Dye mixtures of fiber-reactive azo dyes, their production and use

0001The invention is in the technical field of fiber-reactive azo dyes.

0002Dye mixture of fiber-reactive azo dyes and their use for dyeing material containing hydroxyl and carbonamide groups in black shades are, for example, from the documents <patcit id="pcit0001" dnum="US5445654A"><text>US 5,445,654</text></patcit>, <patcit id="pcit0002" dnum="US5611821A"><text>US 5,611,821</text></patcit>, <patcit id="pcit0003" dnum="KR942560"><text>KR 94-2560</text></patcit>, <patcit id="pcit0004" dnum="KRSHO58160362"><text>Sho 58-160362</text></patcit> and <patcit id="pcit0005" dnum="EP0870807A"><text>EP-A-0 870 807</text></patcit> known. However, these have certain application-related deficiencies, such as an excessive dependence of the color yield on changing dye parameters in the dyeing process, or an insufficient or irregular color build-up on cotton (a good color build-up results from the ability of a dye to use the correspondingly stronger color when using increased dye concentrations in the dye bath Coloration). As a result of these shortcomings, poor reproducibility of the available dyeings can result, which ultimately affects the economy of the dyeing process. As a result, there is still a need for new reactive dyes or reactive dye mixtures with improved properties, such as high substantivity with simultaneous good washability of non-fixed portions. In addition, they must also have good dyeing yields and have a high reactivity, in particular dyeings with high degrees of fixation should be supplied.

0003With the present invention, dye mixtures have now been found which have the properties described above to a high degree. The new dye mixtures are characterized above all by high fixing yields and easy wash-out of the portions not fixed on the fiber. In addition, the dyeings have good general fastness properties, such as high light fastness and very good wet fastness properties, and show a low tendency to dye polyamide in cotton / polyamide blended fabrics.

0004The invention thus relates to dye mixtures which contain one or more, such as two or three, preferably 1 or 2, dyes of the general formula (I) specified and defined below,<chemistry id="chem0001" num="0001"><img file="EP1490441B2_D0001.tif" /></chemistry>one or more, such as two or three, preferably 1 or 2, dyes of the general formula (II) indicated and defined below<chemistry id="chem0002" num="0002"><img file="EP1490441B2_D0002.tif" /></chemistry>and optionally one or more, such as two or three, preferably 1 or 2, dyes of the general formula (III) indicated and defined below<chemistry id="chem0003" num="0003"><img file="EP1490441B2_D0003.tif" /></chemistry>included, in which mean:<ul id="ul0001" list-style="none" compact="compact"><li>D¹, D², D³, D⁴ and D⁵ are independently a group of the general formula (1)<chemistry id="chem0004" num="0004"><img file="EP1490441B2_D0004.tif" /></chemistry>wherein<dl id="dl0001" compact="compact"><dt>R¹ and R²</dt><dd>independently of one another hydrogen, (C₁-C₄) Alkyl, (C₁-C₄) Alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; and</dd><dt>X¹</dt><dd>for hydrogen or a group of the formula -SO₂-Z stands, in which Z -CH = CH₂, -CH₂CH₂Z.¹ or hydroxy means wherein Z.¹ Hydroxy or an alkali-releasable group is or</dd></dl></li><li>D¹, D², D³, D⁴ and D⁵ independently of one another denote a naphthyl group of the general formula (2)<chemistry id="chem0005" num="0005"><img file="EP1490441B2_D0005.tif" /></chemistry>wherein<dl id="dl0002" compact="compact"><dt>R³ and R⁴</dt><dd>independently of one another hydrogen, (C₁-C₄) Alkyl, (C₁-C₄) Alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; and</dd><dt>X²</dt><dd>one of the meanings of X¹ Has; or</dd></dl></li><li>D¹, D², D³, D⁴ and D⁵ are independently a group of the general formula (3)<chemistry id="chem0006" num="0006"><img file="EP1490441B2_D0006.tif" /></chemistry>wherein<dl id="dl0003" compact="compact"><dt>R⁵ and R⁶</dt><dd>independently one of the meanings of R¹ and R² to have;</dd><dt>R⁷</dt><dd>is hydrogen, (C₁-C₄) Alkyl, unsubstituted or by (C₁-C₄) Alkyl, (C₁-C₄) Alkoxy, sulfo, halogen or carboxy substituted phenyl; and</dd><dt>Z.²</dt><dd>is a group of the general formula (4) or (5) or (6)<chemistry id="chem0007" num="0007"><img file="EP1490441B2_D0007.tif" /></chemistry>wherein V represents fluorine or chlorine; U¹, U² are independently fluorine, chlorine or hydrogen; and Q¹, Q² chlorine, fluorine, cyanamido, hydroxy, (C₁-C₆) Alkoxy, phenoxy, sulfophenoxy, mercapto, (C₁-C₆) -Alkylmercapto, pyridino, carboxypyridino, carbamoylpyridino or a group of the general formula (7) or (8)<chemistry id="chem0008" num="0008"><img file="EP1490441B2_D0008.tif" /></chemistry>wherein R⁸ Hydrogen or (C₁-C₆) Alkyl, sulfo- (C₁-C₆) Alkyl or phenyl which is unsubstituted or substituted by (C₁-C₄) Alkyl, (C₁-C₄) Alkoxy, sulfo, halogen, carboxy, acetamido, ureido; R⁹ and R¹⁰ independently of one another have one of the meanings of R.⁸, or form a cyclic ring system of the formula - (CH₂)_j- where j is 4 or 5, or alternatively - (CH₂)₂-E- (CH₂)₂-, where E is oxygen, sulfur, sulfonyl, -NR¹¹ with R¹¹ = (C₁-C₆) Alkyl; W is phenylene which is unsubstituted or substituted by 1 or 2 substituents, such as (C₁-C₄) Alkyl, (C₁-C₄) Alkoxy, carboxy, sulfo, chlorine, bromine, or is (C₁-C₄) Alkylene arylene or (C₂-C₆) Alkylene, which can be interrupted by oxygen, sulfur, sulfonyl, amino, carbonyl, carbonamido, or is phenylene-CONH-phenylene, which is unsubstituted or by (C₁-C₄) Alkyl, (C₁-C₄) Alkoxy, hydroxy, sulfo, carboxy, amido, ureido or halogen, or is naphthylene which is unsubstituted or substituted by one or two sulfo groups; and Z has the meaning given above; or</dd></dl></li><li>D¹, D², D³, D⁴ and D⁵ independently of one another represent a group of the general formula (9)<chemistry id="chem0009" num="0009"><img file="EP1490441B2_D0009.tif" /></chemistry>wherein<dl id="dl0004" compact="compact"><dt>R¹²</dt><dd>Hydrogen, (C₁-C₄) Alkyl, aryl or a substituted aryl radical;</dd><dt>R¹³ and R¹⁴</dt><dd>independently of one another hydrogen, (C₁-C₄) Alkyl, (C₁-C₄) Alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; and</dd><dt>A</dt><dd>is a phenylene group of the general formula (10)<chemistry id="chem0010" num="0010"><img file="EP1490441B2_D0010.tif" /></chemistry>wherein R¹⁵ and R¹⁶ independently of one another hydrogen, (C₁-C₄) Alkyl, (C₁-C₄) -Alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen; or</dd><dt>A</dt><dd>is a naphthylene group of the general formula (11)<chemistry id="chem0011" num="0011"><img file="EP1490441B2_D0011.tif" /></chemistry>wherein R¹⁷ and R¹⁸ independently of one another hydrogen, (C₁-C₄) Alkyl, (C₁-C₄) -Alkoxy, hydroxy, sulfo, carboxy, cyano, nitro, amido, ureido or halogen;</dd><dt>X³</dt><dd>one of the meanings of X¹ Has; and</dd><dt>R⁰</dt><dd>represents a group of the general formula (4) or (5) or a group of the general formula (13)<chemistry id="chem0012" num="0012"><img file="EP1490441B2_D0012.tif" /></chemistry>means where;</dd><dt>R²¹</dt><dd>(C.₁-C₆) Alkyl, sulfo- (C₁-C₆) Alkyl, carboxy- (C₁-C₆) Alkyl or phenyl which is unsubstituted or substituted by (C₁-C₄) Alkyl, (C₁-C₄) Alkoxy, sulfo, halogen, carboxy, acetamido, ureido; and</dd></dl></li><li>b, f, v are independently 0 or 1; and</li><li>R *, hydrogen, (C₁-C₄) Alkyl or a group of formula (14)         -CH₂-SO₃M (14) are;<dl id="dl0005" compact="compact"><dt>T</dt><dd>for hydroxy or NH₂ stands for T is NH₂ v stands for 0 and</dd><dt>M</dt><dd>Hydrogen, an alkali metal or an equivalent of an alkaline earth metal means, wherein in the mixtures the dyes of the general formulas (I) - (III) contain at least one fiber-reactive group of the formula -SO₂-Z or -Z² contain.</dd></dl></li></ul>

0005In the general formulas above and in the general formulas below, the individual formula elements, both of different and of the same designation, can have the same or different meanings from one another within the scope of their meaning.

0006R (C₁-C₄) -Alkyl groups can be straight-chain or branched and mean in particular methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl and tert-butyl. Methyl and ethyl are preferred. The same applies to (C₁-C₄) Alkoxy groups.

0007Aryl groups for substituents R are in particular the phenyl group. One for R⁸ to R¹⁰, R¹² or R²¹ standing substituted aryl group is in particular one with one, two or three mutually independent groups from the series (C₁-C₄) Alkyl, (C₁-C₄) Alkoxy, hydroxy, sulfo, carboxy, amido or halogen substituted phenyl group. Halogen standing for substituents R is in particular fluorine, chlorine and bromine, with fluorine and chlorine being preferred.

0008Alkaline eliminable substituents Z¹which are in the β-position of the ethyl group of Z are, for example, halogen atoms, such as chlorine and bromine, ester groups of organic carboxylic and sulfonic acids, such as alkyl carboxylic acids, optionally substituted benzene carboxylic acids and optionally substituted benzenesulfonic acids, such as the alkanoyloxy groups of 2 to 5 carbon atoms, of which in particular acetyloxy, benzoyloxy, sulfobenzoyloxy, phenylsulfonyloxy and tolylsulfonyloxy, furthermore acidic ester groups of inorganic acids, such as phosphoric acid, sulfuric acid and thiosulfurated acid (phosphato) sulfate, , also dialkylamino groups with alkyl groups of 1 to 4 carbon atoms, such as dimethylamino and diethylamino.

0009Z is preferably vinyl, β-chloroethyl and particularly preferably β-sulfatoethyl.

0010The groups "sulfo", "carboxy", "thiosulfato", "phosphato", and "sulfato" include both their acid form and their salt form. Accordingly, sulfo groups mean groups corresponding to the general formula --SO₃M, thiosulfato groups according to the general formula -S-SO₃M, carboxy groups according to the general formula -COOM, phosphato groups according to the general formula -OPO₃M₂ and sulfato groups according to the general formula -OSO₃M, each with M of the meaning given above.

0011The dyes of the general formulas (I) to (III) can have different fiber-reactive groups -SO within the meaning of Z.₂Own Z. In particular, the fiber-reactive groups -SO₂Z on the one hand vinylsulfonyl groups and on the other hand -CH₂CH₂Z.¹, preferably β-sulfatoethylsulfonyl groups. If the dyes of the general formulas (I) to (III) partially contain vinylsulfonyl groups, the proportion of the particular dye with the vinylsulfonyl group is up to about 30 mol%, based on the respective total amount of dye.

0012Alkali for M is in particular lithium, sodium and potassium. M is preferably hydrogen or sodium.

0013The radical R * in the general formula (II) preferably denotes hydrogen, methyl or a group of the formula (14), hydrogen or a group of the formula (14) being particularly preferred. The leftovers R¹ and R² are preferably hydrogen, (C₁-C₄) Alkyl groups, (C₁-C₄) Alkoxy groups, sulfo or carboxy and particularly preferably hydrogen, methyl, methoxy or sulfo. The leftovers R³ to R⁶ and R¹² to R¹⁸ are preferably hydrogen, R³ to R⁶, R¹⁷ and R¹⁸ are also preferred sulfo. The leftovers R⁷ to R¹⁰ are preferably hydrogen or methyl, R.⁷ and R⁸ are also preferably phenyl and R.⁹ and R¹⁰ are preferably 2-sulfoethyl, 2-, 3- or 4-sulfophenyl or R.⁹ and R¹⁰ form a cyclic ring system, which preferably has the formula - (CH₂)₂-O- (CH₂)₂- corresponds.

0014Examples of groups D¹ to D⁵ of the general formulas (1) and (2) are 2- (β-sulfatoethylsulfonyl) phenyl, 3- (β-sulfatoethylsulfonyl) phenyl, 4- (β-sulfatoethylsulfonyl) phenyl, 2-carboxy-5- (β- sulfatoethylsulfonyl) phenyl, 2-chloro-4- (β-sulfatoethylsulfonyl) phenyl, 2-chloro-5- (β-sulfatoethylsulfonyl) phenyl, 2-bromo-4- (β-sulfatoethylsulfonyl) phenyl, 2-sulfo -4- (β-sulfatoethylsulfonyl) phenyl, 2-sulfo-5- (β-sulfatoethylsulfonyl) phenyl, 2-methoxy-5- (β-sulfatoethylsulfonyl) phenyl, 2-ethoxy-5- (β-sulfatoethylsulfonyl) -phenyl, 2,5-dimethoxy-4- (β-sulfatoethylsulfonyl) phenyl, 2-methoxy-5-methyl-4- (β-sulfatoethylsulfonyl) phenyl, 2-methyl-4- (β-sulfatoethylsulfonyl) phenyl, 2- or 3- or 4- (β-thiosulfatoethylsulfonyl) phenyl, 2-methoxy-5- (β-thiosulfatoethylsulfonyl) phenyl, 2-sulfo-4- (β-phosphatoethylsulfonyl) phenyl, 2- or 3- or 4- Vinylsulfonylphenyl, 2-sulfo-4-vinylsulfonylphenyl, 2-chloro-4- (β-chloroethylsulfonyl) phenyl, 2-chloro-5- (β-chloroethylsulfonyl) phenyl, 3- or 4- (β- Acetoxyethylsulfonyl) phenyl, 6- or 8- (β-sulfatoethylsulfonyl) naphth-2-yl, 6- (β-sulfatoethylsulfonyl) -1-sulfo-naphth-2-yl and 8- (β-sulfatoethylsulfonyl) -6-sulfonaphth-2-yl , of which preferred are 3- (β-sulfatoethylsulfonyl) phenyl, 4- (β-sulfatoethylsulfonyl) phenyl, 2-sulfo-4- (β-sulfatoethylsulfonyl) phenyl, 2-methoxy-5- (β-sulfatoethylsulfonyl) - phenyl, 2,5-dimethoxy-4- (β-sulfatoethylsulfonyl) phenyl, 2-methoxy-5-methyl-4- (β-sulfatoethylsulfonyl) phenyl and 3- or 4-vinylsulfonylphenyl, or D¹ to D⁵ correspond to a group of the general formulas (3) or (9), where R⁵ to R⁷ and R¹² to R¹⁴ have the preferred meanings described above.

