DE1768756A1 - Pigment dyes - Google Patents

Description

FARBENFABRIKENBAYERAG 1768756 LIVIHKUIIN-

*H. June

Pigment dyes

The present invention relates to dyes of the formula

(D

where Y is hydrogen «halogen such as fluorine, chlorine or bromine,

a hydroxyl, alkoxy, amino or arylamino group,

an X hydrogen, halogen, an amino, arylamino,

Acylamino, hydroxy or alkoxy group, the other X

denotes the radical -NH-R and R stands for the grouping -CO-B-

GO-NH-E, where the rings C and D optionally "

may have further substituents,

as well as their production and use as pigments. In the grouping -CO-B-CO-NH-E, B means a single bond or a saturated or unsaturated one which is optionally further substituted or interrupted by heteroatoms Alkylene radical or an optionally further substituted one or polynuclear arylene or heteroarylene radical, E is an optionally interrupted by heteroatoms

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BAD ORlGiMAL

Saturated or unsaturated having substituents Alkyl or cycloalkyl radical or an optionally one or several halogen atoms such as chlorine, fluorine or bromine, nitro groups, Alkyl groups with 1-12 carbon atoms, cycloalkyl groups, fused-on cyclohexyl or benzene rings, trifluoromethyl groups, aryl amino groups, hydroxyl groups, alkoxy groups with 1_3 carbon atoms, phenoxy groups, alkylsulfonyl groups, arylsulfonyl groups, Alkyl carbonyl groups, aryl carbonyl groups, carboxyl groups, carboxylic acid ester groups, unsubstituted carbonamide groups, optionally »-substituted sulfamoyl groups, alkylsulfonylamino groups, Arylsulfonylamino groups, phenylazo or phenylazoxy groups or an optionally containing aryl radical substituted heteroaryl radical.

Suitable radicals X are, for example, hydrogen, halogens such as chlorine or bromine, amino groups , optionally substituted arylamino groups, alkylcarbamoyl groups, optionally substituted arylcarbamoyl groups, hydroxyl groups or alkoxy groups with 1-3 carbon atoms.

Suitable radicals Y are, for example)

Hydrogen, halogens such as fluorine, chlorine or bromine, amino groups, optionally substituted ary! Amino groups, hydroxyl groups or Alkoxy groups with 1-3 carbon atoms.

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BATH ORIGINAL

Suitable radicals B are, for example, the following: Optionally branched, saturated or unsaturated alkylene radicals with 1-17 carbon atoms, cycloalkylene radicals with up to 6 carbon atoms, optionally substituted phenylene radicals, naphthylene radicals or Heteroarylene reete with 5-6 ring members, biphenylene residues, residues of azobenzene, axoxybenzene, hydrazobenzene, benzophenone, diphenylmethane, Diphenyl ethers, diphenyl sulfones or azobiphenyls.

GeelÄn "te alkyl radicals E are especially saturated or unsaturated alkyl radicals having 1-18 m-saturated carbon atoms, aralkyl, in particular benzyl radicals, or cycloalkyl groups with up to 9 C atoms, hydroxyalkyl and carboxyalkyl groups with 1-6 C atoms, alkoxyalkyl, Alkylthioalkyl and iminoether radicals with 4-11 carbon atoms or radicals of cycloalkylene sulfones.

Suitable aryl radicals E are in particular the phenyl, naphthyl, Anthracenyl or pyrenyl radicals.

Substituents for rings C and D in Prague include: halogen atoms such as fluorine, chlorine or bromine, nitro groups, alkylcarbonylBmino groups with 1-18 carbon atoms, arylcarbonylamino groups, for example benzoyl or naphthoylamino groups, hydroxyl groups, alkoxy groups, especially those with 1-3 Carbon atoms,

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optionally substituted phenyl, phenoxy, phenyl mercapto, Phenylsulfonyl or phenobulfonic acid ester groups, carboxy groups, garbamoyl groups or carbalkoxy groups with 1-5 carbon atoms.

Preferred dyes of the general formula (I) are those in where Y and X are a hydroxyl group and the other X is the radical -NH-R, where R is the radical -CO-B-CO-NH-E, where B and E have the meaning given above. Particularly preferred in this series are dyes in which B stands for one Arylene radical, in particular a Phenylenreet "

The compounds according to the invention are prepared according to processes known per se, for example by acylation of anthraquinone derivatives of the formula

in which the rings C and D can have further substituents and in which Y has the meaning given above and one X _{1 is} X with the meaning given above and the other X _{1 is} the radical -NHp,

with reactive derivatives of dicarboxylic acids of the general formula

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BAD ORKäfNAL HO-CO-B-CO-OH (III)

in which B has the meaning given,

and subsequent reaction with at least 2 moles of an amine of the formula

H ₂ NE (IV)

in which E has the meaning given above.

The compounds according to the invention can also be prepared by acylation of anthraquinone derivatives of the formula

X ₁ 0

(V)

wherein Y has the meaning given above, one X _{1 is} X and the other X _{1 is} HeSt-NH ₂ ,

with reactive derivatives of N-substituted dicarboxylic acid mono- " amides of the formula

HOOC-B-CO-NH-E (VI)

in which B and E have the meaning given above «

take place, wherein 1 mole of (V) is reacted with at least 2 moles of a reactive derivative of (VI).

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The preparation of the compounds according to the invention according to the first-mentioned process, can be carried out, for example, that one mole of an amine of the formula (II) with at least 2 moles of a dicarboxylic acid halide of the formula

A'-CO-B-CO-A ¹ (VII)

in which B has the meaning given above and A ^{1 is} halogen such as fluorine, chlorine or bromine,

at temperatures between 40 ° C and 220 ⁰ C in an organic solvent such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene, optionally basic in the presence of catalysts such as pyridine, piperidine, morpholine, Trlmethylamin, Collidln, picoline, lutidine, quinoline with or without the addition of acid-binding agents such as soda, potash, sodium or potassium bicarbonate or quick lime converts to compounds of the formula

X ₀ 0 NH-CO-B-CO-A *

I I Γ c IT Tl D I (viii)

in which A ·, B and Y have the meaning given above, one X ₂ for X _{1 is} CO-A *

one X _{2 stands} for X ₁ and the other Xp stands for the radical -NH-CO-B-

reacted and then after separation from the reaction solution or without isolation with at least 2 moles of an amine formula

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H ₂ NE (IV)

in which E has the meaning given above,

at temperatures between 40 ° C and 22O ⁰ C using the amine (IV) as a solvent or in an organic solvent such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene, optionally in the presence of basic catalysts such as pyridine, Peperidin, morpholine, Trimethylamine collidine, picoline, lutidine, quinoline with or without the addition of acid-binding agents such as soda, potash, sodium or potassium bicarbonate or quick lime.

As examples of those for the preparation of the compounds according to the invention preferably used amino-anthraquinones of the formula (II) may be mentioned: 1,5- and 1,8-diamino-anthraquinone, 1,4,5,8-tetraamino-anthraquinone, 4-chloro-l, 5-diamino-anthraquinone, 2,4,6,8-tetrabromo-l, 5-diamino-anthraquinone, 3-chloro-4,8-diaminol, 5-bis- (4-methyl-anilino) -anthraquinone, 4,5-diamino-l-benzoylamino-anthraquinone, 4,8-diamino-1-hydroxy-anthraquinone, 4,8-diamino-1,5-dihydroxy-anthraquinone, 4,5-diamino-l, 8-dihydroxyanthraquinone, 4,5,8-triamino-l-hydroxy-anthraquinone, 4,8-diamino-1,5-dimethoxy-anthraquinone, 2,6-dibromo-l, 5-diamino-4,8-dihydroxyanthraquinone, the mixture that is used in the bromination of 4,8-diamino-l, 5-dihydroxy or from 4,5-diamino-1,8-dihydroxyanthraquinone in e.g. sulfuric acid, and that about one atom Bromine per mole of 4,8-diamino-1,5-dihydroxy- or 4,5-diamino-1,8-dihydroxy-anthraquinone contains, 3-bromo-l, 4,8-triamino-5-hydro: iiy-

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anthraquinone 2-bromo-4,5,8-triamino-1-hydroxy-anthraquinone or 2- (4-methoxypheriyl) -1,5-diamino-4,8-dihydroxy-anthraquinone.

Under reactive derivatives of dicarboxylic acids are in particular the halides, in particular the fluorides, chlorides and bromides, as well as the esters and anhydrides.

