migration and excellent properties are obtained Lightfastness.

A laminate paper with the same fastness properties is obtained by laminating a paper that has been gravure printing with a printing ink was printed, the one of the pigment doughs given in Example Ic and contains water-soluble or saponifiable binders.

m) 0.2 parts of l, 4-di- (penta chloro-benzoylamino) anthraquinone be made into a paste in 50 parts of water at 50 ⁰ C and in a 25 - 30 ⁰ C warm solution of 1.2 parts by volume of sodium hydroxide solution of 38 Be and 1 Part of sodium hydrosulfite poured into 150 parts of water. In the red-brown vat obtained after 20-30 minutes, 10 parts of cotton are dyed with the addition of 4 parts of Glauber's salt for 45 minutes at 25-30 ° C. After dyeing, it is rinsed in cold running water until it is completely oxidized, acidified and soaped at the boil. A scarlet dye with excellent fastness properties is obtained.

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Example 2: "^

A mixture of 1 * 50 parts of nitrobenzene, 25.3 parts of pentachlorobenzoic acid and 10 parts by volume of thionyl chloride is heated in a glass apparatus with stirrer, thermometer and reflux condenser to 140 ° C. in one hour and kept at this level for one hour. It is then ^{allowed to cool to 100 °} C. and dry air is passed through the apparatus for 5 minutes. At the same temperature one carries 10 parts of a finely powdered 1,5-diamino-anthraquinone, the temperature is raised within one hour to 200-210 ⁰ C and holding for 3 hours at this level. The precipitated dye is filtered off at 200 ⁰ C ^on a preheated suction filter and the product is washed twice with 50 ml of nitrobenzene of 200 ⁰ C. It is then washed with methanol until there is no more nitrobenzene present. 30.2 parts of 1,5-di- (pentachlor-benzoylamino) -anthraquinone are obtained in the form of reddish-tinged yellow cuboid prisms which dissolve in concentrated sulfuric acid to a reddish-tinged yellow. The process of Examples Ib to Im gives yellow pigmentations and dyeings with very good fastness properties.

If, instead of the 1,5-diamino-anthraquinone, equivalent amounts of MjS-diamino-ljS-dihydroxy-anthraquinone are used, 32.1 is obtained Parts of 4,8-di (pentachloro-benzoylamino) -1,5-dihydroxy-anthraquinone in the form of red-violet prisms, which dissolve light brown in concentrated sulfuric acid and according to the method of Examples Ib result in up to 11 red pigmentations of excellent fastness properties. Colored according to Example Im, a purple color is obtained Cotton with very good fastness properties.

Example 3?

A mixture of 21.1 parts of pentachlorobenzoic acid, 500 parts of o-dichlorobenzene and 9 parts by volume of thionyl chloride is treated as in Example 2. After cooling to 100 ° C., 6.5 parts of pyridine and 10 parts of 1,5-diamino-4-hydroxy-anthraquinone in finely powdered form are added, the temperature is increased to 170-180 ° C. within one and a half hours and is kept there for three and a half hours Height. The precipitated dye is at 150 ⁰ C

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filtered off with suction on a pre-heated suction filter, the product is washed until the effluent was colorless with o-dichlorobenzene of 150 ⁰ C. It is then washed with methanol and then with hot water. 23 »7 parts of 1,5-di- (pentachlor-benzoylamino) -4-hydroxy-anthraquinone are obtained in the form of brown prisms which dissolve orange-brown in concentrated sulfuric acid. The process of Examples Ib to 11 gives brown pigmentations with very good fastness properties.

Example 4:

A mixture of 8.6 parts of pentachlorobenzoic acid, 5 parts by volume of thionyl chloride and 200 parts of nitrobenzene is treated as in Example 2. Then one carries at 100 ⁰ C 10 parts of 4-amino-l- (4-chlorobenzoylamino) anthraquinone one, heated in one hour to reflux temperature and the reaction mixture was maintained for 3 hours under gentle reflux at the boiling point. After working up according to Example la or 2, 14.5 parts of 4- (4-chloro-benzoylamino) -l-fcentachlor-benzoylamino) -anthraquinone are obtained in the form of brownish-red cuboid prisms which dissolve red in concentrated sulfuric acid and are used according to the Examples Ib to Im give orange pigmentations and dyeings with very good fastness properties.

Instead of 200 parts of nitrobenzene, 150-800 parts of nitrobenzene, trichlorobenzene, dichlorobenzene, o-chloronitrobenzene can be used or use naphthalene.