0015In the event that D¹ to D⁵ for a group of the general formula (1) and X¹ for - SO₂Z stand, the SO stands₂Z group preferably in the meta or para position to the diazo group and in the event that D¹ to D⁵ represents a group of the general formula (2), the bond which leads to the diazo group is preferably bonded to the naphthalene nucleus in the β-position.

0016In the event that A is phenylene and X³ for -SO₂Z stand, the SO stands₂Z group preferably in the meta or para position to the nitrogen atom. In the group of the general formula (9), the carbonamide group is preferably in the para or meta position to the diazo group. In the event that A is naphthylene, the bond which leads to the nitrogen atom is preferably bonded to the naphthalene nucleus in the β-position.

0017Examples of substituents for A are in particular 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2-chloro-1,4-phenylene, 2-chloro-1, 5-phenylene, 2-bromo 1,4-phenylene, 2-sulfo-1,4-phenylene, 2-sulfo-1,5-phenylene, 2-methoxy-1,5-phenylene, 2-ethoxy-1,5-phenylene, 2.5- Dimethoxy-1,4-phenylene, 2-methoxy-5-methyl-1,4-phenylene, 2-methyl-1,4-phenylene, 2,6-naphthylene, 2,8-naphthylene, 1-sulfo-2, 6-naphthylene, 6-sulfo-2,8-naphthylene.

0018A particularly preferably represents 1,3-phenylene, 1,4-phenylene, 2-sulfo-1,4-phenylene, 2-methoxy-1,5-phenylene, 2,5-dimethoxy-1,4-phenylene, 2 -Methoxy-5-methyl-1,4-phenylene means.

0019W is preferably 1,3-phenylene, 1,4-phenylene, 2-sulfo-1,4-phenylene, 2-methoxy-1,5-phenylene, 2,5-dimethoxy-1,4-phenylene, 2-methoxy -5-methyl-1,4-phenylene, 1,2-ethylene, 1,3-propylene.

0020Examples for groups Q¹ and Q² in the general formula (5), independently of one another, fluorine, chlorine, hydroxy, methoxy, ethoxy, phenoxy, 3-sulfophenoxy, 4-sulfophenoxy, methylmercapto, cyanamido, amino, methylamino, ethylamino, morpholino, piperidino, phenylamino, methylphenylamino, 2- Sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 2,4-disulfophenylamino, 2,5-disulfophenylamino, 2-sulfoethylamino, N-methyl-2-sulfoethylamino, pyridino, 3-carboxypyridino, 4-carboxypyridino, 3-carbamoylpyridino Carbamoylpyridino, 2- (2-sulfatoethylsulfonyl) phenylamino, 3- (2-sulfatoethylsulfonyl) phenylamino, 4- (2-sulfatoethylsulfonyl) phenylamino, N-ethyl-3- (2-sulfatoethylsulfonyl) phenylamino, N-ethyl-4- (2-sulfatoethylsulfonyl) phenylamino, 2-carboxy-5- (2-sulfatoethylsulfonyl) phenylamino), 2-chloro-4- (2-sulfatoethylsulfonyl) phenylamino, 2-chloro-5- (2-sulfatoethylsulfonyl) phenylamino , 2-bromo-4- (2-sulfatoethylsulfonyl) phenylamino, 2-sulfo-4- (2-sulfatoethylsulfonyl) phenylamino, 2-sulfo-5- (2-sulfatoethylsulfonyl) phenylamino, 2-methoxy-5- (2-sulfatoethylsulfonyl) phenylamino, 2,5-dimethoxy-4- (2-sulfatoethylsulfonyl) phenylamino, 2-methoxy-5- methyl-4- (2-sulfatoethylsulfonyl) phenylamino, 2-methyl-4- (2-sulfatoethylsulfonyl) phenylamino, 2- (vinylsulfonyl) phenylamino, 3- (vinylsulfonyl) phenylamino, 4- (vinylsulfonyl) phenylamino) , N-ethyl-3- (vinylsulfonyl) phenylamino, N-ethyl-4- (vinylsulfonyl) phenylamino, 6- (2-sulfatoethylsulfonyl) naphth-2-ylamino, 8- (2-sulfatoethylsulfonyl) naphth-2-ylamino, 8- (2-sulfatoethylsulfonyl) -6-sulfo-naphth-2-ylamino, 3- (2- (2-sulfatoethylsulfonyl) ethylcarbamoyl) phenylamino, 4- (2- (2-sulfatoethylsulfonyl) ethylcarbamoyl) phenylamino, 3- (2- (vinylsulfonyl) ethylcarbamoyl) phenylamino, 4- (2- (2-vinylsulfonyl) ethylcarbamoyl) phenylamino, 4- (N-methyl -2- (2-sulfatoethylsulfonyl) ethylcarbamoyl) phenylamino, 4- (N-phenyl-2- (2-sulfatoethylsulfonyl) ethylcarbamoyl) phenylamino, 4- (3- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino, 4- (4- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino, 3- (3- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino, 3- (4- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino, 3- (2-sulfatoethylsulfonyl) propylamino, N-methyl-N- (2- (2-sulfatoethylsulfonyl) ethyl) amino, N-phenyl-N- (2- (2-sulfatoethylsulfonyl) ethyl) amino, N-phenyl-N- (2- (2-sulfatoethylsulfonyl) propyl) amino.

0021The groups Q are preferably¹ and Q² in the general formula (5) independently of one another for fluorine, chlorine, cyanamido, morpholino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, N-methyl-2-sulfoethylamino, 3-carboxypyridino, 4-carboxypyridino, 3-carbamoylpyridino, 4-carbamoylpyridino, 3- (2-sulfatoethylsulfonyl) phenylamino, 4- (2-sulfatoethylsulfonyl) phenylamino, 3- (vinylsulfonyl) phenylamino, 4- (vinylsulfonyl) phenylamino), 4- (3- (2-sulfatoethylsulfonyl) ) -phenylcarbamoyl) -phenylamino, 4- (4- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino, 3- (3- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino, 3- (4- (2-sulfatoethylsulfonyl) phenylcarbamoyl) phenylamino, N- Methyl-N- (2- (2-sulfatoethylsulfonyl) ethyl) amino, N-phenyl-N- (2- (2-sulfatoethylsulfonyl) ethyl) amino.

0022Groups Q are particularly preferred¹ and Q² in the general formula (5) independently of one another for fluorine, chlorine, cyanamido, morpholino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 3- (2-sulfatoethylsulfonyl) phenylamino, 4- (2-sulfatoethylsulfonyl) phenylamino, 3- (vinylsulfonyl) phenylamino, 4- (vinylsulfonyl) phenylamino), N-methyl-N- (2- (2-sulfatoethylsulfonyl) ethyl) amino, N-phenyl-N- (2- (2-sulfatoethylsulfonyl) ) -ethyl) -amino.

0023Examples for group Z² are 2,4-difluoropyrimidin-6-yl, 4,6-difluoropyrimidin-2-yl, 5-chloro-2,4-difluoropyrimidin-6-yl, 5-chloro-4,6-difluoro -pyrimidin-2-yl, 4,5-difluoropyrimidin-6-yl, 5-chloro-4-fluoropyrimidin-6-yl, 2,4,5-trichloropyrimidin-6-yl, 4,5 -Dichloropyrimidin-6-yl, 2,4-dichloropyrimidin-6-yl, 4-fluoropyrimidin-6-yl, 4-chloropyrimidin-6-yl, or a group of the general formula (5) with the above examples for Q¹ and Q² or a group of the general formula (6).

0024Preferably Z means² 2,4-difluoropyrimidin-6-yl, 4,6-difluoropyrimidin-2-yl, 5-chloro-2,4-difluoropyrimidin-6-yl, 5-chloro-4,6-difluoro- pyrimidin-2-yl or a group of the general formula (5) with the preferred groups Q indicated above¹ and Q².

0025Z is particularly preferably² for 2,4-difluoropyrimidin-6-yl, 5-chloro-2,4-difluoropyrimidin-6-yl or for a group of the general formula (5) with the particularly preferred groups Q given above¹ and Q².

0026In formula (III), T is preferably hydroxyl or amino, bonded to the naphthalene nucleus in the α-position, with hydroxyl being particularly preferred. b and v are preferably 1 and f are 0. R⁰ particularly preferably represents acetyl, 2,4-dichloro-1,3,5-triazin-6-yl or 2,4-difluoropyrimidin-6-yl.

0027The dye mixtures according to the invention contain bisazo dyes of the general formula (I) in an amount of 30 to 95% by weight, preferably 50 to 90% by weight and dyes of the general formula (II) in an amount of 1 to 70% by weight, preferably 5 up to 50% by weight.

0028Optionally, the dye mixtures according to the invention can also contain one or more monoazo dyes of the general formulas (15) to (18) in an amount of up to 10% by weight, preferably up to 5% by weight,<chemistry id="chem0013" num="0013"><img file="EP1490441B2_D0013.tif" /></chemistry><chemistry id="chem0014" num="0014"><img file="EP1490441B2_D0014.tif" /></chemistry>where D², D³, M, R * and R ** have the meanings given above.

0029D are preferably² and D³ independently for 3- (β-sulfatoethylsulfonyl) phenyl, 4- (β-sulfatoethylsulfonyl) phenyl, 2-sulfo-4- (β-sulfatoethylsulfonyl) phenyl, 2-methoxy-5- (β-sulfatoethylsulfonyl) phenyl , 2,5-dimethoxy-4- (β-sulfatoethylsulfonyl) phenyl, 2-methoxy-5-methyl-4- (β-sulfatoethylsulfonyl) phenyl, 3- or 4-vinylsulfonylphenyl, 2-sulfo-4- (vinylsulfonyl) phenyl, 2-methoxy-5- (vinylsulfonyl) phenyl, 2,5-dimethoxy-4- (vinylsulfonyl) phenyl or 2-methoxy-5-methyl-4- (vinylsulfonyl) phenyl.

0030The dye mixtures according to the invention can optionally also contain one or more, such as two or three, preferably 1 or 2, dyes with, for example, the general formulas (Ga) - (Gf) specified and defined below as further mixing or shading components<chemistry id="chem0015" num="0015"><img file="EP1490441B2_D0015.tif" /></chemistry><chemistry id="chem0016" num="0016"><img file="EP1490441B2_D0016.tif" /></chemistry><chemistry id="chem0017" num="0017"><img file="EP1490441B2_D0017.tif" /></chemistry><chemistry id="chem0018" num="0018"><img file="EP1490441B2_D0018.tif" /></chemistry>wherein<dl id="dl0006" compact="compact"><dt>D⁶, D⁷, D⁸, D⁹, D¹⁰</dt><dd>one of the meanings of D¹, D², D³, D⁴ or D⁵ own, where D⁶if R³¹ does not represent a group of the general formula (4) or (5), and D⁷ or D⁸ and D¹⁰ at least one fiber-reactive group of the formula -SO₂Z or Z² contain;</dd><dt>R³¹</dt><dd>Is hydrogen, acetyl, carbamoyl, sulfomethyl or represents a group of the general formula (4-1) or (5-1),<chemistry id="chem0019" num="0019"><img file="EP1490441B2_D0019.tif" /></chemistry></dd></dl>wherein<dl id="dl0007" compact="compact"><dt>V¹</dt><dd>Means fluorine or chlorine;</dd><dt>U¹¹, U²¹</dt><dd>are independently fluorine, chlorine or hydrogen; and</dd><dt>Q¹¹, Q²¹</dt><dd>chlorine, fluorine, cyanamido, hydroxy, (C₁-C₆) Alkoxy, phenoxy, sulfophenoxy, mercapto, (C₁-C₆) -Alkylmercapto, pyridino, carboxypyridino, carbamoylpyridino or a group of the general formula (7-1) or (8-1)<chemistry id="chem0020" num="0020"><img file="EP1490441B2_D0020.tif" /></chemistry></dd></dl>wherein<dl id="dl0008" compact="compact"><dt>R⁸¹</dt><dd>Hydrogen or (C₁-C₆) Alkyl, sulfo- (C₁-C₆) Alkyl, or phenyl, which is unsubstituted or replaced by (C₁-C₄) Alkyl, (C₁-C₄) Alkoxy, sulfo, halogen, carboxy, acetamido, ureido;</dd><dt>R⁹¹ and R¹⁰⁰</dt><dd>independently of one another have one of the meanings of R.⁸¹, or form a cyclic ring system of the formula - (CH₂)_j- where j is 4 or 5, or alternatively - (CH₂)₂-E- (CH₂)₂-, where E is oxygen, sulfur, sulfonyl, -NR¹¹ with R¹¹ = (C₁-C₆) Alkyl;</dd><dt>W¹</dt><dd>is phenylene which is unsubstituted or substituted by 1 or 2 substituents, such as (C₁-C₄) Alkyl, (C₁-C₄) Alkoxy, carboxy, sulfo, chlorine, bromine, or is (C₁-C₄) Alkylene arylene or (C₂-C₆) Alkylene, which can be interrupted by oxygen, sulfur, sulfonyl, amino, carbonyl, carbonamido, or is phenylene-CONH-phenylene, which is unsubstituted or by (C₁-C₄) Alkyl, (C₁-C₄) Alkoxy, hydroxy, sulfo, carboxy, amido, ureido or halogen, or is naphthylene which is unsubstituted or substituted by one or two sulfo groups; and</dd><dt>Z.</dt><dd>has the meaning given above, and</dd></dl><dl id="dl0009" compact="compact"><dt>R³²</dt><dd>Is hydrogen or sulfomethyl,</dd><dt>R³³</dt><dd>Methyl, carboxy or carboxyalkyl with C₁- to C₄-Alkyl is</dd><dt>R³⁴</dt><dd>Is hydrogen or methyl,</dd><dt>R³⁵</dt><dd>Is hydrogen, cyano, carbamoyl, carboxy or sulfomethyl,</dd><dt>R³⁶</dt><dd>Is methyl, ethyl or β-sulfoethyl,</dd><dt>R³⁷</dt><dd>Methyl, carboxy or carboxyalkyl with C₁- to C₄-Alkyl is</dd><dt>R³⁸</dt><dd>Is acetamido, ureido or methyl,</dd><dt>R³⁹</dt><dd>Is hydrogen, methyl or methoxy,</dd><dt>m</dt><dd>0 or 1,</dd><dt>n</dt><dd>1, 2 or 3,</dd><dt>Z.³</dt><dd>one of the meanings of Z² has, and</dd><dt>M and Z</dt><dd>have one of the meanings given above.</dd></dl>

0031Preferred dye mixtures contain one or more, such as two or three, preferably 1 or 2, of the specified and defined general formula (I),<chemistry id="chem0021" num="0021"><img file="EP1490441B2_D0021.tif" /></chemistry>one or more dyes of the general formula (II) specified and defined below<chemistry id="chem0022" num="0022"><img file="EP1490441B2_D0022.tif" /></chemistry>and one or more dyes of the general formula (III-a) specified and defined below<chemistry id="chem0023" num="0023"><img file="EP1490441B2_D0023.tif" /></chemistry>in which D¹, D², D³, D⁴ D⁵, R^O, R *, R **, f and M have the meanings given above.