Examples of the derivatives of dicarboxylic acids of the formula (III) used for the preparation of the compounds used according to the invention are preferably the esters, in particular the methyl or ethyl esters and the halides, in particular the fluorides, chlorides or bromides, of aliphatic dicarboxylic acids such as Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, of heteroatom-containing aliphatic dicarboxylic acids such as diglycolic acid, thiodiglycolic acid, methylene-bis-thioglycolic acid, dithiodiglycolic acid, dithiodiglycolic acid (dithiodiglycolic acid), (dithiodiglycolic acid, (1,8) dithiodiglycolic acid, iminodiacetic acid, such as (1,8) 1,9) »Hydroxysuccinic acid, W acetonedicarboxylic acid, acetylamino-succinic acid, 2-acetylaminoglutaric acid, of cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid (1,2) or - (1,4), camphoric acid, of bicyclic dicarboxylic acids such as bicyclo [2.2 , l] -heptene- (5) -dicarboxylic acid- (2,5) of unsaturated dicarboxylic acids acids such as fumaric acid, 1,2,3,6-tetrahydrophthalic acid, mononuclear arylenedicarboxylic acids such as benzene dicarboxylic acid (1,2), - (1,3), or - (1, ¹ I), 4-chloro-isophthalic acid, 5-nitro-isophthalic acid, 2-chloro-terephthalic acid,

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BAD OR! Grf4AL

2-nitro-terephthalic acid, 2,5-dichloroterephthalic acid, 4-hydroxyisophthalic acid, 2,5-dimethoxyterephthalic acid, 2,5-difluoroterephthalic acid, tetrachloro- or tetrafluoroterephthalic acid, of polynuclear. (1,4) - (1,5), or - (2,6), of polynuclear fused arylenedicarboxylic acids such as diphenyl-dicarboxylic acid (^, V), diphenylsulfon-dicarboxylic acid (4,4 '), azobenzene-dicarboxylic acid-C ¹ *, ¹ * '), azoxybenzene-dicarboxylic acid - ^, ^') hydrazobenzene-dicarboxylic acid - ^, ^ -

Benzophenone dicarboxylic acid (2,4 ^> ) j Diphenyl ether dicarboxylic acid | {h, k> ), diphenylmethanedicarboxylic acid-C ¹ *, ¹ ^) p-terphenyldicarboxylic acid- (4,4, * · '), V-carboxy-biphenyl - ^ - azo - ^ - biphenyl-carboxylic acid- (4 *) , or of heteroarylene dicarboxylic acids such as 2,5-puranedicarboxylic acid, 2,5-thiophene-dicarboxylic acid, pyridine-dicarboxylic acid - (2,3), - (2, ^), - (2,5) or - (2,6).

Examples of the amines of the formula (IV) used to prepare the compounds used according to the invention include: aliphatic amines such as methylamine, ethylamine, propylamine, n-, iso- and tert-butylamine, dodecyl-, tetradecyl- or hexadecylamine, 9- Amino-heptadecane, stearylamine, substituted aliphatic amines such as 2-amino- or 1-amino-ethanol, 3-amino-propanol, aminoacetic acid, 6-amino-hexanoic acid, aminoalkanes with a heteroatom in the chain such as 2- (2-amino-ethyl-amino ) -ethanol ~ (1), 5-methoxypropylamine, 3-ethoxy-propylamine, 3-butyloxy-propylamine, 3- (2- ethyl-hexyloxy) -propylamine, 2-amino-diethyl sulfide, alkenylamines such as allylamine, cycloalkylamines such as cyclohexylamine , 2- (2-hydroxy-

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Ethyl-cyclohexylamine, 2-, 3- or 4-methyl-cyclohexylamine, hexahydrobenzylamine, cycloalkylamines with interrupting heteroatoms in the alkylene chain, such as j5-amino-sulpholane, N- (2-amino-ethyl) piperazine. Aralkylamines such as benzylamine, 1-amino-1- or 2-phenylethane, iO -amino-acetophenone, optionally substituted arylamines with optionally fused or fused aryl nuclei such as aniline, 2-, 3- or 4-chloro-aniline, 2,3-, 2,4-, 2,5-, 3,4- or 3,5-dichloroaniline, 2,4,5-trichloroaniline, 2-, 3- or 4-nitroaniline, 4-chloro-2-nitro-aniline, 5 -Chlor-2-nitro-aniline, 3-chloro-4-nitro-aniline, 2,5-dichloro-4-nitro-aniline, 2,4-dinitro-aniline, 6-bromo-2,4-dinitro-aniline , 2-, 3- or 4-aminotoluene, 2-, 3- or 4-aminobenzotrifluoride, 4-chloro-2-aminotoluene, 5-chloro-2-aminobenzotrifluoride, 4,5-dichloro-2-aminotoluene, 4 -, 5- or 6-nitro-2-aminotoluene, 4-chloro-3-aminotoluene or -benzotrifluorine, 2-ethyl-aniline, xylidines, 5-amino-1,3-bis-trifluoromethyl-benzene, 2- Amino-1,3,5-trimethyl-benzene, 4-amino-1-methyl-3,5-diethyl-benzene, 4-amino-1,3-dimethyl-5-ethylbenzene, 4-dodecyl-aniline, 5, 6,7,8-Tetrahydro-naphthyl-amine- (1), or - (2), 4-araino-1-cyclohexylbenzene, 1- or 2-aminonaphthalene, 2-amino-anthra cen, 1-amino-pyrene, 6-aminocrysene, 2- or 4-amino-diphenylamine, 4-amino-4'-methyl-diphenylamine, 3-amino-4-methyl-diphenylamine, 2-, 3- or 4- Amino-diphenyl ether, 2-, 3- or 4-amino-1-methoxy-benzene, 4-chloro-5-nitro-2-amino-1-methoxy-benzene, 4'-amino-4-methoxy-diphenylamine, ( 2-hydroxyethyl) (4-aminophenyl) sulfone, methyl (4-aminopheny 1) sulfone, 4-amino »3-methoxy-diphenylamine, 4-amino-1,3-dimethoxy-benzene, 6-chloro-4-cimino-l, 3-dimethoxy-benzene, 2-amino-l, 4-diethoxy-benzene, 3-amino-4-methoxy-diphenylsulfone, 4-amino-acetophenone, 4-atnino-ben zophenone, 2-, 3- or 4-amino-benzamide, 4-amino-benzoic acid-methy 1- or

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ethyl ester, I-nitro-H-amino-benzamide, 4-chloro-2-amino-benzonitrile _> amino-isophthalic acid dinitrile, 4-amino-isophthalic acid diamide, 6-amine naphthoic acid amide- (2), 5- or 4-amino-benzenesulphonic acid amide , J> - Amino-benzenesulfonic acid- (2-hydroxyethyl) -amide, 4-Amino-benzenesulfonic acid-anilide, 2-Amino-benzoic acid.- sulfonic acid- (4) -diamide, 4-Amino-azobenzene, 4-Amino-azobenzene carbonamide - (4 ⁱ ) or heteroaromatic amines such as 3- or 2-amino-dibenzofuran, 2-aminopyridine, 2-aminomethyl-pyridine, Oz-ethyl - ^ - amino-carbazole, 2-amino-4-methyl-pyridine, J- Amino-l ^^ - triazole, 5-amino-2-phenyl-f benzotriazole ^ -amino-thiazole, 2-amino-benzothiazole, 6-amino-2-methyl-benzothiazole, or 6-methoxy-2-aminobenzthiazole .

The dyes produced fall into one suitable for pigments Form or can be converted into a suitable for pigments Form can be converted into fine distribution by post-treatment known per se, for example by dissolving or swelling in strong inorganic acids such as sulfuric acid and discharging on ice. The fine division can also be done by grinding with or without Grinding aids such as inorganic salts or sand, optionally | in the presence of solvents such as toluene, xylene, dichlorobenzene or N-methyl-pyrrolldon achieved v / earth. Color strength and transparency of the pigment can be influenced by varying the aftertreatment.

The pigments used according to the invention can be used to produce very real pigmented systems, such as mixtures with others St.offen, preparations, paints, printing inks, colored paper and colored macromolecular substances are used.

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When mixed with other substances, for example, those with inorganic white pigments such as titanium dioxide (rutile) or understood with cement. Preparations are, for example, plush pastes with organic liquids or doughs and fine doughs with water / water, dispersants and, if necessary, preservatives. The term paint is available for Example for physically or oxidatively drying paints, stoving paints, reactive paints, two-component paints, emulsion paints for weatherproof coatings and glue paints. Under

W Printing inks are those for paper, textile and metal printing. The macromolecular substances can be of natural origin such as rubber, obtained by chemical modification such as acetyl cellulose, cellulose butyrate or viscose, or produced synthetically such as polymers, polyadducts and polycondensates. Plastic compounds such as polyvinyl chloride, polyvinyl acetate, polyvinyl propionate, polyolefins for example polyethylene or polypropylene, polyesters for example polyethylene terephthalate, polyamides, super polyamides, may be mentioned.

| Polymers and copolymers made from acrylic esters, Methacryleeti Acrylonitrile, acrylamide, butadiene, styrene and polyurethanes and polycarbonates. The pigmented with the claimed products th substances can be in any form.

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The compounds used according to the invention have excellent pigment properties and are not only excellent water-fast, oil-resistant, acid-fast, lime-fast, alkali-resistant, solvent-resistant, over-lacquer-proof, spray-proof, sublimation-proof, heat-resistant, vulcanization-resistant, but also very productive, easy to distribute in plastic masses and excellent Light and weather resistance.
The parts given in the examples are parts by weight.