Example 5:

Half to three quarters of a solution of 33.7 parts of pentachlorobenzoyl chloride in 180 parts of nitrobenzene is ^{added dropwise within minutes at 45-50 °} C. to a mixture of 25 parts of 1,4-diaminoanthraquinone, 15 parts of collidine and 400 parts of nitrobenzene. It is heated to 12O ⁰ C. After cooling to 45-50 ^° C., the remainder of the solution is added dropwise over the course of one hour, ^{heated again to 120 °} C. and allowed to cool. It is suctioned off at 20 ^° C., covered with cold nitrobenzene, the nitrobenzene is washed out with methanol, and washed with hot water

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after drying, 49.4 parts of 4-amino-1- (pentachlorobenzoylamino) anthraquinone are obtained as a shiny metallic product consisting of violet bar-shaped prisms that is concentrated in Sulfuric acid dissolves bluish red. The compound is suitable as an intermediate for further conversion. Used according to Examples Ib, lc, Ie and 11 it results violet pigmentation with excellent light fastness and good migration fastness.

Instead of collidine, equivalent amounts of pyridine, Use lutidine, quinoline or Ν, Ν-dimethylaniline. The solution of the pentachlorobenzoyl chloride can according to Example 3 or 4 by reacting equivalent amounts of pentachlorobenzoic acid can be obtained.

Example 6:

It is a mixture of 500 parts of nitrobenzene, 25.5 parts of pentachlorophenol-benzoic acid and 10 parts by volume of thionyl chloride according to Example 2 in order, but carries at 100 ⁰ C, a 10 parts of finely powdered 1,4-diamino-anthraquinone and 0.2 parts of dimethylformamide and receives after further reaction according to Example 2, 26.5 parts of 1,4-di- (pentachlorobenzoylamino) anthraquinone, which is identical to the dye mentioned in Example 1 and resembles it in its dye and pigment properties.

example J :

According to Example 4 using 8.6 parts of pentachlorobenzoic acid and 15.1 parts of the 4-amino-1- (pentachlorobenzoylamino) -anthraquinone described in Example 5 instead of 10 parts of 4-amino-1-benzoylamino-anthraquinone one 12.1 parts of the 1,4-di- (pentachlor-benzoylamino) -anthraquinones described in Examples 1 and 6.

Example 8;

Genäd example la, but with replacement of the 10 parts of 1,4-diamino mnthraquinone by 14.7 parts of the dye that is obtained,

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if you jije-diamino-ljS-dihydroxy-anthraquinone in sulfuric acid brominated in such a way that the reaction product contains about one atom of bromine per mole of 4,8-diamino-1,5-dihydroxy-anthraquinone, one arrives at to a dye which, according to the method of Examples Ib to Ig, produces true pigmentation with a violet hue *

Example 9:

According to Example 2 using the amount of pentachloro-benzoic acid specified there and replacing the 10 parts of 1,5-diaminoanthraquinone equivalent amounts of other diamino-anthraquinones or diamino-anthraquinone derivatives give the in the following table indicated dyes, which by the method of Examples Ib to 11 real pigmentations with the deliver the colors specified in the table.

Dye hue

1,6-di- (pentachlorobenzoylamino) - green-yellow

anthraquinone

1,8-di- (pentachlorobenzoylamino) - yellow

anthraquinone

2,6-di- (pentachlor-b enzoylamino) - yellowIi ch

anthraquinone

ll-chloro-ljS-di-ipentachlor-benzoylamino) - yellow anthraquinone

5-nitro-1,4-di- (pentachlorobenzoylamino) - brown-red anthraquinone

5,8-dichloro-1,4-di- (pentachloro red

benzoylamino) anthraquinone

4,5-di- (pentachloro-benzoylamino) - purple

1,8-dihydroxy-anthraquinone

1,4-di (pentachlorobenzoylamino) - red

5,8-dihydroxyanthraquinone

3,7-dibromo-4,8-di (pentachlor violet

benzoylamino) -1,5-dihydroxy-anthraquinone

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Example 10; Λ3

According to Example 4 using the amount of pentachlorobenzoic acid specified there and replacing the 10 parts of 4-amino-1- (4-chlorobenzoylamino) anthraquinone by equivalent amounts of other amino-aroylamino-anthraquinones one obtains the in the The following table indicated dyes which, according to the method of Examples Ib and Ic, were genuinely pigmented paints with the colors specified in the following table.