0032Preferred mixtures also contain one or more dyes of the general formula (I)<chemistry id="chem0024" num="0024"><img file="EP1490441B2_D0024.tif" /></chemistry>where D¹, D² and M have the meanings given above and one or more dyes of the general formula (II)<chemistry id="chem0025" num="0025"><img file="EP1490441B2_D0025.tif" /></chemistry>where D³, D⁴, R *, R ** and M have the meanings given above, and one or more dyes of the general formulas (Ga) to (Gf).

0033Further preferred dye mixtures contain one or more, such as two or three, preferably 1 or 2, dyes of the general formula (I) specified and defined below,<chemistry id="chem0026" num="0026"><img file="EP1490441B2_D0026.tif" /></chemistry>and one or more, such as two or three, preferably 1 or 2, dyes of the general formula (II-a) indicated and defined below<chemistry id="chem0027" num="0027"><img file="EP1490441B2_D0027.tif" /></chemistry>wherein<ul id="ul0002" list-style="none" compact="compact"><li>D¹, D², D³, D⁴, R * and M have the meanings given above. D are particularly preferably¹, D², D³ and D⁴ independently for 3- (β-sulfatoethylsulfonyl) phenyl, 4- (β-sulfatoethylsulfonyl) phenyl, 2-sulfo-4- (β-sulfatoethylsulfonyl) phenyl, 2-methoxy-5- (β-sulfatoethylsulfonyl) phenyl , 2,5-dimethoxy-4- (β-sulfatoethylsulfonyl) phenyl, 2-methoxy-5-methyl-4- (β-sulfatoethylsulfonyl) phenyl, 3- or 4-vinylsulfonylphenyl, 2-sulfo-4- (vinylsulfonyl) phenyl, 2-methoxy-5- (vinylsulfonyl) phenyl, 2,5-dimethoxy-4- (vinylsulfonyl) phenyl or 2-methoxy-5-methyl-4- (vinylsulfonyl) phenyl.</li></ul>

0034Particularly preferred mixtures according to the invention contain one or more dyes of the general formula (Ib),<chemistry id="chem0028" num="0028"><img file="EP1490441B2_D0028.tif" /></chemistry>one or more dyes of the general formula (II-d)<chemistry id="chem0029" num="0029"><img file="EP1490441B2_D0029.tif" /></chemistry>and one or more dyes of the general formula (III-b)<chemistry id="chem0030" num="0030"><img file="EP1490441B2_D0030.tif" /></chemistry>

0035In the general formulas (Ib), (II-d) and (III-b), M and Z have the meanings given above.

0036In the general formulas (Ib), (II-d) and (III-b), R¹⁰¹ to R¹¹⁰ independently of one another preferred for hydrogen, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, sulfo, carboxy or halogen and Z for vinyl or β-sulfatoethyl, in the formulas (Ib), (II-d) and (III-b) R are very particularly preferred¹⁰¹ to R¹¹⁰ independently of one another hydrogen, methyl, methoxy or sulfo and Z vinyl or β-sulfatoethyl. In the general formula (III-b), R⁰ one of the meanings mentioned above.

0037The dye mixtures according to the invention can be present as a preparation in solid or in liquid (dissolved) form. In solid form they contain, as far as necessary, the electrolyte salts that are customary in water-soluble and in particular fiber-reactive dyes, such as sodium chloride, potassium chloride and sodium sulfate, and can furthermore contain the auxiliaries customary in commercial dyes, such as buffer substances, which have a pH in aqueous solution between 3 and 7 can adjust, such as sodium acetate, sodium citrate, sodium borate, sodium hydrogen carbonate, Sodium dihydrogenphosphate and disodium hydrogenphosphate, as well as coloring aids, dustproofing agents and small amounts of siccatives; if they are in liquid, aqueous solution (including the content of thickeners, as is customary in printing pastes), they can also contain substances which ensure the durability of these preparations, such as mold-preventing agents.

0038In solid form, the dye mixtures according to the invention are generally in the form of powders or granules containing electrolytes (hereinafter generally referred to as preparation), optionally with one or more of the abovementioned auxiliaries. The preparations contain 20 to 90% by weight of the dye mixture, based on the preparation contained. The buffer substances are generally present in a total amount of up to 5% by weight, based on the preparation.

0039If the dye mixtures according to the invention are in aqueous solution, the total dye content in these aqueous solutions is up to about 50% by weight, for example between 5 and 50% by weight, the electrolyte salt content in these aqueous solutions preferably being below 10% by weight. -%, based on the aqueous solution, is; the aqueous solutions (liquid preparations) can generally contain the abovementioned buffer substances in an amount of up to 5% by weight, preferably up to 2% by weight.

0040Dyes of the general formula (I) have been described in numerous literature and, for example, from <patcit id="pcit0006" dnum="US2657205A"><text>U.S. Patent 2,657,205</text></patcit> and from the Japanese patent application publication <patcit id="pcit0007" dnum="JPSHO58160362B"><text>Sho-58-160 362</text></patcit> as well as from the <patcit id="pcit0008" dnum="US4257770A"><text>U.S. Patent 4,257,770</text></patcit> and the literature mentioned there and dyes of the general formula (II) are in <patcit id="pcit0009" dnum="DE19600765A1"><text>DE 196 00 765 A1</text></patcit> described. Dyes of the general formula (III) have also been described in large numbers and can be obtained using standard synthetic methods. Dyes of the general formulas (15) to (18) are partially formed during the synthesis of dyes of the general formulas (I) and (II) and are also accessible via standard synthesis methods. Dyes of the general formulas (15) and (16) are usually used as shading components. Dyes of the formula (Ga) - (Gf) are known from the literature and are accessible by standard processes.

0041The dye mixtures according to the invention can be prepared in a conventional manner, such as by mechanical mixing of the individual dyes, whether in the form of their dye powders or granules or their synthesis solutions or of aqueous solutions of the individual dyes in general, which may also contain conventional auxiliaries or by diazotization and coupling of suitable mixtures of diazo and coupling components in the desired proportions, which are familiar to the person skilled in the art.

0042For example, if the diazo components with groups D¹, D⁴ and D⁵ according to the general formulas (I), (II) and (III) have the same meaning (D¹ = D⁴ = D⁵), an amine of the general formula (19)         D¹ - NH₂     (19), where D¹ is as defined above, diazotized in a conventional manner and then the diazonium compound obtained with an aqueous solution or suspension of a mixture with a fixed ratio of a monoazo dye according to the general formula (15), a monoazo dye according to the general formula (17) and a coupling component of the general Formula (20)<chemistry id="chem0031" num="0031"><img file="EP1490441B2_D0031.tif" /></chemistry>where T, R⁰, M, b, f and v are defined as specified above.

0043In the event that groups D² and D³ as well as D¹, D⁴ and D⁵ according to the general formulas (I), (II) and (III) have the same meaning (D² = D³ and D¹ = D⁴ = D⁵), the dye mixture according to the invention can be prepared by using an amine of the general formula (21),         D² - NH₂     (21), where D² is as defined above, diazotized in a conventional manner and onto a mixture of the coupling components of the general formulas (22) and (23)<chemistry id="chem0032" num="0032"><img file="EP1490441B2_D0032.tif" /></chemistry>wherein M, R * and R ** are as defined above, couples at a pH below 3 in the first stage, the reaction mixture obtained is mixed with another coupling component of the general formula (20) and then an amine of the general formula 19) diazotized and coupled with the resulting mixture of the monoazo dyes of the general formulas (15) and (17) and the coupling component of the general formula (20).

0044Alternatively, the dye mixture according to the invention in the event that groups D¹ to D⁵ according to the general formulas (I), (II) and (III) have the same meaning (D¹ = D² = D³ = D⁴ = D⁵), can be prepared by diazotizing an amine of the general formula (19) in a conventional manner and on a mixture with a fixed ratio of the coupling components of the general formulas (20), (22) and (23) first at a pH below 3 couples in a first stage to a mixture of the monoazo dyes of the general formulas (15) and (17) and the coupling component of the general formula (20), and then, by increasing the pH, carries out the second coupling to mix the dyes of the general formulas (I), (II) and (III).

0045The dye mixture according to the invention is isolated in a manner known per se by salting out, for example with sodium chloride or potassium chloride, or by spray drying or evaporation.

0046The solutions obtained in the synthesis of the dyes of the general formulas (1), (II) and (III), if appropriate after adding a buffer substance and if appropriate after concentration, can also be used directly as liquid preparations for dyeing.

0047Dye mixtures which, in addition to β-chloroethylsulfonyl or β-thiosulfatoethylsulfonyl or β-sulfatoethylsulfonyl groups, also have vinylsulfonyl groups as reactive radicals, can be synthesized not only from appropriately substituted vinylsulfonyl anilines or naphthylamines, but also by reacting a dye mixture, in which Z for β Chloroethyl, β-thiosulfatoethyl, or β-sulfatoethyl, can be obtained with an amount of alkali required for the desired proportion and conversion of the β-substituted ethylsulfonyl groups mentioned into vinylsulfonyl groups. This transfer takes place in a manner familiar to the person skilled in the art.

0048The dye mixtures according to the invention have valuable performance properties. They are used for dyeing or printing materials containing hydroxyl and / or carbonamide groups, for example in the form of sheets, such as paper and leather or of films, for example made of polyamide, or in bulk, for example of polyamide and polyurethane, but in particular of these Materials used in fiber form. The solutions of the dye mixtures according to the invention obtained in the synthesis, if appropriate after adding a buffer substance, if appropriate also after concentrating or diluting, can be used directly as a liquid preparation for dyeing.

0049The present invention thus also relates to the use of the dye mixtures according to the invention for dyeing or printing these materials or processes for dyeing or printing such materials in procedures which are conventional per se, in which a dye mixture according to the invention or its individual components (dyes) are used individually together as colorants starts. The materials are preferably used in the form of fiber materials, in particular in the form of textile fibers, such as fabrics or yarns, such as in the form of strands or packages.

0050Materials containing hydroxyl groups are of natural or synthetic origin, such as, for example, cellulose fiber materials or their regenerated products and polyvinyl alcohols. Cellulose fiber materials are preferably cotton, but also other vegetable fibers, such as linen, hemp, jute and ramie fibers; Regenerated cellulose fibers are, for example, cellulose and viscose rayon, as well as chemically modified cellulose fibers, such as aminated cellulose fibers or fibers, as described for example in<patcit id="pcit0010" dnum="WO9637641A"><text>WO 96/37641</text></patcit> and <patcit id="pcit0011" dnum="WO9637642A"><text>WO 96/37642</text></patcit> as in <patcit id="pcit0012" dnum="EP0538785A"><text>EP-A-0 538 785</text></patcit> and <patcit id="pcit0013" dnum="EP0692559A"><text>EP-A-0 692 559</text></patcit> are described.

0051Materials containing carbonamide groups are, for example, synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hair, silk, leather, polyamide-6,6, polyamide-6, polyamide-11 and polyamide-4.

0052The dye mixtures according to the invention can be applied and fixed on the substrates mentioned, in particular on the fiber materials mentioned, by the application techniques known for water-soluble, in particular for the fiber-reactive dyes. So you get with them on cellulose fibers by the exhaust process from both short and long liquors, for example in the ratio of goods to liquor from 1: 5 to 1: 100, preferably 1: 6 to 1: 30, using a wide variety of acid-binding agents and if necessary, neutral salts, if necessary, such as sodium chloride or sodium sulfate, dyeings with very good color yields. Dyeing is preferably carried out in an aqueous bath at temperatures between 40 and 105 ° C., if appropriate at a temperature up to 130 ° C. under pressure, but preferably at 30 to 95 ° C., in particular 45 to 65 ° C., and if appropriate in the presence of customary dyeing auxiliaries . One can proceed in such a way that the material is introduced into the warm bath and this is gradually heated to the desired dyeing temperature and the dyeing process is completed at this temperature. The neutral salts which accelerate the removal of the dyes can, if desired, also be added to the bath only after the actual dyeing temperature has been reached.

0053After the padding process, excellent color yields and a very good color build-up are also obtained on cellulose fibers, by staying at room temperature or elevated temperature, for example up to about 60 ° C., or in continuous dyeing processes, for example using a pad-dry-pad-steam process , can be fixed in the usual way by steaming or with dry heat.

0054Also according to the usual printing processes for cellulose fibers which are single-phase, for example by printing with a printing paste containing sodium bicarbonate or another acid-binding agent and subsequent steaming at 100 to 103 ° C., or two-phase, For example, printing with neutral or weakly acidic printing ink and subsequent fixing can be carried out either by passing through a hot electrolyte-containing alkaline bath or by padding with an alkaline electrolyte-containing pad liquor and then lingering or steaming or treating with dry heat of the alkaline-padded material Prints with good contours and a clear white background. The failure of the prints is only slightly dependent on changing fixing conditions.