Example 1:

a) 8 parts of 1,5-dihydroxy- ¹ ! , 8-di - (^ - phenylcarbamoyl-benzoylaminc) -anthraquinones, which were finely divided by grinding in a grinding mill with 2 parts of xylene and 160 parts of sodium chloride and washing out of the common salt, are coated with a stoving varnish made from 25 parts of xoconut oil alkyd resin ( ¹ 10 $ 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. It carries the mixture to be painted on substrate, curing the coating by baking at ™ 130 ⁰ C and receives blue deck strong coatings excellent fastness and excellent light and weather fastness.

Pigmented stoving enamels with the same fastness properties are obtained by adding 15-25 parts of the specified alkyd resin or an alkyd resin based on cottonseed oil, castor oil, castor oil or synthetic fatty acids and used instead of the specified

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Amount of melamine resin 10-15 parts of the mentioned melamine resin or a condensation product of formaldehyde with urea or with benzoguanamine is used. Pigmented stoving enamels with similar good fastness properties and a similar shade are obtained if, instead of the specified 1,5-dihydroxy- ^, 8-di- ( ¹ -phenylcarbamoyl-benzoylamino) -anthraquinone, corresponding amounts of fine-divided l ^ -dihydroxy- ¹ }, 8-di - (^ - methylcarbamoyl-benzoylamino) -anthraquinone, 1,5-dihydroxy- ¹ *, B-di- ^ i-butylcarbanoyl-benzoylaminoj-anthraquinone, 1,8-dihydroxy- ¹ }, 5 ^ i ( ¹ I-phenylcarbamoylbenzoylamino) anthraquinone, 1,8-dihydroxy- ¹ ! , 5-di- ^ nethylcarbamoyl-benzoylamino) anthraquinone, ^{1,5-dihydroxy-1} J, 8-di- £ M- (2-chloro-phenylcarbamoyl) -benzoylamino] -anthraquinone or ^{1,5-dihydroxy-1]} , 8-di (n-dodecylcarbamoylbenzoylamino) anthraquinone is used.

b) Instead of the specified amount of pigment, 1 to 10 parts of a mixture of titanium dioxide (rutile type) with one of the im Example la pigments specified in a ratio of 0.5-50: 1 in the lacquer specified in example la are obtained with the same Further processing Coatings with the same fastness properties and with increasing titanium dioxide content to blue shifted to white Hue.

c) The 1,5-dihydroxy- ¹ described in Example la! , 8-di- (* <- phenylcarbamoyl-benzoylamino) -anthraquinone is prepared, for example, by adding 20 parts of ¹ l, S-diamino-l ^ -dihydroxy-anthraquinone at 80 ° C. with stirring to a solution of 100 Parts of terephthalic acid dichloride in 250 parts of aniline-free dry nitrobenzene

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and 20 parts of pyridine and stirred at 80 ° to 115 ° until all of the 8-diamino-1,5-dihydroxy-anthraquinone has been acylated. The precipitate is filtered from the precipitated l, 5-dihydroxy-4 _J 8-di- (4-chloroformyl-benzoylarnino) anthraquinone, which is present as violet prisms off, washed with dry nitrobenzene excess terephthaloyl dichloride, and sets the nitrobenzene moist filter cake after dilution ¹ 100 parts of dry nitrobenzene with stirring with 6o parts of aniline at 14o-16o ° C until acylation is complete. At 100 ⁰ C of the dark blue in the form of prisms is suctioned precipitated product filtered off, washed with hot nitrobenzene to colorless flow, ™ then with alcohol and hot V.'asser and dried at 50 ° in a convection oven.

If, instead of aniline, 25 parts of 2-chloro-aniline or 28 parts of dodecylamine are used in the presence of 12 parts of Μ, Ν-dimethylaniline, or instead of aniline at 14o-l ° C, it is replaced with 22 parts of n-butylamine at 70 to 80 ° or by bubbling methylamine at 100 ⁰ C to, or one goes from 4, S-diamino-LJS-dihydroxy-anthraquinone, so one obtains the other, in example 1 a specified compounds.

The other compounds according to the invention are prepared analogously. G

Example 2;

In 100 parts of a nitrocellulose lacquer that consists of 44 parts Collodion wool (low viscosity, 35 pounds, butanol moist), 5 parts Dibutyl phthalate, 40 parts of ethyl acetate, 20 parts of toluene, 4 parts n-butanol and 10 parts of glycol monomethyl ether, 6 parts of 1,5-di- [4- (n-butyl = carbamoyl J-benzoylamino ^ -anthraquinone rubbed in.

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After spreading and drying, red-tinged_geibe coatings of excellent lightfastness and fastness to overcoating are obtained.

The same results are obtained when using nitro lacquers with 10-15 parts nitrocellulose content, 5-10 parts soft • maker content and 70-85 parts of solvent mixture preferred use of aliphatic esters such as ethyl acetate, butyl acetate and aromatics such as toluene and xylene and smaller Shares of aliphatic ethers such as glycol ethers and alcohols such as ^ butanol. The term `` verifiers '' can be understood as meaning, for example Phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, phosphoric acid esters, castor oil alone or in combination with oil-modified alkyl resins.

Coatings with similar fastness properties are obtained from Use of other physically drying fuel, zapon and nitro lacquers, of air-drying oil, synthetic resin and nitro combination lacquers, oven- and air-drying epoxy resin paints ", optionally in combination with urea, melamine, alkyd or phenolic resins.

Coatings with similar fastness properties and yellow Color is obtained when using appropriate amounts in fine distribution

1,5-Di-3- (isobuty2carbamoyl) -benzoylamino] -anthraquinone, 1,5 -Di-T ¹ J- (tert-butyl carbarnoyl.) - benzoylarnino [] - anthraquinone, 1,5-1) 3- [^ - (l-dodecyl carbarr.oyl J-benzoylßrnino ^ -anthraquinone, 1,5-di ~ ^ - (stearyl carbarnoyl.) - benzoylemino] -anthraquinone,

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1,5-Di- £ 4- (cyclohexylcarbaiTioyl) -benzoylanino] -anthraquinone, · 1,5-Di- [ ¹ U (ß-phenyl-ethyl carbamoyl) -benzoylamino [] -anthraquinone, 1,5-Di- [ ¹ U (4-dodecyl-phenylcarbamoyl) -benzoylaralno [J-anthraquinone, 1,5-di [ ¹ U (4-trifluoromethyl-phenylcarbamoyl) -benzoylamino] J-anthraquinone,
1,5-Di - [^ ¹ U ( ¹ U chloro-S-trifluoromethyl-phenylcarbarrioyl) -benzoylamino ~

antrachinone,

1,, 5-Di- ^ ¹ U (3-sulfamoyl-phenylcarbamoyl) -benzoylamino]] - anthrachi-

non or

1,5-Di- { ¹ l- [5- (N-phenylsulf amoyl J-phenylcarba ^ oyJbenzoylarnino Vanthra-

chinon instead

1,5-di- [4- (n-butylcarbamoyl) benzoylamino]] anthraquinone.

example J> \

5 parts finely divided 1,8-Di-T ^ - (4-methyl-phenyl = carbamoyl) -benzoylamino ^ j-anthraquinone ground in 100 parts of a paraffin-free drying unsaturated polyester resin in a porcelain ball mill. With the grinding process, 10 parts of styrene monomer, 5 parts of melamine-formaldehyde resin, and 1 part be thoroughly stirred a paste of 4o parts of cyclohexanone peroxide and δθ parts f dibutyl phthalate and finally k parts Dryer solution (10 ^ sodium Xobaltnaphthenat in white spirit) and 1 part SiIikonbllösung (l 5 ^ in xylene) added. The mixture is applied to primed wood, and a high-gloss, waterproof and weatherproof golden-yellow coating of excellent lightfastness is obtained.

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Instead of the reactive varnish based on unsaturated polyester resin, min-hardening epoxy resin varnishes are used Dipropylenetriamine as the amine component is yellow Paintwork with excellent vetting and blooming resistance.

Example 4;

100 parts of a 65% solution of an aliphatic polyester with about 8 $ free hydroxyl groups in glycol monoethyl ether acetate are finely divided with 5 parts of 4 - Hydroxy - 1, ¹ I [^ - (2,5-dichloro-phenylcarbamoyl) benzoylamino] anthraquinone W and then mixed well with 44 parts of a 67% solution of the reaction product of 1 mole of trimethylolpropane with 3 moles of toluene diisocyanate. After application of the mixture and reaction of the components, high-gloss red-violet polyurethane coatings with excellent blooming, light and weather fastness result without impairing the pot life.

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, and with moisture-drying polyisocyanate lacquers which produce polyurea lacquers. pigmentations of similar fastness properties and blue hues are obtained when using appropriate amounts of 1,5-dihydroxy-4,8-di - ^ - methylcarbamoyl-benzoylaminoJ-anthraquinone, 1,5-dihydroxy-4,8-di- ( ¹ »-phenylcarbanioyl- benzoylarr.ino) -anthraquinone, 1.5 ^ 1l-hydroxy, 4,8-di- [ ^I <- (4-chloro-phenylcarbamoyl) -benzoyla.T, inOj-anthraquinone,] _# 5-

) -benzoyl-

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aminoj-anthraquinone, 1,5-dihydroxy- ¹ }, 8-Ui- [ ² U (*! - anilino-phenylcarbamoylj-benzoylaminoj-anthraquinone,!, s-dihydroxy- ^ e-di-

ri | - (ij-carbamoyl-phenylcarbamoyl) -benzoyla: nino ""? - anthraquinone or l, 5-dihydroxy- ¹ l, 8-di- [ ¹ <- (pyrenyl- (l) -carbamoyl) -benzoylatnino [] -anthraquinone instead of the above in the example * l

specified dye.