Dye hue

4-Benzoylamino-1- (pentachloro red

benzoylamino) anthraquinone

4- (4-fluoro-benzoy lamino) -l- (pentachlor-orange

benzoylamino) anthraquinone

4- (3-chloro-benzoylamino) -l- (pentachloro red

benzoylamino) anthraquinone

4- (pentachlorobenzoylamino) -! - red

(2-brombenzoy lamino) anthraquinone

4- (pentachlorobenzoylamino) -l- orange

(3-nitro-benzoylamino) anthraquinone

4- (P entachlor-benzoylamino) -1- orange

(4-nitro-benzoylamino) anthraquinone

4- (pentachlorobenzoylamino) -l- orange

(2-chlor-5-nitro-benzoylanu.no) -anthraquinone

4- (pentachlorobenzoylamino) -1- orange

(3-trifluoromethyl-benzoylamino) -anthraquinone

4- (pentachlorobenzoylamino) -1- red

(4-methylbenzoylamino) anthraquinone

4- (pentachlorobenzoylamino) -1- brown

(3-carbamoy1-benzoylamino) -

anthraquinone

4- (pentachlorobenzoylamino) -l- brown

(2-methoxy-benzoylamino) -

anthraquinone

4- (pentachlorobenzoylamino) -l- brown

(4-methoxy-benzoylamino) -

anthraquinone

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dye

hue

5-Benzoylamino-1- (pentachlorobenzoylamino) anthraquinone

5- (2-Fluoro-4-chloro-benzoylamino) -lpentachloro-benzoylamino) -anthraquinone

5- (Pentachlorobenzoylamino) -1-4-chloro-3-nitro-benzoylamino) anthraquinone

5- (pentachlorobenzoylamino) -1- (4-nitr o-2-me thy 1-benzoy lamino) anthraquinone

5- (pentachlorobenzoylamino) -1- (4-carboxy-benzoylamino) anthraquinone yellow yellow yellow

yellow yellow

Example 11:

According to Example 4 using the amount of pentachloro-benzoic acid indicated there and replacing the 10 parts of 4-amino-1- (4-chloro-benzoylamino) anthraquinone by equivalent amounts of anthraquinone derivatives with an acylatable amino group the dyes given in the table below are obtained which, according to the method of Examples Ib to Ig, give true pigmentations with the colors specified in the following table.

dye

hue

1- (pentachlorobenzoylamino) anthraquinone

4-anilino-1- (pentachlorobenzoylamino) anthraquinone

4- (4 -Chloranilino) - 1-fcent achlorbenzoy lamino) -anth rachin on

4- (2,4-dichloro-anilino) -I- (pent achlorbenzoy lamino) anthraquinone

4- (4-methoxy-anilino) -! - (pentachlorobenzoy lamino) anthraquinone

6-chloro-1- (pentachlorobenzoylamino) anthraquinone

7-chloro-1- (pentachloro-benzoylamino) -anthraquinone yellow blue-violet blue-violet blue-violet blue yellow yellow