0055Hot air from 120 to 200 ° C is used for fixation using dry heat using the usual heat-setting processes. In addition to the usual steam from 101 to 103 ° C, superheated steam and pressure steam at temperatures up to 160 ° C can also be used.

0056The acid-binding agents and the fixation of the dyes of the dye mixtures according to the invention on the cellulose fibers are, for example, water-soluble basic salts of the alkali metals and also alkaline earth metals of inorganic or organic acids or compounds which release alkali in the heat, and further alkali silicates. In particular, the alkali metal hydroxides and alkali metal salts of weak to moderately strong inorganic or organic acids should be mentioned, the alkali compounds preferably referring to the sodium and potassium compounds. Such acid-binding agents are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium trichloroacetate, trisodium phosphate or water glass or mixtures thereof, such as, for example, mixtures of sodium hydroxide solution and water glass.

0057The dye mixtures according to the invention are notable for their excellent color strength on the cellulose fiber materials when used in the dyeing and printing processes, some of which can be achieved even in the presence of little or no alkali or alkaline earth compounds. In these special cases, for example, no electrolyte salt is required for a low color depth, no more than 5 g / l of electrolyte salt for a medium color depth and no more than 10 g / l of electrolyte salt for large color depths. A shallow depth of color denotes the use of 2% by weight of dye based on the substrate to be colored, a medium depth of color indicates the use of 2 to 4% by weight of dye based on the substrate to be colored and a large depth of color indicates the use of 4 to 10% by weight of dye based on the substrate to be colored.

0058The dyeings and prints obtainable with the dye mixtures according to the invention have clear shades; in particular, the dyeings and prints on cellulose fiber materials have good lightfastness and in particular good wet fastnesses, such as wash, walk, water, seawater, over-dyeing and acidic and alkaline perspiration fastnesses, furthermore good pleating fastness, ironing fastness and rubbing fastness. Furthermore, the cellulose dyeings after the customary aftertreatment by rinsing to remove unfixed dye components show excellent wet fastness properties, particularly since unfixed dye components can be easily washed out because of their good solubility in cold water.

0059Furthermore, the dye mixtures according to the invention can also be used for fiber-reactive dyeing of wool. Wool can also be finished with or without felt (cf. for example<nplcit id="ncit0001" npl-type="b"><text>H. Rath, Textbook of Textile Chemistry, Springer-Verlag, 3rd edition (1972), pp. 295-299</text></nplcit>, especially the equipment according to the so-called <nplcit id="ncit0002" npl-type="s"><text>Hercosett process (p. 298</text></nplcit>); <nplcit id="ncit0003" npl-type="s"><text>J. Soc. Dyers and Colorists 1972, 93-99</text></nplcit>, and <nplcit id="ncit0004" npl-type="s"><text>1975, 33-44</text></nplcit>) dye with very good fastness properties. The process of dyeing on wool is carried out in the usual and known way of dyeing from an acidic environment. For example, acetic acid and / or ammonium sulfate or acetic acid and ammonium acetate or sodium acetate can be added to the dyebath in order to obtain the desired pH. In order to achieve a useful levelness of the coloring, it is advisable to add conventional leveling aids, such as, for example, based on a reaction product of cyanuric chloride with three times the molar amount of an aminobenzenesulfonic acid and / or an aminonaphthalenesulfonic acid or on the basis of a reaction product of, for example, stearylamine with ethylene oxide. For example, the dye mixture according to the invention is preferably first subjected to the exhaust process from an acidic dye bath with a pH of about 3.5 to 5.5 while checking the pH, and then, towards the end of the dyeing time, the pH is neutral and optionally weak alkaline range shifted to a pH of 8.5, to bring about the full reactive bond between the dyes of the dye mixtures according to the invention and the fiber, in particular in order to achieve high color depths. At the same time, the nonreactively bound dye component is removed.

0060The procedure described here also applies to the production of dyeings on fiber materials made from other natural polyamides or from synthetic polyamides and polyurethanes. As a rule, the material to be dyed is introduced into the bath at a temperature of approx. 40 ° C, agitated there for some time, the dyebath is then adjusted to the desired weakly acidic, preferably weakly acetic acid, pH value and the actual dyeing at one Temperature between 60 and 98 ° C carried out. The dyeings can also be carried out at boiling temperature or in closed dyeing machines at temperatures up to 106 ° C. Since the water mixtures of the dye mixtures according to the invention are very good, they can also be used advantageously in conventional continuous dyeing processes. The color strength of the dye mixtures according to the invention is very high.

0061The dye mixtures according to the invention provide, on the materials mentioned, preferably fiber materials, navy blue to deep black dyeings with very good fastness properties.

0062The following examples serve to illustrate the invention. The parts are parts by weight, the percentages are percentages by weight, unless stated otherwise. Parts by weight relate to parts by volume such as kilograms to liters. The compounds described by formula in the examples are written in the form of the sodium salts, since they are generally prepared and isolated in the form of their salts, preferably sodium or potassium salts, and are used for dyeing in the form of their salts. The starting compounds mentioned in the examples below, in particular table examples, can be used in the synthesis in the form of the free acid or likewise in the form of their salts, preferably alkali metal salts, such as sodium or potassium salts.

example 1

006370 Parts of an electrolyte-containing dye powder which contains the navy blue disazo dye of the formula (I-1)<chemistry id="chem0033" num="0033"><img file="EP1490441B2_D0033.tif" /></chemistry>contains 75%, 18 parts of an electrolyte-containing dye powder which contains the scarlet disazo dye of the formula (II-1)<chemistry id="chem0034" num="0034"><img file="EP1490441B2_D0034.tif" /></chemistry>contains 70% and 12 parts of an electrolyte-containing dye powder which contains the orange azo dye of the formula (III-1)<chemistry id="chem0035" num="0035"><img file="EP1490441B2_D0035.tif" /></chemistry>contains 75%, are mixed mechanically.

0064The resulting dye mixture according to the invention provides deep black dyeings and prints under the dyeing conditions customary for reactive dyes, for example on cotton.

Example 2

006575 Parts of an electrolyte-containing dye powder which contains the navy blue disazo dye of the formula (I-1) in a 70% proportion, 15 parts of an electrolyte-containing dye powder which contains the scarlet disazo dye of the formula (II-2)<chemistry id="chem0036" num="0036"><img file="EP1490441B2_D0036.tif" /></chemistry>contains in 75% and 10 parts of an electrolyte-containing dye powder, which contains the orange-colored azo dye of the formula (III-1) in 80%, are dissolved in 700 parts of water and the dye solution obtained to pH 5.5-6 , 5 set. Evaporation of this dye solution gives a dye mixture which produces deep black dyeings and prints on cotton under the dyeing conditions customary for reactive dyes.

Example 3

0066580 Parts of 4- (β-sulfatoethylsulfonyl) aniline are suspended in 1400 parts of ice water and 371 parts of 30% hydrochloric acid and diazotized by dropwise addition of 357 parts of 40% sodium nitrite solution. After removal of the excess nitrite with amidosulfonic acid, 210 parts of 1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid and 67 parts of 4-hydroxy-7- (sulfomethyl-amino) -naphthalene-2-sulfonic acid are added to this, by reaction 48 parts of 7-amino-4-hydroxy-naphthalene-2-sulfonic acid with 32 parts of formaldehyde sodium bisulfite were prepared in an aqueous medium at pH 5.5-6 and 45 ° C. and initially couples in the first stage at pH 1 to 1.5 below 20 ° C. to a mixture of two monoazo dyes according to the formulas (15-1) and (17-1). The specified pH range is adjusted by adding solid sodium bicarbonate and maintained during the coupling reaction.<chemistry id="chem0037" num="0037"><img file="EP1490441B2_D0037.tif" /></chemistry>After the first coupling has ended, 76 parts of 7-acetylamino-4-hydroxy-naphthalene-2-sulfonic acid are added to this mixture and the pH is adjusted to 5.5-6.5 below 25 ° C. with sodium carbonate. The 65:20:15 mixture of the three azo dyes (I-1), (II-1) and (III-2) formed after the second coupling reaction has ended is isolated by spray drying.<chemistry id="chem0038" num="0038"><img file="EP1490441B2_D0038.tif" /></chemistry>

0067Alternatively, the dye solution obtained can also be buffered at pH 5.5-6 by adding a phosphate buffer and adjusted as a liquid brand of certain strength by further dilution or concentration. The dye mixture according to the invention obtained dyes cotton in black tones.

Example 4

0068515 Parts of 4- (β-sulfatoethylsulfonyl) aniline are suspended in 1200 parts of ice water and 330 parts of 30% hydrochloric acid and diazotized by dropwise addition of 318 parts of 40% sodium nitrite solution. After removing the excess nitrite with amidosulfonic acid, 210 parts of 1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid are added and the first stage is coupled at pH 1 to 1.5 below 20 ° C to a red monoazo dye of the formula (15 -1). The specified pH range is adjusted by adding solid sodium bicarbonate and maintained during the coupling reaction. After the first coupling has ended, 76 parts of 6-acetylamino-4-hydroxy-naphthalene-2-sulfonic acid and an aqueous solution of 143 parts of the scarlet monoazo dye of the formula (17-2) are added to the reaction mixture,<chemistry id="chem0039" num="0039"><img file="EP1490441B2_D0039.tif" /></chemistry>by diazotization of 65 parts of 2-amino-5- (β-sulfatoethylsulfonyl) benzenesulfonic acid with 31.5 parts of 40% sodium nitrite solution in an acidic medium and subsequent coupling to 60 parts of 4-hydroxy-7- (sulfomethylamino) naphthalene 2-sulfonic acid was obtained at pH 1-2. The pH is then adjusted below 5.5 ° C. using sodium carbonate pH 5.5-6.5 and the 65:20:15 mixture of the three dyes (I-1), (II-2) and (III-3) formed after the coupling reaction has ended. isolated by evaporation in a vacuum or by spray drying.<chemistry id="chem0040" num="0040"><img file="EP1490441B2_D0040.tif" /></chemistry>The dye mixture according to the invention obtained dyes cotton in black tones.

Example 5

0069<ol id="ol0001" compact="compact"><li>a) 230 parts of 4- (β-sulfatoethylsulfonyl) aniline are suspended in 550 parts of ice water and 148 parts of 30% hydrochloric acid and diazotized by dropwise addition of 142 parts of 40% sodium nitrite solution. After removal of the excess nitrite with amidosulfonic acid, 187 parts of 1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid and 64 parts of 4-hydroxy-7- (sulfomethylamino) -naphthalene-2-sulfonic acid, as in Example 3 were prepared, and coupled in the first stage at pH 1 to 1.5 below 20 ° C to a mixture of the two monoazo dyes according to formulas (15-1) and (17-1). The specified pH range is adjusted by adding solid sodium bicarbonate and maintained during the coupling reaction. After the first coupling reaction has ended, 120 parts of a coupler of the formula (20-1) are added to this mixture.<chemistry id="chem0041" num="0041"><img file="EP1490441B2_D0041.tif" /></chemistry></li><li>b) In a second, separate reaction vessel, 316 parts of 2-methoxy-5- (β-sulfatoethylsulfonyl) aniline are suspended in 950 parts of ice water and 183 parts of 30% hydrochloric acid and diazotized by dropwise addition of 177 parts of 40% sodium nitrite solution. The excess nitrite is then removed with amidosulfonic acid solution and the diazo suspension obtained is pumped to the coupler mixture from a).</li></ol>The pH is then adjusted below 5.5 ° C. using sodium carbonate 5.5-6.5 and the 60:20:20 mixture of the three dyes (I-2), (II-3) and (III-4 ) isolated by evaporation in a vacuum or by spray drying.<chemistry id="chem0042" num="0042"><img file="EP1490441B2_D0042.tif" /></chemistry>The dye mixture according to the invention obtained dyes cotton in black tones.

Example 6

0070<ol id="ol0002" compact="compact"><li>a) 351 parts of 4- (β-sulfatoethylsulfonyl) aniline are suspended in 850 parts of ice water and 225 parts of 30% hydrochloric acid and diazotized by dropwise addition of 216 parts of 40% sodium nitrite solution. To this are added 319 parts of 1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid and 83 parts of 4-hydroxy-7- (sulfomethylamino) -naphthalene-2-sulfonic acid, which were prepared as described in Example 3, and couples in the first stage at pH 1 to 1.5 below 20 ° C to a mixture of the two monoazo dyes according to formulas (15-1) and (17-1). The specified pH range is adjusted by adding solid sodium bicarbonate and maintained during the coupling reaction.</li><li>b) In a second, separate reaction vessel, 427 parts of 2,5-dimethoxy-4- (β-sulfatoethylsulfonyl) aniline are suspended in 1200 parts of ice water and 226 parts of 30% hydrochloric acid and by dropwise addition of 217 parts of 40% sodium nitrite solution diazotized. The excess nitrite is then removed with amidosulfonic acid solution and the resulting diazo suspension is pumped to the solution of the two monoazo dyes from a) after the first coupling has ended.</li></ol>Then it is adjusted below 25 ° C. with sodium carbonate pH 5-6 and the dye solution obtained after the second coupling reaction has been mixed with 250 parts of an orange dye of the formula (III-5). The resulting 67:17:16 mixture of the three azo dyes (I-3), (II-4) and (III-5) can be isolated by evaporation in vacuo or by spray drying.<chemistry id="chem0043" num="0043"><img file="EP1490441B2_D0043.tif" /></chemistry>The dye mixture according to the invention thus obtained dyes cotton in black tones.

Example 7

007150 Parts of an electrolyte-containing dye powder which contains the greenish navy-blue disazo dye of the formula (I-4)<chemistry id="chem0044" num="0044"><img file="EP1490441B2_D0044.tif" /></chemistry>contains 70%, 25 parts of an electrolyte-containing dye powder which contains the navy blue disazo dye of the formula (I-1) in 75% proportion, 20 parts of an electrolyte-containing dye powder which contains the scarlet disazo dye of the formula (II-2) also contains 75% and 5 parts of an electrolyte-containing dye powder, that contains the orange-colored azo dye of the formula (III-1) in an 80% proportion are dissolved in 500 parts of water and the dye solution obtained is adjusted to pH 5.5-6.5 and buffered with phosphate buffer. Evaporation of this solution gives a dye mixture which gives deep black dyeings and prints to cotton under the dyeing conditions customary for reactive dyes.