Example 5:

5 parts of a fine dough, obtained by kneading 50 parts of l, 5-dihydroxy-4 ^ Q-di - ^ - ^ - sulfarnoyl-phenylcarb- j

amoyl-benzoylamino ^ -anthraquinone with 15 parts of an aryl polyglycol ether emulsifier and 55 parts of water are mixed with 10 parts of heavy spar as filler, 10 parts of titanium dioxide (rutile type) as V / ice pigment and ko parts of an aqueous emulsion paint, contain approx. 503 polyvinyl acetate, mixed. The color is spread and, after drying, blue paints are obtained with very good fastness to lime and zenium and excellent fastness to clogging and light.

The fine dough obtained by kneading is equally suitable for pigmenting clear polyvinyl acetate emulsion paints, ™ for emulsion paints containing copolymers of styrene and maleic acids as binders, as well as disperse dyes. based on polyvinyl propionate, polymethacrylate or butadiene styrene.
Paints of similar color and similar fastness properties are obtained if , instead of the specified 1,5-dihydroxy- ^, 8-Uisülfamoyl-phenylcarbamoyl) -benzoylamino] -anthraquinone

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corresponding amounts of 1,5-dihydroxy- ¹ ! , 8-di - (^ - phenylcarbarr.oylbenzoylamino) -anthraquinone, 1,5-dihycroxy- ¹ }, B-di-j ^ - (2-chlorophenylcarbamoylj-benzoylamino ^ -anthraquinone, 1,5-dihydroxy- ¹ J, e-di-f ^ - (il-chloro-phenylcarbamoylj-benzoylamino ^ - anthraquinone, 1,5-dihydroxy- ¹ 1,8-CJi - [^ - (n-butylcarbamoyl) -benzoylarrinoj-anthraquinone, 1,5 -Dihydroxy- ¹ 1,8-di-C5- (n-butylcarbamoyl) -valerylamino-anthraquinone, 1,5-dihydroxy - ^, B-di - ^ - ^ - nitro-phenylcarbamoyl) -benzoylamino] -anthraquinone, 1, 5-dihydroxy- ^, 8-di - [] ^ - (5-nitro-phenylcarbamoyl) -benzoylainino] -anthraquinone, 1,5-dihydroxy- ^, 8-di_r ^ _ (Il_nitro-phenylcarbanioyl) -benzoylamino]] - anthraquinone or 1,5-dihydroxy-'l, 8-di- [ ⁱ l- (jJ ^ -dichloro-pheriylcarbaittoylJ-benzoylätninoJ-anchrachinon used.

Example 6;

10 parts of the pigment paste mentioned in Example 5 are used with a mixture of 5 parts chalk and 5 parts 20 ^ iger Glue solution mixed. You get a blue wallpaper coating color, with which one achieves excessive excellent lightfastness. Others cannot produce the pigment dough either ionic emulsifiers such as the reaction products of nonylphenyol with ethylene oxide or ionic wetting agents such as sodium salts of Alkylnrylsulfonsäuren, for example the Dinaphthylmethandisulfonsaure, Sodium salts of substituted sulfofatty acid esters and sodium salts of paraffin sulfonic acids in combination with; Alky]] H) lyg] ycol ethers can be used.

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BATH

Example 7;

A mixture of 65 parts of polyvinyl chloride, 35 parts of diisooctyl phthalate, 2 parts of dibutyltin mercaptide, 0.5 part of titanium dioxide and 0.5 part of H-hydroxy

^ 5_Di-FH (n-butylcarbamoyl -) benzoylamino] anthraquinone, which has been brought by grinding with sodium chloride in the presence of test gas in fine distribution is inked on a roll mill at 165 ° C. The result is an intensely broth-colored mass which can be used for the production of foils or

FormkbYpern can serve. The coloring is excellent Light and very good fastness to repairs.

Colorations of yellow shades and similar fastness properties are obtained if the specified 4-hydroxy-1,5-di- (H-butylcarbanpyl-benzoylamino) -anthraquinone is obtained by corresponding amounts of 1,5-di- (H-phenylcarbarr.oylbenzoylamino) -anthraquinone , 1,5-di- £ H- (methylcarbarcoyl) -. benzoylamino ^ -anthraquinone,!, S-Di-C ^ -P - ^^ yicarbamoy ^ -benzoylamino] -anthraquinone, 1,5-di- [5- (H-chlorophenylcarba.T _: oyl) -benzoylaminojanthraquinone, 1 , 8-Di- [H- (methylcarbamoyl) -benzoylamino [] -anthra = quinone,!, S-Di-iH-phenylearbamoyl-benzoylaminoJ-anthraquinone, 1,8-di-J ^ H- (H-, sulfamoyl. -phenylcarbamoyl) benzoylamino] anthraquinone, l, ö-di- [] ¹ l- (H-carbamoyl-phenylcarbamoyl) -benzoylamino] j-anthraquinone or l, 5-Di - [] H- (H-carbaiiioyl-phenylcarbamoyl ) -benzoylaminoj-anthraquinone replaced.

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Example 8;

0.2 part, finely divided, l ^ -dihydroxy- **, 0-di- (methylcarbamoylbenzoylamino) anthraquinone v; earth mixed with IGO parts polyethylene, polypropylene or polystyrene granulate. the Mixing can either be done at 220 to 28o ° C directly in an injection molding machine sprayed, or processed into colored rods in an extrusion press or into colored skins on the mixing mill will. The rods or pellets are optionally granulated and ground sprayed in an injection molding machine.

Moldings have very good light and migration fastness. Similarly, at 28O-3OO ° C, optionally below Nitrogen atmosphere, synthetic polyamides made from caprolactan or Adipic acid and hexamethylenediamine or the condensates of terephthalic acid and ethylene glycol colored v / earth.

example 9 '

1 part placed on the fine division 1,5-di- ^[1 I- (4-methyl-phenyl = carbamoyl) -benzoylamino "| anthraquinone, 10 parts of titanium dioxide (rutile type) and 100 parts of this interpolymer in powder form based on acrylonitrile butadiene-styrene are mixed and alzwerk inked on a V / at I4o-l8o °. an orange-coat, which is granulated and molded in an Spritzguömaschine at 200-25C ⁰ C. this gives orange moldings very good light and migration fastness and excellent heat resistance.

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Else, but colored similarly V / at a temperature of l80-220 ° C and without the addition of titanium dioxide v / ground synthetic materials based on cellulose acetate, cellulose butyrate and their mixtures with similar fastnesses.

Example 10;

0.2 parts !, P

anthraquinone are mixed in finely divided form η3t 100 parts of a polycarbonate plastic based on in an extruder or in a kneading screw ^ at 25O-28o ° C and processed into granulate. A blue, transparent granulate of excellent lightfastness and heat resistance is obtained.

example 11:

90 parts of a weakly branched polypropylene glycol with a molecular weight of 2500 and a hydroxyl number of 5 ^, 0.25 part of endoethylene piperazine, 0.5 part of tin (JI) octoate, 1.0 part of a polyether siloxane, 5.5 parts of water, 12 , 0 parts of a grind of 10 parts, finely divided 3, 5-Di-J ^ - ( ¹ J-nie thoxy-phenyl = carbamoyl) -benzoylamino] ~ anthraquinone in 50 parts of the specified polypropylene glycol are mixed well together and then with ^ 5 Parts of toluene diisccyanate (8θ £?, ** - and 20 $ 2,6-isomer) are intimately mixed and poured into a mold. The mixture becomes cloudy after 6 seconds and foam formation occurs. After 70 seconds an intensely yellow colored, soft polyurethane cha ums t off has formed, the pigmentation of which has excellent lightfastness.

109882 / U47 ^{Le A 11 572} -25- '

Reddish blue flexible polyurethane fabrics similarly more lightfast Pigmentation is obtained when the 1,5-di-f4- (4-methoxyphenylcarbamoyl) is replaced ) -benzoylamino3 ~ anthraquinone by corresponding amounts of 1,5-dihydroxy-4,8-di- {~ 4. {methylcarb ·: = amoyl) benzoylamino 3-anthraquinone, 1,5-dihydroxy-4,8-di- [4- (n-butylcarbamoyl ) benzoylamino] anthraquinone, 1,5-dihydroxy-4,8-dl- £ 4- (n-dodecyl carbamoyl) benzoylamino "i-anthraquinone, 1,5-dihydroxy-4,8-di-r4- (4-chloro-phenyl carbamoyl) -benzoyl = amino] anthraquinone, 1,5-dihydroxy-4,8-di-f4- (4-carbamoyl-) phenylcarbamoyl) benzoylamino "1-anthraquinone, 1,5-dihydroxy-4,8-di- £ 4- (4-sulfamoyl - phenylcarbamoyl) -benzoylaminej-anthra = quinone or 1,8-dihydroxy-4,5-di- [4- (4-sulfamoyl-phenylcarb amoyl) -benzoylaminoj-anthraquinone. .-. .