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dye

hue

5,8-dichloro-1- (pentachlorobenzoylamino) - yellow anthraquinone

6,7-dichloro-1- (pentachloro-benzoylamino) - yellow anthraquinone

6,7-difluoro-1- (pentachlorobenzoylamino) - yellow anthraquinone

4-acetylamino-1- (pentachlorobenzoylamino) - orange anthraquinone

5-acetylamino-1- (pent achlor-b enzoylamino) - yellow anthraquinone

5-propionylamino-l- (pentaclor yellow

benzoylamino) anthraquinone

5-butyrylamino-1- (pent achlor-b enzoy1- yellow

amino) anthraquinone

5-Laurylamino-1- (pentachloro-benzoylamino) - yellow anthraquinone

5-palmitylamino-l- (pentachlorobenzoyl yellow

amino) anthraquinone

5-stearoylamino-1- (pentachlor-benzoy1- yellow

amino) anthraquinone

8-Benzoylamino-1- (pentachlor-benzoy1- yellow

amino) anthraquinone

1,4-dibenzoylamino-5- (pentachlororange

benzoylamine ο) -anthr aquinone

4- (pentachloro-benzoylamino) -1-phenyl-red

acetylamino-anthraquinone

4- (Pent achlor-benzoylamino) -1- red brown

(4-nitrophenylacetylamino) anthraquinone

4- (pentachlorobenzoylamino) -1- red brown

(4-methylpheny1-acetylamino) -

anthraquinone

8-nitro-4- (pentachlorobenzoylamino) - red

1,5- dihy dr oxy -an th r ac hin on

5-nitro-4- (pentachlorobenzoylamino) - red

1,8-dihydroxy-anthraquinone

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Dye 2_ shade

8- (pentachlorobenzoyiamino) -1, 4,5- red

trihydroxy anthraquinone

8-chloro-4- (pentachloro-benzoylamino) - orange

1-hydroxy-anthraquinone

e-Chlor-M-Cpentachior-benzoylamino) - orange

1-methoxy-anthraquinone

l- (pentachlorobenzoylamino) -6- yellow

methylmercapto-anthraquinone

l- (pentachlorobenzoylamino) -6- yellow

phenylmercapto-anthraquinone

1- (Pentachloro-benzoylamino) -6- yellow

methylsulfonyl anthraquinone

1- (Pent achlor-benzoylamino) -6- yellow

(4-chloro-phenylsulfonyl) -anthraquinone

Example 12:

According to Example 7 using the amount of pentachlorobenzoic acid specified there and replacing the 15 * 1 parts of 4-amino-l (pentachlor-benzoylaminoi-anthraquinone by the equivalent amount of the amino (ρentachlorbenzoy lamino) -anthraquinone one receives the l, 5-di- (pentachlorbenzoylamino) -anthraquinone, which is identical to the dye mentioned in Example 2 and its dyeing and Pigment properties are the same.

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Claims (1)

Claims where R stands for a substituent, ρ the numbers 0-6, m is the number 5 and η is the number 1 or 2. 2) Anthraquinone dyes of the formula • R, 0 R ₁ I 4 H, ' wherein RJR _{4 is} hydrogen or a substituent with the proviso that one or two of the radicals R ₁ -R. for a rest -NHCO- / ⁷ (Cl) stand and where R stands for a substituent, ρ stands for the numbers 0-6 and m stands for the number 5. 3) Anthraquinone dyes of the formula NHCO- (Cl) NHCO - // (Cl) where R stands for a substituent, ρ stands for the numbers 0-6 and m stands for the number 5 . Le A 12 081-1 - 23 - 109825/2053 ORIGINAL SüiPECTED 4) Anthraquinone dyes of the formula / Q2.) 0 NHOO-jOk " ^m where R stands for a substituent and ρ stands for the numbers 0-6 and m stands for the number 5. ' 5) Anthraquinone dyes of the formula ~ 4 ° ^R 1 wherein R ₁ -R ^ are hydrogen or a substituent with the proviso that one or two of the radicals R ₁ -R ^ are a radical -NHCO- stand, where m is the number 5, R is a substituent and ρ is the numbers 0-6 and where at least one of the radicals R or R ₄ -R. a rest 1 (Y) _n represents, where Y for a substituent and q for the Numbers 0-5 stands. 6) Process for the preparation of anthraquinone dyes of the Formula. Le A 12 081 -I - 24 - 109825/2053 ORtGiNAL INSPECTÖJ, NHO Ο- where R stands for a substituent, ρ the numbers 0.-6, m is the number 5 and η is the number 1 or 2, characterized in that one aminoanthraquinones of the formula wherein R, ρ and η have the meaning given above, with at least η mol of a reactive derivative of a carboxylic acid the formula G ¹ OOH (01) where m has the meaning given above, 7) '/ experience according to claim 6, characterized in ₉ dall. the reaction in Seganv / type basic catalysts, optionally in the presence of acid-binding agents in inert organic solvents at temperatures of sfewa. 40-220 ° 0. 8) Use of the anthracite dyes of Anspivuchs 1 as 9) Use of the anthracite paints that claim 1 with pigmentation of taoksn and paints. le A 12 031 35 09825/2053 to ... 1ü) Use of the anthraquinone dyes of claim 1 for Bulk coloring of polymers, polycondensates, polyaddition products and Vuikanisaten as well as for the coloring of printed albums and printing inks, 11) Use of the anthraquinone dyes of claim 1 for Bulk dyeing of polyvinyl chloride, polyacrylonitrile, polyesters, Polypropylene, polyethylene and cellulose derivatives, 12) Polymers, polycondensates, polyaddition products, Pigmented printing inks, inks, varnishes and paints or »mass-colored with the dyes of the claim U A 12 ObI-T - 26