Example 9

007270 Parts of an electrolyte-containing dye powder which contains the navy blue disazo dye of the formula (I-6)<chemistry id="chem0045" num="0045"><img file="EP1490441B2_D0045.tif" /></chemistry>contains 70%, 18 parts of an electrolyte-containing dye powder which contains the scarlet disazo dye of the formula (II-1) in a 75% proportion and 12 parts of an electrolyte-containing dye powder which contains the orange-colored azo dye of the formula (III-1) contains 70%, are mixed together as described in Example 1 or 2.

0073The resulting dye mixture according to the invention provides deep black dyeings under the dyeing conditions customary for reactive dyes and with a reduced amount of salt compared to the standard method, for example on cotton.

Examples 11 to 448

0074The following table examples describe further mixtures according to the invention of the dyes of the general formulas (I) - (III), which are each given in the form of the sodium salts. The mixing ratios are given in percent by weight. The dye mixtures provide gray to deep black dyeings using the dyeing methods customary for reactive dyes, for example on cotton.

Dye mixtures according to Example 1 or 2

0075<tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="16mm" /><colspec colnum="2" colname="col2" colwidth="62mm" /><colspec colnum="3" colname="col3" colwidth="56mm" /><colspec colnum="4" colname="col4" colwidth="60mm" /><colspec colnum="5" colname="col5" colwidth="33mm" colsep="0" /><thead><row><entry valign="top">Example</entry><entry valign="top">Dye according to general formula (I)</entry><entry valign="top">Dye according to general formula (II)</entry><entry valign="top">Dye according to formula (III)</entry><entry valign="top">Ratio (I) :( II) :( III)</entry></row></thead><tbody><row><entry>11</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry>(III-4)</entry><entry>65 : 20 : 15</entry></row><row><entry>12</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry>(III-6)</entry><entry>68 : 20 : 12</entry></row><row><entry>13</entry><entry>(I-1)</entry><entry>(II-2)</entry><entry>(III-2)</entry><entry>67 : 20 : 13</entry></row><row><entry>14</entry><entry>(I-1)</entry><entry>(II-2)</entry><entry>(III-4)</entry><entry>65 : 21 : 14</entry></row><row><entry>15</entry><entry>(I-1)</entry><entry>(II-2)</entry><entry>(III-6)</entry><entry>65 : 22 : 13</entry></row><row><entry>16</entry><entry>(I-1)</entry><entry>(II-2)</entry><entry>(III-7)</entry><entry>64 : 18 : 18</entry></row><row><entry>23</entry><entry>(I-1)</entry><entry><chemistry id="chem0046" num="0046"><img file="EP1490441B2_D0046.tif" /></chemistry></entry><entry>(III-1)</entry><entry>65 : 20 : 15</entry></row><row><entry>24</entry><entry>(I-1)</entry><entry><chemistry id="chem0047" num="0047"><img file="EP1490441B2_D0047.tif" /></chemistry></entry><entry><chemistry id="chem0048" num="0048"><img file="EP1490441B2_D0048.tif" /></chemistry></entry><entry>70 : 20 : 10</entry></row><row><entry>30</entry><entry>(I-1)</entry><entry><chemistry id="chem0049" num="0049"><img file="EP1490441B2_D0049.tif" /></chemistry></entry><entry><chemistry id="chem0050" num="0050"><img file="EP1490441B2_D0050.tif" /></chemistry></entry><entry>60 : 22 : 18</entry></row><row><entry>31</entry><entry>(I-1)</entry><entry><chemistry id="chem0051" num="0051"><img file="EP1490441B2_D0051.tif" /></chemistry></entry><entry>(III-1)</entry><entry>72 : 18 : 10</entry></row><row><entry>33</entry><entry>(I-1)</entry><entry><chemistry id="chem0052" num="0052"><img file="EP1490441B2_D0052.tif" /></chemistry></entry><entry>(III-7)</entry><entry>70 : 20 : 10</entry></row><row><entry>36</entry><entry>(I-1)</entry><entry><chemistry id="chem0053" num="0053"><img file="EP1490441B2_D0053.tif" /></chemistry></entry><entry>(III-1)</entry><entry>66 : 22 : 12</entry></row><row><entry>40</entry><entry>(I-1)</entry><entry><chemistry id="chem0054" num="0054"><img file="EP1490441B2_D0054.tif" /></chemistry></entry><entry>(III-1)</entry><entry colsep="1">67 : 22 : 11</entry></row><row><entry>41</entry><entry>(I-1)</entry><entry><chemistry id="chem0055" num="0055"><img file="EP1490441B2_D0055.tif" /></chemistry></entry><entry><chemistry id="chem0056" num="0056"><img file="EP1490441B2_D0056.tif" /></chemistry></entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>42</entry><entry>(I-1)</entry><entry><chemistry id="chem0057" num="0057"><img file="EP1490441B2_D0057.tif" /></chemistry></entry><entry>(III-1)</entry><entry colsep="1">68 : 20 : 12</entry></row><row><entry>43</entry><entry>(I-1)</entry><entry><chemistry id="chem0058" num="0058"><img file="EP1490441B2_D0058.tif" /></chemistry></entry><entry>(III-2)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>47</entry><entry>(I-1)</entry><entry><chemistry id="chem0059" num="0059"><img file="EP1490441B2_D0059.tif" /></chemistry></entry><entry>(III-10)</entry><entry>64 : 20 : 16</entry></row><row><entry>51</entry><entry>(I-1)</entry><entry><chemistry id="chem0060" num="0060"><img file="EP1490441B2_D0060.tif" /></chemistry></entry><entry>(III-2)</entry><entry>68 : 20 : 12</entry></row><row><entry>53</entry><entry>(I-1)</entry><entry><chemistry id="chem0061" num="0061"><img file="EP1490441B2_D0061.tif" /></chemistry></entry><entry>(III-1)</entry><entry>70 : 15 : 15</entry></row><row><entry>54</entry><entry>(I-1)</entry><entry><chemistry id="chem0062" num="0062"><img file="EP1490441B2_D0062.tif" /></chemistry></entry><entry>(III-12)</entry><entry>65 : 20 : 15</entry></row><row><entry>57</entry><entry>(I-1)</entry><entry><chemistry id="chem0063" num="0063"><img file="EP1490441B2_D0063.tif" /></chemistry></entry><entry>(III-2)</entry><entry>70 : 15 : 15</entry></row><row><entry>58</entry><entry>(I-1)</entry><entry><chemistry id="chem0064" num="0064"><img file="EP1490441B2_D0064.tif" /></chemistry></entry><entry>(III-10)</entry><entry>65 : 23 : 12</entry></row><row><entry>61</entry><entry>(I-1)</entry><entry><chemistry id="chem0065" num="0065"><img file="EP1490441B2_D0065.tif" /></chemistry></entry><entry>(III-1)</entry><entry>64 : 22 : 14</entry></row><row><entry>63</entry><entry>(I-1)</entry><entry><chemistry id="chem0066" num="0066"><img file="EP1490441B2_D0066.tif" /></chemistry></entry><entry>(III-7)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>65</entry><entry>(I-1)</entry><entry><chemistry id="chem0067" num="0067"><img file="EP1490441B2_D0067.tif" /></chemistry></entry><entry>(III-1)</entry><entry colsep="1">69 : 20 : 11</entry></row><row><entry>66</entry><entry>(I-2)</entry><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>67</entry><entry>(I-2)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>68</entry><entry>(I-2)</entry><entry>(II-7)</entry><entry>(III-1)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>70</entry><entry>(I-2)</entry><entry>(II-24)</entry><entry>(III-13)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>71</entry><entry>(I-2)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>74</entry><entry>(I-2)</entry><entry>(II-45)</entry><entry>(III-1)</entry><entry colsep="1">60 : 25 : 15</entry></row><row><entry>77</entry><entry>(I-3)</entry><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>78</entry><entry>(I-3)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>81</entry><entry>(I-3)</entry><entry>(II-7)</entry><entry>(III-14)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>85</entry><entry>(I-3)</entry><entry>(II-24)</entry><entry>(III-8)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>86</entry><entry>(I-3)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>89</entry><entry>(I-3)</entry><entry>(II-37)</entry><entry>(III-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>91</entry><entry>(I-3)</entry><entry>(II-45)</entry><entry>(III-13)</entry><entry colsep="1">60 : 25 : 15</entry></row><row><entry>94</entry><entry>(I-4)</entry><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>95</entry><entry>(I-4)</entry><entry>(II-2)</entry><entry>(III-7)</entry><entry colsep="1">63 : 21 : 16</entry></row><row><entry>98</entry><entry>(I-4)</entry><entry>(II-7)</entry><entry>(III-14)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>102</entry><entry>(I-4)</entry><entry>(II-24)</entry><entry>(III-8)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>103</entry><entry>(I-4)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>106</entry><entry>(I-4)</entry><entry>(II-37)</entry><entry>(III-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>108</entry><entry>(I-4)</entry><entry>(II-45)</entry><entry>(III-13)</entry><entry colsep="1">60 : 25 : 15</entry></row><row><entry>111</entry><entry>(I-5)</entry><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>112</entry><entry>(I-5)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>115</entry><entry>(I-5)</entry><entry>(II-7)</entry><entry>(III-14)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>119</entry><entry>(I-5)</entry><entry>(II-24)</entry><entry>(III-8)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>120</entry><entry>(I-5)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>123</entry><entry>(I-5)</entry><entry>(II-37)</entry><entry>(III-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>125</entry><entry>(I-5)</entry><entry>(II-45)</entry><entry>(III-13)</entry><entry colsep="1">60 : 25 : 15</entry></row><row><entry>128</entry><entry>(I-6)</entry><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>129</entry><entry>(I-6)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>132</entry><entry>(I-6)</entry><entry>(II-7)</entry><entry>(III-14)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>137</entry><entry>(I-6)</entry><entry>(11-24)</entry><entry>(III-8)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>138</entry><entry>(I-6)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>141</entry><entry>(I-6)</entry><entry>(II-37)</entry><entry>(III-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>143</entry><entry>(I-6)</entry><entry>(II-41)</entry><entry>(III-1)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>145</entry><entry>(I-6)</entry><entry>(II-45)</entry><entry>(III-13)</entry><entry colsep="1">60 : 25 : 15</entry></row><row><entry>148</entry><entry>(I-7)</entry><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>149</entry><entry>(I-7)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>152</entry><entry>(I-7)</entry><entry>(II-7)</entry><entry>(III-14)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>156</entry><entry>(I-7)</entry><entry>(II-24)</entry><entry>(III-8)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>157</entry><entry>(I-7)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>160</entry><entry>(I-7)</entry><entry>(II-37)</entry><entry>(III-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>161</entry><entry>(I-7)</entry><entry>(II-42)</entry><entry>(III-12)</entry><entry colsep="1">62 : 22 : 16</entry></row><row><entry>163</entry><entry>(I-7)</entry><entry>(II-45)</entry><entry>(III-13)</entry><entry colsep="1">60 : 25 : 15</entry></row><row><entry>166</entry><entry><chemistry id="chem0068" num="0068"><img file="EP1490441B2_D0068.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>167</entry><entry>(I-8)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>169</entry><entry>(I-8)</entry><entry>(II-7)</entry><entry>(III-14)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>171</entry><entry>(I-8)</entry><entry>(II-24)</entry><entry>(III-8)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>172</entry><entry>(I-8)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>175</entry><entry>(I-8)</entry><entry>(II-45)</entry><entry>(III-13)</entry><entry colsep="1">60 : 25 : 15</entry></row><row><entry>178</entry><entry><chemistry id="chem0069" num="0069"><img file="EP1490441B2_D0069.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>179</entry><entry>(I-9)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>182</entry><entry>(I-9)</entry><entry>(II-7)</entry><entry>(III-14)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>186</entry><entry>(I-9)</entry><entry>(II-24)</entry><entry>(III-8)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>187</entry><entry>(I-9)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>190</entry><entry>(I-9)</entry><entry>(II-37)</entry><entry>(III-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>192</entry><entry>(I-9)</entry><entry>(II-45)</entry><entry>(III-13)</entry><entry colsep="1">60 : 25 : 15</entry></row><row><entry>195</entry><entry><chemistry id="chem0070" num="0070"><img file="EP1490441B2_D0070.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>196</entry><entry>(I-10)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>198</entry><entry>(I-10)</entry><entry>(II-7)</entry><entry>(III-14)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>200</entry><entry>(I-10)</entry><entry>(II-24)</entry><entry>(III-8)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>201</entry><entry>(I-10)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>204</entry><entry>(I-10)</entry><entry>(II-45)</entry><entry>(III-13)</entry><entry colsep="1">60 : 25 : 15</entry></row><row><entry>207</entry><entry><chemistry id="chem0071" num="0071"><img file="EP1490441B2_D0071.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>208</entry><entry>(I-11)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry>65 : 20 : 15</entry></row><row><entry>211</entry><entry>(I-11)</entry><entry>(II-7)</entry><entry>(III-14)</entry><entry>67 : 20 : 13</entry></row><row><entry>215</entry><entry>(I-11)</entry><entry>(II-24)</entry><entry>(III-8)</entry><entry>65 : 22 : 13</entry></row><row><entry>216</entry><entry>(I-11)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry>66 : 20 : 14</entry></row><row><entry>219</entry><entry>(I-11)</entry><entry>(II-37)</entry><entry>(III-1)</entry><entry>70 : 20 : 10</entry></row><row><entry>221</entry><entry>(I-11)</entry><entry>(II-45)</entry><entry>(III-13)</entry><entry>60 : 25 : 15</entry></row><row><entry>224</entry><entry><chemistry id="chem0072" num="0072"><img file="EP1490441B2_D0072.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>225</entry><entry>(I-12)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>228</entry><entry>(I-12)</entry><entry>(II-7)</entry><entry>(III-14)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>232</entry><entry>(I-12)</entry><entry>(II-24)</entry><entry>(III-8)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>233</entry><entry>(I-12)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>236</entry><entry>(I-12)</entry><entry>(II-37)</entry><entry>(III-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>238</entry><entry>(I-12)</entry><entry>(II-45)</entry><entry>(III-13)</entry><entry colsep="1">60 : 25 : 15</entry></row><row><entry>241</entry><entry><chemistry id="chem0073" num="0073"><img file="EP1490441B2_D0073.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>242</entry><entry>(I-13)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>245</entry><entry>(I-13)</entry><entry>(II-7)</entry><entry>(III-14)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>249</entry><entry>(I-13)</entry><entry>(II-24)</entry><entry>(III-8)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>250</entry><entry>(I-13)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>253</entry><entry>(I-13)</entry><entry>(II-37)</entry><entry>(III-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>255</entry><entry>(I-13)</entry><entry>(II-45)</entry><entry>(III-13)</entry><entry colsep="1">60 : 25 : 15</entry></row><row><entry>258</entry><entry><chemistry id="chem0074" num="0074"><img file="EP1490441B2_D0074.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">68 : 16 : 16</entry></row><row><entry>259</entry><entry>(I-14)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>262</entry><entry>(I-14)</entry><entry>(II-7)</entry><entry>(III-14)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>266</entry><entry>(I-14)</entry><entry>(II-24)</entry><entry>(III-8)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>267</entry><entry>(I-14)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>270</entry><entry>(I-14)</entry><entry>(II-37)</entry><entry>(III-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>272</entry><entry>(I-14)</entry><entry>(II-45)</entry><entry>(III-13)</entry><entry colsep="1">60 : 25 : 15</entry></row><row><entry>275</entry><entry /><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>276</entry><entry>(I-15)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>279</entry><entry>(I-15)</entry><entry>(II-7)</entry><entry>(III-14)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>284</entry><entry>(I-15)</entry><entry>(II-24)</entry><entry>(III-8)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>285</entry><entry>(I-15)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>288</entry><entry>(I-15)</entry><entry>(II-37)</entry><entry>(III-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>290</entry><entry>(I-15)</entry><entry>(II-41)</entry><entry>(III-5)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>292</entry><entry>(I-15)</entry><entry>(II-45)</entry><entry>(III-13)</entry><entry colsep="1">60 : 25 : 15</entry></row><row><entry>295</entry><entry><chemistry id="chem0075" num="0075"><img file="EP1490441B2_D0075.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>296</entry><entry>(I-16)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>299</entry><entry>(I-16)</entry><entry>(II-7)</entry><entry>(III-14)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>303</entry><entry>(I-16)</entry><entry>(II-24)</entry><entry>(III-8)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>304</entry><entry>(I-16)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>307</entry><entry>(I-16)</entry><entry>(II-37)</entry><entry>(III-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>308</entry><entry>(I-16)</entry><entry>(II-42)</entry><entry>(III-1)</entry><entry colsep="1">67 : 22 : 11</entry></row><row><entry>310</entry><entry>(I-16)</entry><entry>(II-45)</entry><entry>(III-13)</entry><entry colsep="1">60 : 25 : 15</entry></row><row><entry>313</entry><entry><chemistry id="chem0076" num="0076"><img file="EP1490441B2_D0076.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>314</entry><entry>(I-17)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>317</entry><entry>(I-17)</entry><entry>(II-7)</entry><entry>(III-14)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>321</entry><entry>(I-17)</entry><entry>(II-24)</entry><entry>(III-8)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>322</entry><entry>(I-17)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>325</entry><entry>(I-17)</entry><entry>(II-37)</entry><entry>(III-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>328</entry><entry>(I-17)</entry><entry>(II-45)</entry><entry>(III-13)</entry><entry colsep="1">60 : 25 : 15</entry></row><row><entry>331</entry><entry><chemistry id="chem0077" num="0077"><img file="EP1490441B2_D0077.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>332</entry><entry>(I-18)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>335</entry><entry>(I-18)</entry><entry>(II-7)</entry><entry>(III-14)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>339</entry><entry>(I-18)</entry><entry>(II-24)</entry><entry>(III-8)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>340</entry><entry>(I-18)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>343</entry><entry>(I-18)</entry><entry>(II-37)</entry><entry>(III-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>345</entry><entry>(I-18)</entry><entry>(II-45)</entry><entry>(III-13)</entry><entry colsep="1">60 : 25 : 1 5</entry></row><row><entry>348</entry><entry><chemistry id="chem0078" num="0078"><img file="EP1490441B2_D0078.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>349</entry><entry>(I-19)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>352</entry><entry>(I-19)</entry><entry>(II-7)</entry><entry>(III-14)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>356</entry><entry>(I-19)</entry><entry>(II-24)</entry><entry>(III-8)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>357</entry><entry>(I-19)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>360</entry><entry>(1-19)</entry><entry>(II-37)</entry><entry>(III-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>362</entry><entry>(I-19)</entry><entry>(II-45)</entry><entry>(III-13)</entry><entry colsep="1">60 : 25 : 15</entry></row><row><entry>365</entry><entry><chemistry id="chem0079" num="0079"><img file="EP1490441B2_D0079.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>366</entry><entry>(I-20)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>369</entry><entry>(I-20)</entry><entry>(II-7)</entry><entry>(III-14)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>373</entry><entry>(I-20)</entry><entry>(II-24)</entry><entry>(III-8)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>374</entry><entry>(I-20)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>377</entry><entry>(I-20)</entry><entry>(II-37)</entry><entry>(III-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>379</entry><entry>(I-20)</entry><entry>(II-45)</entry><entry>(III-13)</entry><entry colsep="1">60 : 25 : 15</entry></row><row><entry>382</entry><entry><chemistry id="chem0080" num="0080"><img file="EP1490441B2_D0080.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>383</entry><entry>(I-21)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>386</entry><entry>(I-21)</entry><entry>(II-7)</entry><entry>(III-14)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>390</entry><entry>(I-21)</entry><entry>(II-24)</entry><entry>(III-8)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>391</entry><entry>(I-21)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>394</entry><entry>(I-21)</entry><entry>(II-37)</entry><entry>(III-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>395</entry><entry>(I-21)</entry><entry>(II-38)</entry><entry>(III-1)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>397</entry><entry>(I-21)</entry><entry>(II-45)</entry><entry>(III-13)</entry><entry colsep="1">60 : 25 : 15</entry></row><row><entry>400</entry><entry><chemistry id="chem0081" num="0081"><img file="EP1490441B2_D0081.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(III-2)</entry><entry colsep="1">65 : 18 : 17</entry></row><row><entry>401</entry><entry>(I-22)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>404</entry><entry>(I-22)</entry><entry>(II-7)</entry><entry>(III-14)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>408</entry><entry>(I-22)</entry><entry>(II-24)</entry><entry>(III-8)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>409</entry><entry>(I-22)</entry><entry>(II-26)</entry><entry>(III-1)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>412</entry><entry>(I-22)</entry><entry>(II-37)</entry><entry>(III-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>415</entry><entry>(I-22)</entry><entry>(II-45)</entry><entry>(III-13)</entry><entry colsep="1">60 : 25 : 15</entry></row></tbody></tgroup></table></tables>