Example 12;

90 parts of a weakly branched polyester of adipic acid, diethylene glycol and trimethylolpropane with a MoÜcular weight of 2000 and a hydroxyl number of 60 are mixed with the following components: 1.2 parts of dimethylbenzylamine, 2.5 parts of sodium castor oil sulfate, 2.0 parts of an oxethylated, benzyliei »· th oxydiphenyls, 1.75 parts of water, 12 parts of a paste, prepared by grinding 10 parts of finely divided l-benzoylamino- ^ b-di-L ^ -i ^ -carBamoyl-phenyl-" carbamoyl *) "-benzoylamino ^ -anthraquinone in 50 parts of the above polyester. After mixing, 40 parts of toluene diisocyanate (65 # 2,4- and 35 $ 2,6-isomer) are stirred in with stirring and the mixture is poured into a mold and foamed.

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After 60 seconds a red-violet colored polyurethane foam has formed, the coloring of which is characterized by very good lightfastness. Green-blue colorations of similar lightfastness are obtained when using appropriate amounts of 3-chloro 1-, 5-di- ( ⁱ 4-methyl-anilino) ^-1 <, 8-di- [4_ (2 _J 3-dichlorophenylcarbamoyl) -benzoylamino] -anthraquinone, 5-amino-1-hydroxy- ¹ t, 8-di- | [ ¹ l- (2,5-dichloro-phenylcarbamoyli-benzoylamino ^ -anthraquinone, ^, o-dibromo- ^ jB-dihydroxy ~ l _f 5-di- [ ¹ »- ( ⁱ l-carbamoyl-phenylcarbamoyl) -benzoylaniino-3-anthraquinone, H , 8-diamino ^{-1,5-di- [i} {- (n-butylcarbamoyl) -benzoylamino] -anthraquinone instead of the specified l-Benzoylamino- ¹ », 5-di- '. [^ - (Jl-carbarnayl-phenylcarbamoyli-benzoylamino-anthraquinone.

Green-blue colorations of similar lightfastness are obtained if instead of the specified l-Benzoylamino- ^ S-di - ^ - ^ - carbamoyl-

phenylcarbamoyl) benzoylamino] j-anthraquinone corresponding amounts uses one of the two dyes that you get after the preparation example Ic proceeds, but instead of 20 parts of 1,4-diamino-anthraquinone 29 parts of one of the two dyes are used, which are obtained when one!, S-dihydroxy- ^ e-diamino- or 1,8-dihydroxy-4,5-diamino-anthraquinone brominated in sulfuric acid so that the reaction product is about one atom of bromine per mole of l, 5-dihydroxy-4,8-dlamlno- or 1,8-dihydroxy-4,5-diamino-anthraohinone contains.

Example 13;

With a printing ink made by grinding 35 parts in Pin distribution brought 1,5-dihydroxy-4,8-di- (4-phenyloarbamoylbenzoy1-amino) -anthraquinone and 65 parts of linseed oil and adding 1 part

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Siccatlv (co-naphthenate, 50% in white spirit) are blue offset prints high brilliance and color strength and very good light and paintwork get authenticity. Use of this printing ink in book, light, '' Stone or steel engraving leads to blue prints with similar fastness properties. If the pigment is used to color tinplate printing or low-viscosity gravure printing inks or printing inks, the result is blue Prints of similar fastness.

If you replace the 1,5-dihydroxy- ¹ ! , 8-di - (^ - phenylcarbamoyl-benzoyla.Tiino) -anthraquinone by corresponding amounts of 1,5-dihydroxy- ¹ 1,8-di - (^ - methylcarbamoyl-benzoylamino) -anthraquinones 1,5-dihydroxy- * \ , 8- ^ i- [ ¹ U (n-butylcarbamoyl-benzoylaminoj-anthraquinone, 1,5-dihydroxy- ^, 8-di - [] 5- (a-butylcarbamoylj-valerylamino ^ -anthraquinone, 1,5-dihydroxy- ¹ I, 8-di- [| ^{2,5-dichloro-1} l- (n-dodecylcarbamoyl) -benzoylamino ~ j-anthraquinone, ^{1,5-dihydroxy-1} ', 8-di- (H-hydroxy-3-phenylcarbamoyl -benzoylamino) anthraquinone, 1,5-dihydroxy- ¹ *, 8-dl- (6-phenylcarbamGyl-naphthoyl- (2) -amJno) -anthraquinone, 1,5-dihydroxy- ^ , 8-di-

^ _ (J) -phenylcarbamoyl-phenyl J-benzoylaminoJ-anthraquinone, 1,5-dihydroxy - ^, 8-di - ^ - (^ - phenylcarbamoyl-phenoxyj-benzoylaminoj-anthraquinone, 1,5-dihydroxy- ⁱ », 8 di- [] ^l <- (2-phenylcarbamoyl-benzoyl) -benzoylaminoj-anthraquinone or 1,5-dihydroxy- ¹ ', S-di-f ¹ - (^ -phenylcarbamoylphenylsulfonyl) benzoylamino]] - anthraquinone, receives one prints of similar color and similar authenticity.

From 10 parts of the fine pigment dough given in Example 5, 100 parts of 3 # gum tragacanth, 100 parts of an aqueous 50% egg album in solution and 25 parts of a nonionic wetting agent is a Preparing printing paste. A textile fiber is printed on and steamed

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BAD ORiQfNAL

100 ° C and receives a blue print; which is characterized by excellent fastness properties, especially light fastness. Instead of tragacanth and egg albumin, other binders that can be used for fixing on the paper, for example those based on synthetic resin, British gum or cellulose glycolate, can be used in the printing approach. Example 15;

A mixture of 100 parts of crepe light, 2.6 parts of 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 g (anatase type) is on a mixing roll mill at 50 ⁰ C colored with 2 parts 1,8-Dt £ ^ - (5,5-dichlorophenyicarbamoyl -) -benzoylamino] -anthraquinone and then vulcanized at 140 ° C for 12 minutes. A yellow-colored vulcanizate of very good lightfastness is obtained.

Example 16;

100 parts of a 20 #Lgen aqueous paste of 1,5-di-F ¹ J- ( ¹ USuIfamoyl-phenylcarbamoyl J-benzoylamino ^ -anthraquinone, prepared for example by dissolving the dye in 96% sulfuric acid, pouring onto ice , filtering and washing until neutral with Viasser, 22500 parts of an aqueous, approximately 9% viscose solution are added in a stirrer.The colored mass is stirred for 15 minutes, then deaerated and subjected to a spinning and desulphurisation process.Yellow colored threads or films with very good lightfastness are obtained.

"Γθ9882 / η * 7

Wine-red pigmented threads or foils of similar authenticity are obtained if a 20 # solution of anthraquinone dyed with the H -hydroxy 1,5-άί - [_ 1- (4 -sulfamoyl-phenylcarbamoyl) -benzoylamino] -anthraquinone, which has been finely divided Acetyl cellulose in acetone or a 15-25 £ ίε solution of polyacrylonitrile in dimethylformamide is subjected to a dry spinning process.

Example 17:

10,000 parts of a paper pulp containing 4 parts of cellulose per ICO are treated in the Hollander for about 2 hours. ^{During this time, 1} l parts of resin glue are added at quarter-hour intervals, then 30 parts of an approximately 15% pigment dispersion, obtained by grinding in a ball mill, 1.8 parts of 1., 5-dihydroxy- ¹ ! 8-di- (^ -methylcarbamoyl. -Benzoylaminoj-anthachinon with ¹ J ^ O parts of dinaphthylmethanedisulfonic acid and 22 parts of water, then 5 parts of aluminum sulfate. After finishing on a paper machine, a paper of excellent lightness is obtained.

Example 18:

The hergestelltefclaipigmentierte of Example 17 paper is impregnated with the 55 ^ solution of a urea-formaldehyde resin in n-butanol and baked at 1 ⁰ C ^ O. A reddish-tinged blue laminate paper of very good migration and excellent lightfastness is obtained.
Laminate paper with the same fastness properties is obtained by lamination

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a paper that is gravure with a printing ink Was printed, the specified in Example 5, flat pigment paste and contains water-soluble or saponifiable binders.

Examples 19-102:

According to Example la, but using the corresponding amounts of the dyes given in the table below, finely divided instead of l, 5-D ^ hxdro; cy- ² i, 8-di- ( ⁱ l-methylcarbamoyl J-benzcylamino ^ - anthraquinone, you get real pigmented stoving enamels in the colors given in the table:

Belsp. Farfaetoff hue

! 9 1,5-di- (4-phenylcarbamoyl-i) enzoylamino) - yellow anthraquinone

20 1,5-Di- [ ¹ U (methylcarbarnoyl) -benzoylamino] - yellow anthraquinone

21 1,5-Di- [3- (methylcarbamoyl) -benzoylamino] - yellow | anthraquinone

22 l, 5-di - [] 3 - (^ - chlorophenylcarbanioyl) benzoyl = yellow amino] anthraquinone

23 l, 8-Di- [4- (methyicarbamoyl) -benzoyla.Tiino] - yellow * anthraquinone

24!, E-Di-C ^ -phenylcarbamoyl-benzoylaminoJ-anthra-yellow chihon "■

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Ex.