Dye mixtures according to Example 3

0076<tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="16mm" /><colspec colnum="2" colname="col2" colwidth="38mm" /><colspec colnum="3" colname="col3" colwidth="40mm" /><colspec colnum="4" colname="col4" colwidth="40mm" /><colspec colnum="5" colname="col5" colwidth="33mm" colsep="0" /><thead><row><entry valign="top">example</entry><entry valign="top">Dye according to general formula (I)</entry><entry valign="top">Dye according to general formula (II)</entry><entry valign="top">Dye according to formula (III)</entry><entry valign="top">Ratio (I) :( II) :( III)</entry></row></thead><tbody><row><entry>418</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry>(III-1)</entry><entry>65 : 20 : 15</entry></row><row><entry>419</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry>(III-3)</entry><entry>63 : 20 : 1 7</entry></row><row><entry>420</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry>(III-5)</entry><entry>68 : 20 : 12</entry></row><row><entry>421</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry>(III-7)</entry><entry>64 : 18 : 18</entry></row><row><entry>422</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry>(III-13)</entry><entry>70 : 18 : 12</entry></row><row><entry>423</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry>(III-14)</entry><entry>62 : 19 : 19</entry></row></tbody></tgroup></table></tables>

Dye mixtures according to Example 4

0077<tables id="tabl0003" num="0003"><table frame="all"><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="16mm" /><colspec colnum="2" colname="col2" colwidth="30mm" /><colspec colnum="3" colname="col3" colwidth="30mm" /><colspec colnum="4" colname="col4" colwidth="62mm" /><colspec colnum="5" colname="col5" colwidth="30mm" /><thead><row><entry valign="top">example</entry><entry valign="top">Dye according to general formula (I)</entry><entry valign="top">Dye according to general formula (II)</entry><entry valign="top">Dye according to formula (III)</entry><entry valign="top">Ratio (I) :( II) :( III)</entry></row></thead><tbody><row><entry>424</entry><entry>(I-1)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry>65 : 20 : 15</entry></row><row><entry>425</entry><entry>(I-1)</entry><entry>(II-24)</entry><entry>(III-13)</entry><entry>63 : 20 : 17</entry></row><row><entry>427</entry><entry>(I-1)</entry><entry>(II-45)</entry><entry>(III-7)</entry><entry>64 : 18 : 18</entry></row><row><entry>428</entry><entry>(I-4)</entry><entry>(II-4)</entry><entry><chemistry id="chem0082" num="0082"><img file="EP1490441B2_D0082.tif" /></chemistry></entry><entry>65 : 20 : 15</entry></row><row><entry>430</entry><entry>(I-14)</entry><entry>(II-8)</entry><entry><chemistry id="chem0083" num="0083"><img file="EP1490441B2_D0083.tif" /></chemistry></entry><entry>68 : 17 : 15</entry></row><row><entry>432</entry><entry>(I-14)</entry><entry>(II-17)</entry><entry>(III-16)</entry><entry>66 : 14 : 20</entry></row></tbody></tgroup></table></tables>

Dye mixtures according to Example 5

0078<tables id="tabl0004" num="0004"><table frame="all"><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="16mm" /><colspec colnum="2" colname="col2" colwidth="31mm" /><colspec colnum="3" colname="col3" colwidth="31mm" /><colspec colnum="4" colname="col4" colwidth="58mm" /><colspec colnum="5" colname="col5" colwidth="31mm" /><thead><row><entry valign="top">example</entry><entry valign="top">Dye according to general formula (I)</entry><entry valign="top">Dye according to general formula (II)</entry><entry valign="top">Dye according to formula (III)</entry><entry valign="top">Ratio (I) :( II) :( III)</entry></row></thead><tbody><row><entry>433</entry><entry>(I-2)</entry><entry>(II-3)</entry><entry>(III-8)</entry><entry>65 : 20 : 15</entry></row><row><entry>435</entry><entry>(I-3)</entry><entry>(II-4)</entry><entry>(III-15)</entry><entry>68 : 20 : 12</entry></row><row><entry>436</entry><entry>(I-6)</entry><entry>(II-41)</entry><entry><chemistry id="chem0084" num="0084"><img file="EP1490441B2_D0084.tif" /></chemistry></entry><entry colsep="0">64 : 20 : 16</entry></row><row><entry>437</entry><entry>(I-7)</entry><entry>(II-14)</entry><entry><chemistry id="chem0085" num="0085"><img file="EP1490441B2_D0085.tif" /></chemistry></entry><entry colsep="0">70 : 18 : 12</entry></row><row><entry>438</entry><entry>(I-9)</entry><entry>(II-17)</entry><entry>(III-16)</entry><entry colsep="0">66 : 19 : 15</entry></row><row><entry>440</entry><entry>(I-21)</entry><entry>(II-38)</entry><entry><chemistry id="chem0086" num="0086"><img file="EP1490441B2_D0086.tif" /></chemistry></entry><entry colsep="0">64 : 21 : 15</entry></row></tbody></tgroup></table></tables>

Dye mixtures according to Example 6

0079<tables id="tabl0005" num="0005"><table frame="all"><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="16mm" /><colspec colnum="2" colname="col2" colwidth="38mm" /><colspec colnum="3" colname="col3" colwidth="40mm" /><colspec colnum="4" colname="col4" colwidth="40mm" /><colspec colnum="5" colname="col5" colwidth="33mm" /><thead><row><entry valign="top">example</entry><entry valign="top">Dye according to general formula (I)</entry><entry valign="top">Dye according to general formula (II)</entry><entry valign="top">Dye according to formula (III)</entry><entry valign="top">Ratio (I) :( II) :( III)</entry></row></thead><tbody><row><entry>441</entry><entry>(I-2)</entry><entry>(II-3)</entry><entry>(III-14)</entry><entry>65 : 18 : 17</entry></row><row><entry>443</entry><entry>(I-3)</entry><entry>(II-4)</entry><entry>(III-8)</entry><entry>67 : 20 : 13</entry></row><row><entry>444</entry><entry>(I-6)</entry><entry>(II-41)</entry><entry>(III-13)</entry><entry>65 : 20 : 15</entry></row><row><entry>445</entry><entry>(I-7)</entry><entry>(II-14)</entry><entry>(III-12)</entry><entry>64 : 22 : 14</entry></row><row><entry>446</entry><entry>(I-9)</entry><entry>(II-17)</entry><entry>(III-7)</entry><entry>66 : 19 : 15</entry></row><row><entry>448</entry><entry>(I-21)</entry><entry>(II-38)</entry><entry>(III-13)</entry><entry>64 : 22 : 14</entry></row></tbody></tgroup></table></tables>

Example 449

008073 Parts of an electrolyte-containing dye powder which contains the navy blue disazo dye of the formula (I-1) in a 70% proportion, 15 parts of an electrolyte-containing dye powder which contains the scarlet disazo dye of the formula (II-2) in a 75% proportion and 13 Parts of an electrolyte-containing dye powder which contains the orange azo dye of the formula (III-21)<chemistry id="chem0087" num="0087"><img file="EP1490441B2_D0087.tif" /></chemistry>contains 80%, are dissolved in 700 parts of water and the resulting dye solution adjusted to pH 5.5-6.5. Evaporation of this dye solution gives a dye mixture which produces deep black dyeings and prints on cotton under the dyeing conditions customary for reactive dyes.