Dye-

hue

25 4-chloro-1,5-di £ 4- (n-butylcarbamoyl) - yellow • benzoylamino]] - anthraquinone

26 ^ -Chlor-1,5-di £ ^ ~ (n-tetradecylcarbanioyl) - yellow benzoylamino l-anthraquinone

27 4-chloro ~ 1,5-di £ ^ - (n-hexadecylcarbamoyl) - yellow benzoylamino]] anthraquinone

28 4-chloro-1,5-di- [4- (heptadecyl- (9) -carbamoyl) - yellow benzoylamino]] anthraquinone

29 4-Chloro-1,5-di - (^ - allylcarbamoyl _T • yellow benzoylamino) anthraquinone

30 4-chloro _T 1,5-di - [] ^ - (2-hydroxyethyl-carbamoyl) - yellow benzoylamino]] - anthraquinone

31. 4-chloro ~ 1,5- ^ i-Hl- (5-carboxypentyl-carbamoyl) - yellow

benzoylamino]] anthraquinone

32 4-chloro ~ 1, 5-di- [it - [] 2- (2-hydroxyethyl-amino) - yellow ethylcarbaraoylj-benzoylaraino | -anthraquinone

33 ^ -Chlor-1,5-di- £ 4 ~ (3-butoxy-propylcarbamoyl) - yellow benzoylamino]] - to thrachinone

3 ^ 4-chloro-1,5-di - [] 4 ~ (3-sulfa-cyclopentyl-yellow S, S-dioxide-carbamoyl) -benzoylamino ^ -anthraquinone

35 ^ -Chlor-1,5-di - [] U- (3-chloro-phenylcarbamoyl) - yellow benzoylamino]] anthraquinone

36 4-Chloro-1,5-di [] 4- (2,4-dichloro-phenylcarbamoyl) - yellow benzoylamino]] anthraquinone

37 4-chloro-i, 5-di-J] 4- (2 _f ^ -dinitro-phenylcarbamoyl) - yellow benzoylamino]] - to thraquinone

38s 4-hydroxy-1,5-di- (it-ynethylcarbaraoyl-narron

benzeylamino) anthraquinone

39 4-Hydroxy-1,5-di - [] 4- (n -dodecylcarbamoyl) - bordo benzoylamino]] anthraquinone

J ^ O 4-Hydroxy-1, S-di-iU-cyclohexylcarbamoyl-r bordo benzoylamino) anthraquinone

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Beiap.

17697%

dye

hue

4-Hydroxy-1, S-di-J ^ -phenylcarbamoyl-marron • benzoylamino) anthraquinone

4-Hydroxy-1,5-di- £ 4- (4-trifluoromethyl-phenyl = bordo carbamoyl) -b32nzoylamino ^ j-anthraquinone

1, S-dihydroxy - ^. E-di - ^ - ethylcarbamoyl blue benzoylamino) anthranhinone

1 _r 5-dihydroxy-4,8-di- £ 4- (iso-butylcarbamoy3) - blue benzoylaminoJ-anthraquinone

1 _t 5-dihydroxy-4,8, di- (4-cyclohexylcarbamoyl blue benzoylamino) anthraquinone

1 _f 5-dihydroxy-4,8-di- £ 4- (2-hydroxyethyl- · blue carbamoylj-benzoylamino ^ -anthraquinone

1,5-dihydroxy-4,8-di - [] 4- (2-ethyl mercapto blue ethylcarbamoyl) benzoylaminojj-anthraquinone

1,5-dihydroxy-4,8-di- £ 4- (4-methyl-cyclo = blue hexylcarbamoylj-benzoylamino ^ -anthraquinone

1,5-dihydroxy-4,8-di (4-benzylcarbamoyl blue benzoylamino) anthraquinone

1,5-dihydroxy-4 _t 8-di- £ 4- (benzoyl-methyl. "Blue c _a rbamoyl) benzoylamino] anthraquinone

1,5 ~ dihydroxy-4,8-di- [4- (2,3-dichloro blue phenylcarbamoyl) -benzoylamino ^ -anthraquinone,

1,5-dihydroxy-4,8-di- [4- (2 _L 5-dichloro-blue phenylcarbamoyl) -benzoylaminoI-anthraquinone

1,5-dihydroxy-4,8-di- £ 4- (5-chloro-2-nitro-blue phenylcarbamoyl) benzoylamino] | anthraquinone

1,5-dihydroxy-4,8-di- [4- (4-trifluoromethyl blue phenylcarbamoyl) benzoylamino ^ anthraquinone

1,5-dihydroxy-4 _t 8-di- [4- (2-chloro-5-methyl-blue phenylcarbamoyl) -benzoylamino-1-anthraquinone

1,5-dihydroxy-4,8-di-f4- (2-chloro-5-trifluorine «i blue thyl-phenylcarbamoyl) -benzoylaaino]] - anthraquinone

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Ex

dye

hue

.11 5-Dihydroxy-4, 8-di - [* t- (2, h , 6-trimethylphenylcarbanoyl) -benzoylaminojj-anthraquinone

1,5-dihydroxy-U, 8-di- [i | - (naphthyl- (i) -carbamoylj-benzoylaininoi-anthraquinone

1,5-dihydroxy-U, 8 ~ di- [4- (4-methoxyphenylcarbamoyl) -benzoylaminoj-anthraquinone

1, ^ -dihydroxy - **, 8 ~ di-J [U- (4-carbamoylphenylcarbamoyl) -benzoylaminoj-anthraquinone

1,5-dihydroxy-4,8-di - [^ - (3-sulfamoylphenylcarbamoyl) -benzoylaminoj-anthraquinone

phenylcarbamoyl) -benzoylaminoj-anthraquinone

1,8-Dihydroxy-4,5-di- £ 4- (n-butylcarbamoyl) -benzoylaminoj-anthraquinone

1,8-dihydroxy-U, 5-dx- ^ k- (2,5-dichlorophenylcarbamoyl) -benzoylaraino'j-anthraquinone

1,8-dihydroxy-1,5-di- [U- (2,4,5-trichlorophenylcarbamoyl) -benzoylaminoj-anthraquinone

1,8-dihydroxy-4,5-di- [4- (3,5-bis-trifluoromethylphenylcarbamoyl) -benzaylamino]] - anthraquinone

1,5-dihydroxy-1,8-di- [4- (pyridyl- (2) carbamoyl) -benzoylamino-anthraquinone

blue blue blue blue blue blue violet violet violet violet blue

Examples 68-95

Is used according to Example 2 instead of 1,5-di £ 4- (n-butylcarbainoyj) -benzoylamino ^ I-anthraquinone corresponding amounts of those given in the following table in fine distribution Dyes, this is how genuinely pigmented nitro lacquers are obtained with the color shades given in the table:

Ex.

dye

hue

68 1,5-di (1-phenylcarbamoylformylamino) anthraquinone

69 1 t 5-di ~ (3-butylcarbamoylpropionylamino) - «nthraquinone 109882/1447

H i 11 W2 "- 32 -

yellow yellow

Example dye . hue

70 x 1,5-di- (7-methylcarbamoyl _r heptanoyl) - yellow anthraquinone

71 1 x 5-di- (4-phenylcarbamoyl-3-oxa-butyrylamino) - yellow anthraquinone

72 1,5-di- (4-phenylcarbamoyl-3-sulfa-butyryl = yellow amino) anthraquinone

73 1,5-di- (4-phenylcarbamoyl ~ 3-aza-butyrylamino) - yellow anthraquinone

74 1,5-di- (4-phenylcarbamoyl-hexahydro-benzoyl = yellow . amino) anthraquinone

75 1,5-di- (trans-3-phenylcarbamoyl-acryloyl = yellow amino) anthraquinone

76 1,5-di (2,5-dimethoxy-4-phenylcarbamoyl yellow benzoylamino) anthraquinone

77 1 _t 5-di- £ 4- (6-bromo-2,4-dinitro-phenylcarbainoyl) - orange benzoyl amino] [- an thrachinone

78 1,5-Di- [2,5-difluoro-4- (u-methyl-2 _l 5-diethyl yellow phenyl carbamoyl) benzoylamino] J-anthraquinone

79 1,5-di- [4- (5,6,7,8-tetrahydro-naphthyl- (i) - yellow Carbamoyl) -benzoylaminoj-anthraquinone

80 1,5-di - [] 4- (4-cyclohexyl-phenylcarbamoyl) - yellow benzoylamino]] anthraquinone

81 1,5-di- £ 4- (anthracenyl- (2) -carbamoyl) - yellow benzoylamino] j-an thraquinone