Further dye mixtures according to Example 449

0081<tables id="tabl0006" num="0006"><table frame="all"><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="16mm" /><colspec colnum="2" colname="col2" colwidth="40mm" /><colspec colnum="3" colname="col3" colwidth="40mm" /><colspec colnum="4" colname="col4" colwidth="51mm" /><colspec colnum="5" colname="col5" colwidth="21mm" colsep="0" /><thead><row><entry valign="top">example</entry><entry valign="top">Dye according to general formula (I)</entry><entry valign="top">Dye according to general formula (II)</entry><entry valign="top">Dye according to general formula (III)</entry><entry valign="top">relationship</entry></row></thead><tbody><row><entry>450</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry><chemistry id="chem0088" num="0088"><img file="EP1490441B2_D0088.tif" /></chemistry></entry><entry>70 : 15 : 15</entry></row><row><entry>451</entry><entry>(I-1)</entry><entry>(II-2)</entry><entry><chemistry id="chem0089" num="0089"><img file="EP1490441B2_D0089.tif" /></chemistry></entry><entry>72 : 16 : 12</entry></row><row><entry>453</entry><entry>(I-1)</entry><entry>(II-7)</entry><entry><chemistry id="chem0090" num="0090"><img file="EP1490441B2_D0090.tif" /></chemistry></entry><entry>68 : 20 : 12</entry></row><row><entry>454</entry><entry>(I-1)</entry><entry>(II-24)</entry><entry><chemistry id="chem0091" num="0091"><img file="EP1490441B2_D0091.tif" /></chemistry></entry><entry>72 : 19 : 9</entry></row><row><entry>455</entry><entry>(I-1)</entry><entry>(II-26)</entry><entry><chemistry id="chem0092" num="0092"><img file="EP1490441B2_D0092.tif" /></chemistry></entry><entry>71 : 16 : 13</entry></row><row><entry>457</entry><entry>(I-1)</entry><entry>(II-37)</entry><entry><chemistry id="chem0093" num="0093"><img file="EP1490441B2_D0093.tif" /></chemistry></entry><entry>70 : 15 : 15</entry></row><row><entry>459</entry><entry>(I-1)</entry><entry>(II-45)</entry><entry><chemistry id="chem0094" num="0094"><img file="EP1490441B2_D0094.tif" /></chemistry></entry><entry>70 : 20 : 10</entry></row><row><entry>463</entry><entry>(I-2)</entry><entry>(II-2)</entry><entry><chemistry id="chem0095" num="0095"><img file="EP1490441B2_D0095.tif" /></chemistry></entry><entry>70 : 18 : 12</entry></row><row><entry>464</entry><entry>(I-2)</entry><entry>(II-7)</entry><entry><chemistry id="chem0096" num="0096"><img file="EP1490441B2_D0096.tif" /></chemistry></entry><entry>71 : 15 : 14</entry></row><row><entry>465</entry><entry>(I-7)</entry><entry>(II-2)</entry><entry><chemistry id="chem0097" num="0097"><img file="EP1490441B2_D0097.tif" /></chemistry></entry><entry>70 : 17 : 13</entry></row><row><entry>466</entry><entry>(I-19)</entry><entry>(II-7)</entry><entry><chemistry id="chem0098" num="0098"><img file="EP1490441B2_D0098.tif" /></chemistry></entry><entry>68 : 18 : 14</entry></row><row><entry>467</entry><entry>(I-21)</entry><entry>(II-2)</entry><entry><chemistry id="chem0099" num="0099"><img file="EP1490441B2_D0099.tif" /></chemistry></entry><entry>68 : 20 :12</entry></row></tbody></tgroup></table></tables>

Example 468

008270 Parts of an electrolyte-containing dye powder which contains the navy blue disazo dye of the formula (I-1)<chemistry id="chem0100" num="0100"><img file="EP1490441B2_D0100.tif" /></chemistry>contains 70%, 20 parts of an electrolyte-containing dye powder which contains the scarlet disazo dye of the formula (II-1)<chemistry id="chem0101" num="0101"><img file="EP1490441B2_D0101.tif" /></chemistry>contains 75% and 10 parts of an electrolyte-containing dye powder which contains the yellow disazo dye of the formula (Ga-1)<chemistry id="chem0102" num="0102"><img file="EP1490441B2_D0102.tif" /></chemistry>contains 70%, are mixed mechanically.

0083The resulting dye mixture according to the invention provides deep black dyeings and prints under the dyeing conditions customary for reactive dyes, for example on cotton.

Example 469

008465 Parts of an electrolyte-containing dye powder which contains the navy blue disazo dye of the formula (I-1) in a 70% proportion, 15 parts of an electrolyte-containing dye powder which contains the scarlet disazo dye of the formula (II-2)<chemistry id="chem0103" num="0103"><img file="EP1490441B2_D0103.tif" /></chemistry>contains 75% and 20 parts of an electrolyte-containing dye powder which contains the yellow disazo dye of the formula (Gf-1)<chemistry id="chem0104" num="0104"><img file="EP1490441B2_D0104.tif" /></chemistry>contains 60%, are dissolved in 750 parts of water and the dye solution obtained is adjusted to pH 5.5-6.5. Evaporation of this dye solution gives a dye mixture which produces deep black dyeings and prints on cotton under the dyeing conditions customary for reactive dyes.

Example 470

0085812 Parts of 4- (β-sulfatoethylsulfonyl) aniline are suspended in 1900 parts of ice water and 520 parts of 30% hydrochloric acid and diazotized by dropwise addition of 500 parts of 40% sodium nitrite solution. 319 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 93 parts of 4-hydroxy-7- (sulfomethylamino) -naphthalene-2-sulfonic acid, which are obtained by reacting 67 parts of 7-amino-4 -hydroxy-naphthalene-2-sulfonic acid was prepared with 42 parts of formaldehyde sodium bisulfite in an aqueous medium at pH 5.5 - 6 and 50 ° C, and 31 parts of 2,4-diaminobenzenesulfonic acid and initially couples in the first stage at pH 1 to 1.3 below 20 ° C. to a mixture of three monoazo dyes according to the formulas (15-1), (17-1) and (Ga-3 ). The specified pH range is adjusted by adding solid sodium bicarbonate and maintained during the coupling reaction.<chemistry id="chem0105" num="0105"><img file="EP1490441B2_D0105.tif" /></chemistry><chemistry id="chem0106" num="0106"><img file="EP1490441B2_D0106.tif" /></chemistry>When the first coupling is complete, the pH is adjusted to 5-6 below 25 ° C. with sodium carbonate, and the 70:20:10 mixture of the three disazo dyes (I-1), (II-1) and (Gb-3) formed after the second coupling reaction has ended. isolated by spray drying. Alternatively, the dye solution obtained can also be buffered at pH 5.5-6 by adding a phosphate buffer and adjusted as a liquid brand of certain strength by further dilution or concentration. The dye mixture according to the invention obtained dyes cotton in black tones.<chemistry id="chem0107" num="0107"><img file="EP1490441B2_D0107.tif" /></chemistry>

Example 471

0086677 Parts of 4- (β-sulfatoethylsulfonyl) aniline are suspended in 1570 parts of ice water and 434 parts of 30% hydrochloric acid and diazotized by dropwise addition of 417 parts of 40% sodium nitrite solution. 319 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid are added and the first stage is coupled at pH 1 to 1.3 below 20 ° C. to a red monoazo dye of the formula (15-1). The specified pH range is adjusted by adding solid sodium bicarbonate and maintained during the coupling reaction. After the first coupling has ended, an aqueous solution of 206 parts of the scarlet monoazo dye of the formula (17-2) and 94 parts of the yellow monoazo dye of the formula (Ga-4) is added to the reaction mixture,<chemistry id="chem0108" num="0108"><img file="EP1490441B2_D0108.tif" /></chemistry>by the diazotization of 148 parts of 2-amino- (β-sulfatoethylsulfonyl) -benzenesulfonic acid with 71 parts of 40% sodium nitrite solution in an acidic medium and subsequent coupling to a mixture of 86.5 parts of 4-hydroxy-7- (sulfomethylamino- ) -naphthalene-2-sulfonic acid and 28 parts of 2,4-diaminobenzenesulfonic acid at pH 1-2 was added. Subsequently, the pH is adjusted to 5-6 below 25 ° C. with sodium carbonate, and the 70:20:10 mixture of the three disazo dyes (I-1), (II-2) and (Gb-2) ​​formed after the coupling reaction has ended by evaporation in vacuo or isolated by spray drying. The dye mixture according to the invention obtained dyes cotton in black tones.<chemistry id="chem0109" num="0109"><img file="EP1490441B2_D0109.tif" /></chemistry>

Example 472

0087<ol id="ol0003"><li>a) 406 parts of 4- (β-sulfatoethylsulfonyl) aniline are suspended in 950 parts of ice water and 260 parts of 30% hydrochloric acid and diazotized by dropwise addition of 250 parts of 40% sodium nitrite solution. To this are added 319 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 93 parts of 4-hydroxy-7- (sulfomethylamino) -5-naphthalene-2-sulfonic acid and 31 parts of 2,4-diaminobenzenesulfonic acid and coupling in the first stage at pH 1 to 1.3 below 20 ° C to a mixture of the three monoazo dyes according to the formulas (15-1), (17-1) and (Ga-3). The specified pH range is adjusted by adding solid sodium hydrogen carbonate and maintained during the coupling reaction.</li><li>b) In a second, separate reaction vessel, 451 parts of 2-methoxy-5- (β-sulfatoethylsulfonyl) aniline are suspended in 1300 parts of ice water and 261 parts of 30% hydrochloric acid and diazotized by dropwise addition of 251 parts of 40% sodium nitrite solution. Then the excess nitrite is removed with amidosulfonic acid solution and the resulting diazo suspension is pumped to the solution of the monoazo dyes from a) after the first coupling has ended.</li></ol>Then is adjusted below 25 ° C with sodium carbonate pH 5-6 and the resulting 70:20:10 mixture of the three disazo dyes (I-2), (II-3) and (Gb-1) after evaporation of the second coupling reaction by evaporation in Vacuum or isolated by spray drying.<chemistry id="chem0110" num="0110"><img file="EP1490441B2_D0110.tif" /></chemistry>The dye mixture according to the invention obtained dyes cotton in black tones.

Example 473

0088<ol id="ol0004"><li>a) 351 parts of 4- (β-sulfatoethylsulfonyl) aniline are suspended in 825 parts of ice water and 225 parts of 30% hydrochloric acid and diazotized by dropwise addition of 216 parts of 40% sodium nitrite solution. To this are added 319 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and 83 parts of 4-hydroxy-7- (sulfomethylamino) naphthalene-2-sulfonic acid and coupling in the first stage at pH 1 to 1.3 below 20 ° C to a mixture of the two monoazo dyes according to formulas (15-1) and (17-1). The specified pH range is adjusted by adding solid sodium bicarbonate and maintained during the coupling reaction.</li><li>b) In a second, separate reaction vessel, 427 parts of 2,5-dimethoxy-4- (β-sulfatoethylsulfonyl) aniline are suspended in 1150 parts of ice water and 226 parts of 30% hydrochloric acid and by dropwise addition of 217 parts of 40% sodium nitrite solution diazotized. The excess nitrite is then removed with amidosulfonic acid solution and the resulting diazo suspension is pumped to the solution of the two monoazo dyes from a) after the first coupling has ended.</li></ol>Then it is adjusted below 25 ° C. with sodium carbonate pH 5-6 and 250 parts of a yellow dye of the formula (Gf-2) are added to the dye solution obtained after the second coupling reaction has ended. The resulting 67:17:16 mixture of the three disazo dyes (I-3), (II-4) and (Gf-2) can be isolated by evaporation in vacuo or by spray drying.<chemistry id="chem0111" num="0111"><img file="EP1490441B2_D0111.tif" /></chemistry>The dye mixture according to the invention thus obtained dyes cotton in black tones.

Example 474

008970 Parts of an electrolyte-containing dye powder which contains the greenish navy-blue disazo dye of the formula (I-4)<chemistry id="chem0112" num="0112"><img file="EP1490441B2_D0112.tif" /></chemistry>contains 70% and 30 parts of an electrolyte-containing dye powder which contains the scarlet disazo dye of the formula (II-7)<chemistry id="chem0113" num="0113"><img file="EP1490441B2_D0113.tif" /></chemistry>also contains 70%, water is dissolved in 600 parts and the resulting dye solution is adjusted to pH 5.5-6.5. Evaporation of this dye solution gives a binary dye mixture which produces deep black dyeings and prints on cotton under the dyeing conditions customary for reactive dyes.

Example 475

0090<ol id="ol0005"><li>a) 341 parts of 2,5-dimethoxy-4- (β-sulfatoethylsulfonyl) aniline are suspended in 950 parts of ice water and 180 parts of 30% hydrochloric acid and diazotized by dropwise addition of 173 parts of 40% sodium nitrite solution. 319 parts of 1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid are added and the first stage is coupled at pH 1 to 1.5 below 20 ° C. to a red monoazo dye of the formula (15-2). The specified pH range is adjusted by adding solid sodium bicarbonate and maintained during the coupling reaction.<chemistry id="chem0114" num="0114"><img file="EP1490441B2_D0114.tif" /></chemistry>After the first coupling has ended, an aqueous solution of 254 parts of the scarlet monoazo dye of the formula (17-2) is added to the reaction mixture, which is obtained by diazotizing 116 parts of 2-amino-5- (β-sulfatoethylsulfonyl) benzene sulfonic acid with 55.5 parts 40 % sodium nitrite solution in acidic medium and subsequent coupling to 107 parts of 4-hydroxy-7- (sulfomethylamino) naphthalene-2-sulfonic acid was obtained at pH 1-2.</li><li>b) In a second, separate reaction vessel, 430 parts of 2-methoxy-5-methyl-4- (β-sulfatoethylsulfonyl) aniline are suspended in 1250 parts of ice water and 238 parts of 30% hydrochloric acid, and by dropwise addition of 229 parts of 40% Sodium nitrite solution diazotized. The excess nitrite is then removed with amidosulfonic acid solution and the diazo suspension obtained is pumped to dissolve the monoazo dye mixture from a). Then the pH is adjusted to 5-6 below 25 ° C. with sodium carbonate and the 75:25 mixture of the two disazo dyes (I-5) and (II-8) formed after the second coupling reaction has ended is isolated by evaporation in vacuo or by spray drying.<chemistry id="chem0115" num="0115"><img file="EP1490441B2_D0115.tif" /></chemistry>The resulting binary dye mixture according to the invention dyes cotton in black tones.</li></ol>

Example 476

0091A binary mixture of 1021 parts of the navy blue disazo dye of the formula (I-2) and 335 parts of the scarlet disazo dye of the formula (II-7) prepared analogously to the procedure described in Example 475 is mixed with 168 parts of the yellow disazo dye of the formula (Ge-1 )<chemistry id="chem0116" num="0116"><img file="EP1490441B2_D0116.tif" /></chemistry>added, adjusted to a pH of 5.5-6.5 and isolated by evaporating the aqueous solution. The resulting dye mixture according to the invention dyes cotton in black tones.