82 2,4,6,8-tetrabromo-1,5-di- (4-phenylcarbamoyl-orange benzoylamino) anthraquinone

83 1,5-dihydroxy-4,8-di (4-methylcarbamoyl blue benzoylamino) anthraquinone

84 1,5-dihydroxy-4,8-di-r4- (n-dodecylcarbamoyl) - blue benzoylamino [{-anthraquinone

85 1 _f 5-dihydroxy-4,8-di (4-phenylcarbamoyl blue benzoylamino) anthraquinone

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Example dye hue

86, 1,5-dihydroxy-4,8-di - (^ - phenylcarbamoyl blue butyrylamino) anthraquinone

87 1,5-Dihydroxy-4,8-di (U-chloro-3-methylcarbamoyl blue benzoylamino) anthraquinone

88 1,5-ihydroxy-U, 8-di- [2,5-difluoro-if- (i * -sulf "-blue amoyl-phenylcarbamoyl) -benzoylaminoJ-anthraquinone

89 1,5-Dihydroxy-J |, 8-di- £ 6- (4-trifluoromethyl-blue phenylcarbamoyl) naphthoyl (2) amino] J-anthraquinone

90 1, S-dihydroxy- ^. E-di ^ U-Cl-methylcarbanioyl- blue phenyl) benzoylaraino ^ anthraquinone

91 1,5-dihydroxy- * », 8-di- £ 2- (n-butylcarbamoyl) - blue pyridinoyl- (2) -aminoQ-anthraquinone

92 1, S-Uiwethoxy - ^^ - di-iU-phenylcarbamoyl- violet benzoylamino) anthraquinone

93 3-Bromo-1-amino-5-hydroxy-U, 8-di- (^ phenyl = blue carbamoyl-benzoylamino) anthraquinone

Sk 2-Bromo-5-amino-1-hydroxy-il ·, 8-di- (4-phenyl = blue carbamoyl-benzoylamino) -anthraquinone

95 2- (4-methoxyphenyl) -1, 8-dihydroxy-1, 5-di-blue (Jj-phenylcarbamoyl-benzoylamino) -anthraquinone

Examples 96-113

According to Example 5 * but using appropriate amounts of fine dough made from the dyes given in the table instead of the fine dough made from 1,5-dihydroxy-U, 8-di- £ ** - (4-sulfamoylphenylcarbamoyl ) -benzoylaniino] [- anthraquinone, you get real ones Coatings with the colors specified in the table:

Example dye hue

96 1,5-di (4-phenylcarbamoyl yellow benzoylamino) anthraquinone

97 1 »5-Di- £ 4- £ 4- (U-methyl-aniline ^) - phenylcarb = yellow araoyl] J-benzoylaminoV -anthraquinone

^{1 A 11 Vi} y QQ 3 ^Γ U 4 7 ORIGINAL INSPECTED

Ex.

dye

iaroion

98;

99 100 101 102 103

105 '10b

107 108

yellow

yellow

yellow

yellow

1,5-di- ^[1 J (^ phenoxy-phenylcarbamoyl) -benzoylamino] -anthrach'inon

1,5-Di- [ ¹ I- ( ¹ I-methylsulfonyl-phenylcarbamoyl) -benzoylamino]] anthraquinone

1,5-di- (9-phenylcarbamoyl-octadecanoyl- (1) -amino) -anthraquinone

1,5-di- (2-hydroxy-3-phenylearbamoylpropionylamino) anthraquinone

1,5-di- (2-acetylamino-2-phenyl-carbamoyl-yellow propionylamino) -anthraquinone

1,5-Di-P ¹ I- ( ¹ I-phenylcarbamoyl-phenylsulfo-yellow nyl) -benzoylamino] -anthraquinone

¹ l-hydroxy- ^{1,5-di- (1} ! -Methylcarbamoyl violet '

benzoylamino) anthraquinone

¹ l-hydroxy-l, 5-di- ^[1 l- (3-carbamoyl-phenyl- marron carbamoyl) -3-oxo-butyrylamino] anthraquinone

¹ l-hydroxy-l, 5-di- [2- ( ¹ l-ethoxycarbonyl-phe- marron nylcarbamoyl) - ?, ¹ ! , 5,6-tetrahydro-benzoylamine-3-anthraquinone

M-hydroxy-1,5-Oi-Q ¹ I - ( ¹ I -methylcarbamoyl- violet benzylI-benzoylamino ^ -anthraquinone

¹ I-Hydroxy-1,5- ^ iF ¹⁴ - (^ -benzoyl-phenyl- violet carbamoyl) -benzoylamino ^ j-anthraquinone ¹ I -hydroxy-1,5-di-A - [ ¹ I - (** ' -methylcarbamoylbiphenyl-f ¹ !) -azo> -phenyl - ^ - benzoylamino? -anthraquinone

1,5-dihydroxy- ¹ ! , 8-di- (Ί -methylcarbamoyl blue benzoylamino) anthraquinone

1,5-dihydroxy- ¹ ! , 8-di - / ^ - [^ i- (n-butylcarb-blue amoyl) -phenylazo] -berizoylaminoj-anthraquinone

1,5-dihydroxy- ¹ 1,8-di- [5- ( ¹ i-carbamoyl blue

phenylcarbamoyl) furanoyl (2) amino] J-anthraquinone

marron

1,5-dihydroxy-M, e-di - ^ - ^ - carbamoylphenylcarbamoyl) -thiophenoyl- (2) -amino3-anthrechinone 109882/1447

blue

Le A11 572

In spat le 11 * 1-122;

According to Example 7, but using appropriate amounts of the dyes given in the table below, finely divided instead of ¹ I-hydroxy ^{-1,5-di- [1} l- (n-butylcarbamoyl) -benzoylamino ^ -anthraquinone, Genuine pigmented polyvinyl chloride is obtained with the color shades given in the table.>

Example dye hue

1, B-Di- [ ¹ I- ( ¹ USuIf amoyl-phenylcarbamoyl) -yellow benzoylamino] -anthraquinone

115 1,8-di- (2,3,5,6-tetrachlor- ^ - methyl- yellow carbamoyl-benzoylamino) anthraquinone

116 1,8-di- (2,5,5,6-tetrafluoro _r ^I l-phenylcarb-yellow amoyl-benzoylamino) -anthraquinone

117 1,8-Di- [ ¹ I- (2-nitro - ^ - carbamoyl-phenyl-yellow carbamoyl) -naphthoyl- (1) -amino [] -anthraquinone

118 1,5-dihydroxy- ¹ *, e-di-C 1-4 methylcarbamoyl blue benzoylamino) anthraquinone

119 1,5-dihydroxy- ¹ ! , 8-di- £ ^ - (n-butylcarbamoyj- blue benzoylamino] anthraquinone

120 1,5-dihydroxy- ⁱ *, 8-di- [ ¹ l- ( ¹ ^ -SuIf amoyl-blue phenylcarbamoyl) -benzoylamino]] - anthraquinone

121 1,5-dihydroxy- ¹ », b-di- [ ¹ ) - (2, ii-dicarbamoyl-blue phenylcarbamoylj-benzoylamino ^ -anthraquinone

122 l ^ -dihydroxy- ^^ -di-f ^ -phenylcarbamoyl- blue benzoylamino) anthraquinone

Examples

With printing inks prepared according to Example 13 using appropriate amounts of the dyes indicated in the table instead of 1,5-dihydroxy- ¹ *, 8-Ui ( ¹ I-phenylcarbamoyl-benzoylamino) -anthraquinone, true offset prints are obtained in the specified

Shades / 109882 / 1U7

- 36 -

Example dye

hue

125, 124 125 126 127

128

129

130 131 132

133

135

1,5-dihydroxy- ¹ ! , 8-di- (5-methylcarbarnoyl-blue naphthoyl- (l) -amino) -anthraquinone

1,5-Dihydroxy- ^, 8-Ui-P ¹ I- (5-chloro-2-cyano-blue phenylcarbarnoyl) -benzoylamino-1-anthraquinone

!, S-Dihydroxy-Ji, 8-di- [ ¹ l- (2, ^ - dicyano-phenyl- blue carbamoyl) -benzoylamir.o ^ j-anthraquinone

1, ^ - Dihydroxy- ¹ ), 8-di- { ⁱ t- [2-chloro-5- (2-hydroxyethyl-sulfamoyl) -phenylearb-amoyl [J-benzoylaminoj-anthraquinone

1,5-dihydroxy- ¹ ), 8- ^ i- [ ¹ J- (6-carbamoylnaphthyl- (2) -carbamoyl) -benzoylamino]] -

anthraquinone

blue blue

1.5 ~ dihydroxy- ¹ i, 8-di- [ ¹ ) - (2-carbamoyl- ^ -sulfamoyl-phenylcarbamoylj-benzoylamino] -anthraquinone

l, 5-dihydroxy-4, S-di - ^ - i ^ -phenylazophenylearbamoyl) -benzoylamino]] - anthra-

chinone

1,5-dihydroxy- ¹ », 8-di - (^ - pyridyl- (2) -carbamoyl-benzoylamino) -anthraquinone '

blue

blue

blue blue blue

amoyl) benzoylamino] anthraquinone

1,5-dihydroxy- ¹ 1,8-di-p- (2-phenyl-benzotriazolyl- (5) -carbamoyl) -benzoylamino]] anthraquinone

l, ^{5-dihydroxy-1} l, 8-di- ^(I-l thlazolyl- (2) -carbamoyl-benzoylamino) anthraquinone

1,5-dihydroxy- ¹ ! , 8-di - [^ - (6-methoxy-benzthiazolyl- (2) -carbamoyl) -benzoylamino] janthraquinone

1,5-Dihydroxy- ¹ <, 8-di- [M2-nethyl-benzthia-blue. • i.zolyl-föj-carbamoylj-benzoylamir.o ^ -anthra-

chinone

blue blue

Le A11 572

- 37 -109882/1447

Beispi ele

If a pigmented paper is produced according to Example 17 using the dyes indicated in the table, or printed a paper with a printing ink that matches an example 5 contains pein dough made using the dyes listed below, as well as water-soluble or saponifiable binders, and if the paper pigmented or printed in this way is treated according to Example 18, real laminate papers with the specified values are obtained Shades:

Example dye hue

136 l, 5 - (^ - phenylcarbamoyl-benzoylamino) - yellow anthraquinone

137 1,5-Di- [ ¹ I- ( ¹ I-SuIf amoyl-phenylcarbamoyl) -yellow benzoylamino]] -anthraquinone

138 1,5-Di - [^ - (^ - carbamoyl-phenylcarbamoyl) - yellow benzoylaminoj-anthraquinone

139 1,5-Di- [ ¹ U (2,5-dichloro-phenylcarbamoyl) -yellow benzoylamino] -anthraquinone

I ¹ IO 1,5-dihydroxy- ¹ ! , 8-Ui- [ ¹ U (2,5-dlchlor blue phenylcarbamoylj-benzoylamino] anthraquinone

I ¹ Jl 1,5-dihydroxy- ¹ !, 8 ^ i- [ ¹ U (4-methoxyphenyl blue carbamoyl) -benzoylamino] -anthraquinone

! 1.5-dihydroxy- ^1, 8-Oi ^[1 T- (4-methyl-phenyl carbamoyl blue) benzoylamino]] - anthraquinone

1,5-Dihydroxy-2- ( ¹ l-methoxyphenyl) ^-1 <, 8-di-blue (4-butylcarbamoyl-benzoylamino) -anthraquinone

^ a-di-blue -phenylcarbamoyl-benzoyiamino) -anthraquinone

Le A11 572

- 38 -

109882/1447

Claims (1)

Patent claims: 1. Dyes of the formula wherein Y is hydrogen, halogen, a hydroxyl, alkoxy, amino or arylamino group, an X is hydrogen, halogen, an amino- ^ Arylamino, acylamino, hydroxyl or alkoxy group, the other X denotes the radical -NH-R, the rings C and D optionally may have further substituents and the radical R stands for the group -CO-B-CO-NH-E in which B is a simple one Bond, a saturated or unsaturated bond which is optionally further substituted or interrupted by heteroatoms Alkylene radical or an optionally further substituted mono- or polynuclear arylene or heteroarylene radical and E a saturated or unsaturated one which may have substituents and may be interrupted by heteroatoms Alkyl or cycloalkyl radical or optionally one one or more halogen atoms, nitro groups, alkyl groups with 1-12 carbon atoms, cycloalkyl groups, fused-on cyclohexyl or benzene rings, trifluoromethyl groups, arylamino groups, hydroxyl groups, alkoxy groups with 1-3 carbon atoms, Phenoxy groups, alkylsulfonyl groups, arylsulfonyl groups, Alkyl carbonyl groups, aryl carbonyl groups, carboxyl groups, Carboxylic acid ester groups, non-substituted carboxylic amide groups, optionally N-substituted sulfamoyl groups, alkylsulfonylamino groups, Arylsulfonymamino groups, phenylazo or phenylazoxy groups or an optionally containing aryl radical substituted heteroaryl radical means. Le A 11 572 - 39 - 109882 / U47 Vo 2. Dyes of the formula wherein Y and one X ^{1 is} a hydroxyl group, the other X ^{1 is} the radical NH-R, where R has the meaning given in claim 1 and the rings C and D may optionally have further substituents. . Dyes of the formula X '0 NH-R
ι η ι X '0 wherein Y and one X ^{1 is} a hydroxyl group, the other X ^{1 is} the radical NH-R and R is the radical -CO-B'-CO-NH-E in which E has the meaning given in claim 1 and B ' means a phenylene radical. 4. Use of dyes of claim 1 as pigments 5. Use of the dyes of claim 1 for pigmenting lacquers and paints, for coloring moldings, foils or threads made from polymers, polycondensates or polyadducts in bulk and for coloring printing inks and printing inks. - 40 - Le A11 572 109882/1447 6. Use of the dyes of claim 1 for dyeing vulcanizates, polyvinyl chloride, polyacrylonitrile, polyesters, polypropylene, polyethylene and cellulose derivatives in the wet. 7. Varnishes and paints, moldings, foils or threads made from polymers, polycondensates or polyaddition products, Printing inks and printing inks, colored or mass-colored with the dyes of claim 1. 8. Process for the preparation of dyes of the formula X 0 NH-R I Il I t ti I XOY " wherein Y is hydrogen, halogen, a hydroxyl, alkoxy, amino or arylamino group, an X is hydrogen, halogen, an amino g Arylamino, acylamino, hydroxyl or alkoxy group, the other X denotes the radical -NH-R, the rings C and D optionally may have further substituents and the radical R represents the group -CO-B-CO-NH-E, in which B is a N. double bond, a saturated or unsaturated one which is optionally further substituted or interrupted by heteroatoms Alkylene radical or an optionally further substituted mononuclear or polynuclear arylene or heteroarylene radical and E a saturated or unsaturated one which may have substituents and may be interrupted by heteroatoms Alkyl or cycloalkyl radical or optionally one Le A 11 572 - 41 - 109882 / U47 one or more halogen atoms, nitro groups, alkyl groups with 1-12 carbon atoms, cycloalkyl groups, fused-on cyclohexyl or benzene rings, trifluoromethyl groups, arylamino groups, Hydroxy groups, alkoxy groups with 1-3 carbon atoms, phenoxy groups, alkylsulfonyl groups, arylsulfonyl groups, Alkyl carbonyl groups, aryl carbonyl groups, carboxyl groups, Carboxylic ester groups, unsubstituted carbonamide groups, optionally N-substituted sulfamoyl groups, alkylsulfonylamino groups, Arylsulfonymanino groups, phenylazo or phenylazoxy groups or an "optionally substituted heteroaryl radical means » characterized in that one aminoanthraquinones of the formula X ₁ 0 NH ι 'II I in which the rings C and D can have further subatituents and in which Y has the meaning given above and one X _{1 is} X with the meaning given above and the other X _{1 is} the radical -NH ₂ , initially with at least 2 moles of a reactive derivative of a Dicarboxylic acid of the formula HOOC-B-COOH
where B has the meaning given above, reacted and then with at least 2 moles of an amine the formula 109882/1447 Le A 11 572 - 42 - wherein E has the meaning given above, reacts. 9 · Process for the preparation of dyes of the iormel wherein Y is hydrogen, halogen, a hydroxyl, alkoxy, amino or arylamino group, one X is hydrogen, halogen, an amino-arylamino, acylamino, hydroxy or alkoxy group, the other X is the radical -NH-R, where the rings C and D can optionally have further substituents and the radical R stands for the grouping -CO-B-CO-NH-E in which B is a single bond, an optionally further substituted or interrupted by heteroatoms saturated or unsaturated alkylene radical or an optionally further substituted "mononuclear or polynuclear arylene or heteroarylene radical and E a saturated or unsaturated alkyl or cycloalkyl radical optionally interrupted by heteroatoms or optionally one or more halogen atoms, nitro groups, alkyl groups with 1-12 C atoms, cycloalkyl groups, aticondensed Cyclohexyl or benzene rings, trifluoromethyl groups, arylamine groups, hydroxyl groups, alkoxyg groups with 1-3 carbon atoms, Le A 11 572 _ 43 - 10 9 8 8 2 Mi L 7 BAD CFÜGINAL Phenoxy groups, alkylsulfonyl groups, arylsulfonyl groups, Alkyl carbonyl groups, aryl carbonyl groups, carboxyl groups, carboxylic acid ester groups, unsubstituted carbonamide groups, optionally N-substituted sulfamoyl groups, alkylsulfonyl - amino groups, arylsulfonymamino groups, phenylazo or Aryl radical containing phenylazoxy groups or an "optionally substituted hetercaryl means » as indicated that anthraquinone derivatives of the form B 1 wherein Y has the meaning given above, one X stands for X and the other X-. denotes the ReSt-NH ₂ , with at least 2 mol of a reactive derivative of an N-substituted dicarboxylic acid monoamide of the formula HOOC-B-CO-NH-E in which B and E have the meaning given above. Le A 11 512 '- 44 - 109882/1447