Example 477

009270 Parts of an electrolyte-containing dye powder which contains the navy blue disazo dye of the formula (I-6)<chemistry id="chem0117" num="0117"><img file="EP1490441B2_D0117.tif" /></chemistry>contains 70%, 18 parts of an electrolyte-containing dye powder which contains the scarlet disazo dye of the formula (II-1) in a 75% proportion and 12 parts of an electrolyte-containing dye powder which contains the yellow disazo dye of the formula (Gf-3)<chemistry id="chem0118" num="0118"><img file="EP1490441B2_D0118.tif" /></chemistry>contains 70%, are mixed together as described in Example 468.

0093The resulting dye mixture according to the invention provides deep black dyeings under the dyeing conditions customary for reactive dyes and with a reduced amount of salt compared to the standard method, for example on cotton.

Example 478

0094A binary mixture of 1012 parts of the navy blue disazo dye of the formula (I-7) and 290 parts of the scarlet disazo dye of the formula (II-14) prepared analogously to the procedure described in Example 473 is mixed with 145 parts of the yellow disazo dye of the formula (Ga-2 ) added, adjusted to a pH of 5.5-6.5 and isolated by evaporating the aqueous solution. The resulting dye mixture according to the invention dyes cotton in black tones.<chemistry id="chem0119" num="0119"><img file="EP1490441B2_D0119.tif" /></chemistry>

Example 479

0095<ol id="ol0006"><li>a) A mixture of 70.5 parts of 7-amino-4-hydroxy-naphthalene-2-sulfonic acid and 37.5 parts of 2,4-diaminobenzenesulfonic acid are suspended in 800 parts of water and dissolved by adding sodium hydroxide solution. At a pH of 5.5-6, 79 parts of formaldehyde sodium bisulfite are added and the mixture is stirred at 50-55 ° C. for 4 hours, the specified pH range being maintained by means of dilute sodium hydroxide solution.</li><li>b) In a separate reaction vessel, 843 parts of 4- (β-sulfatoethylsulfonyl) aniline are suspended in 2000 parts of ice water and 540 parts of 30% hydrochloric acid and diazotized by dropwise addition of 520 parts of 40% sodium nitrite solution. After removal of the excess nitrite with amidosulfonic acid solution, 319 parts of 1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid and the mixture of the other coupling components from a) are added and the first step is coupling at pH 0.8 to 1.3 below 20 ° C to a mixture of three monoazo dyes according to the formulas (15-1), (17-1) and (Ga-6). The specified pH range is adjusted by adding solid sodium bicarbonate and maintained during the coupling reaction.<chemistry id="chem0120" num="0120"><img file="EP1490441B2_D0120.tif" /></chemistry></li></ol>After the first coupling is complete, the pH is adjusted to 5-6 below 25 ° C. with sodium carbonate, and the 67:20:13 mixture of the three disazo dyes (I-1), (II-1) and (Gb-5) formed after the second coupling reaction has ended. isolated by spray drying or evaporation in vacuo. Alternatively, the dye solution obtained can also be buffered by adding a phosphate buffer at pH 5.5-6 and by further dilution or Concentration can be set as a liquid brand of a certain strength.<chemistry id="chem0121" num="0121"><img file="EP1490441B2_D0121.tif" /></chemistry>The dye mixture according to the invention obtained dyes cotton in black tones.

Example 480

0096843 Parts of 4- (β-sulfatoethylsulfonyl) aniline are suspended in 2000 parts of ice water and 540 parts of 30% hydrochloric acid and diazotized by dropwise addition of 520 parts of 40% sodium nitrite solution. After removal of the excess nitrite with amidosulfonic acid solution, 319 parts of 1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid and a mixture of further coupling components are added, which is carried out analogously to Example 479 a) by reacting 72 parts of 7-amino-4-hydroxy naphthalene-2-sulfonic acid and 75 parts of 2,4-diaminobenzenesulfonic acid with 112 parts of formaldehyde sodium bisulfite at pH 5.7 and 50 ° C. were obtained, and initially couples in a first stage at pH 0.8 to 1.3 below 20 ° C. to a mixture of three monoazo dyes according to the formulas (15-1), (17-1) and (Ga-6). The specified pH range is adjusted by adding solid sodium bicarbonate and maintained during the coupling reaction. After the first coupling is complete, the pH is adjusted to 5-6 below 25 ° C. with sodium carbonate, and the 64:20:16 mixture of the three azo dyes (I-1), (II-1) and (Ga-6) which has formed after the second coupling reaction has ended. isolated by spray drying or evaporation in vacuo. The dye mixture according to the invention obtained dyes cotton in black tones.

Example 481

0097574 Parts of 4- (β-sulfatoethylsulfonyl) aniline are suspended in 1350 parts of ice water and 368 parts of 30% hydrochloric acid and diazotized by dropwise addition of 354 parts of 40% sodium nitrite solution. After removal of the excess nitrite with amidosulfonic acid solution, an aqueous solution of two coupling components is added to it, which is analogous to Example 479 a) by reacting 74 parts of 7-amino-4-hydroxy-naphthalene-2-sulfonic acid and 39.5 parts of 2,4-diaminobenzenesulfonic acid 83 parts of formaldehyde sodium bisulfite were obtained at pH 5.5-6 and 50 ° C. and initially couples in the first stage at pH 1.0 to 1.3 below 20 ° C. to a mixture of two monoazo dyes according to the formulas (17-1) and (Ga-6). The specified pH range is adjusted by adding solid sodium bicarbonate and maintained during the coupling reaction. After the first coupling is complete, 737 parts of the red monoazo dye of the formula (15-2) are added to the reaction mixture in the form of an aqueous solution which can be obtained as described in Example 475 a). Subsequently, the pH is adjusted to 5-6 below 25 ° C. with sodium carbonate, and the 67:20:13 mixture of the three disazo dyes (I-12), (II-1) and (Gb-5) formed after the second coupling reaction has ended by spray drying or Evaporation in vacuum isolated.<chemistry id="chem0122" num="0122"><img file="EP1490441B2_D0122.tif" /></chemistry>The dye mixture according to the invention obtained dyes cotton in black tones.

Examples 482 to 819

0098The following table examples describe further mixtures according to the invention of the dyes of the general formulas (I) and (II) or (I) and (II) and (G), which are each given in the form of the sodium salts. The mixing ratios are given in percent by weight. The dye mixtures provide gray to deep black dyeings using the dyeing methods customary for reactive dyes, for example on cotton.

Dye mixtures according to Example 468 or 469

0099<tables id="tabl0007" num="0007"><table frame="all"><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="16mm" /><colspec colnum="2" colname="col2" colwidth="62mm" /><colspec colnum="3" colname="col3" colwidth="58mm" /><colspec colnum="4" colname="col4" colwidth="63mm" /><colspec colnum="5" colname="col5" colwidth="33mm" colsep="0" /><thead><row><entry valign="top">example</entry><entry valign="top">Dye according to general formula (I)</entry><entry valign="top">Dye according to general formula (II)</entry><entry valign="top">Dye according to formula (G)</entry><entry valign="top">Ratio (I) :( II) :( G)</entry></row></thead><tbody><row><entry>482</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry>(Ga-2)</entry><entry>63 : 19 : 18</entry></row><row><entry>483</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry>(Ga-3)</entry><entry>68 : 20 : 12</entry></row><row><entry>484</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry>(Gb-2)</entry><entry>67 : 20 : 13</entry></row><row><entry>485</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry><chemistry id="chem0123" num="0123"><img file="EP1490441B2_D0123.tif" /></chemistry></entry><entry>65 : 18 : 17</entry></row><row><entry>486</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry><chemistry id="chem0124" num="0124"><img file="EP1490441B2_D0124.tif" /></chemistry></entry><entry>65 : 20 : 15</entry></row><row><entry>487</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry>(Ge-1)</entry><entry>70 : 20 : 10</entry></row><row><entry>488</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry>(Gf-1)</entry><entry>63 : 18 : 19</entry></row><row><entry>489</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry><chemistry id="chem0125" num="0125"><img file="EP1490441B2_D0125.tif" /></chemistry></entry><entry>70 : 18 : 12</entry></row><row><entry>490</entry><entry>(I-1)</entry><entry>(II-2)</entry><entry>(Ga-1)</entry><entry>67 : 20 : 13</entry></row><row><entry>491</entry><entry>(I-1)</entry><entry>(II-2)</entry><entry>(Ga-2)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>492</entry><entry>(I-1)</entry><entry>(II-2)</entry><entry>(Ga-6)</entry><entry colsep="1">64 : 20 : 16</entry></row><row><entry>493</entry><entry>(I-1)</entry><entry>(II-2)</entry><entry>(Gb-3)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>494</entry><entry>(I-1)</entry><entry>(II-2)</entry><entry>(Gb-5)</entry><entry colsep="1">68 : 20 : 12</entry></row><row><entry>495</entry><entry>(I-1)</entry><entry>(II-2)</entry><entry>(Ge-1)</entry><entry colsep="1">68 : 22 : 10</entry></row><row><entry>496</entry><entry>(I-1)</entry><entry>(II-2)</entry><entry>(Gf-2)</entry><entry colsep="1">64 : 18 : 18</entry></row><row><entry>497</entry><entry>(I-1)</entry><entry>(II-3)</entry><entry>(Ga-1)</entry><entry colsep="1">70 : 18 : 12</entry></row><row><entry>498</entry><entry>(I-1)</entry><entry>(II-3)</entry><entry>(Ga-2)</entry><entry colsep="1">65 : 1 5 : 20</entry></row><row><entry>499</entry><entry>(I-1)</entry><entry>(II-3)</entry><entry>(Gb-2)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>500</entry><entry>(I-1)</entry><entry>(II-3)</entry><entry>(Gb-5)</entry><entry colsep="1">68 : 18 : 14</entry></row><row><entry>501</entry><entry>(I-1)</entry><entry>(II-3)</entry><entry>(Ge-1)</entry><entry colsep="1">72 : 18 : 10</entry></row><row><entry>502</entry><entry>(I-1)</entry><entry>(II-3)</entry><entry>(Gf-1)</entry><entry colsep="1">65 : 15 : 20</entry></row><row><entry>503</entry><entry>(I-1)</entry><entry>(II-4)</entry><entry><chemistry id="chem0126" num="0126"><img file="EP1490441B2_D0126.tif" /></chemistry></entry><entry colsep="1">67 : 18 : 15</entry></row><row><entry>504</entry><entry>(I-1)</entry><entry>(II-7)</entry><entry>(Ga-1)</entry><entry colsep="1">68 : 20 : 12</entry></row><row><entry>505</entry><entry>(I-1)</entry><entry>(II-7)</entry><entry>(Ga-2)</entry><entry colsep="1">66 : 16 : 18</entry></row><row><entry>506</entry><entry>(I-1)</entry><entry>(II-7)</entry><entry>(Gb-2)</entry><entry>70 : 18 : 12</entry></row><row><entry>507</entry><entry>(I-1)</entry><entry>(11-7)</entry><entry>(Gb-5)</entry><entry>67 : 20 : 13</entry></row><row><entry>508</entry><entry>(I-1)</entry><entry>(II-7)</entry><entry>(Ge-1)</entry><entry>73 : 17 : 10</entry></row><row><entry>509</entry><entry>(I-1)</entry><entry>(II-7)</entry><entry>(Gf-1)</entry><entry>65 : 17 : 18</entry></row><row><entry>510</entry><entry>(I-1)</entry><entry>(II-8)</entry><entry><chemistry id="chem0127" num="0127"><img file="EP1490441B2_D0127.tif" /></chemistry></entry><entry>65 : 20 : 15</entry></row><row><entry>511</entry><entry>(I-1)</entry><entry>(II-14)</entry><entry>(Ga-1)</entry><entry>60 : 25 : 15</entry></row><row><entry>512</entry><entry>(I-1)</entry><entry>(II-14)</entry><entry>(Gb-5)</entry><entry>66 : 22 : 12</entry></row><row><entry>513</entry><entry>(I-1)</entry><entry>(II-14)</entry><entry>(Ge-1)</entry><entry>65 : 23 : 12</entry></row><row><entry>514</entry><entry>(I-1)</entry><entry>(II-14)</entry><entry>(Gf-2)</entry><entry>63 : 20 : 17</entry></row><row><entry>515</entry><entry>(I-1)</entry><entry><chemistry id="chem0128" num="0128"><img file="EP1490441B2_D0128.tif" /></chemistry></entry><entry>(Ga-1)</entry><entry>66 : 20 : 14</entry></row><row><entry>516</entry><entry>(I-1)</entry><entry>(II-15)</entry><entry>(Gb-2)</entry><entry>70 : 20 : 10</entry></row><row><entry>517</entry><entry>(I-1)</entry><entry>(II-15)</entry><entry>(Gb-5)</entry><entry>68 : 20 : 12</entry></row><row><entry>518</entry><entry>(I-1)</entry><entry>(II-15)</entry><entry><chemistry id="chem0129" num="0129"><img file="EP1490441B2_D0129.tif" /></chemistry></entry><entry>70 : 20 : 10</entry></row><row><entry>519</entry><entry>(I-1)</entry><entry>(II-15)</entry><entry>(Gf-1)</entry><entry>68 : 17 : 15</entry></row><row><entry>520</entry><entry>(I-1)</entry><entry><chemistry id="chem0130" num="0130"><img file="EP1490441B2_D0130.tif" /></chemistry></entry><entry>(Ga-1)</entry><entry>68 : 20 : 12</entry></row><row><entry>521</entry><entry>(I-1)</entry><entry>(II-54)</entry><entry>(Ga-2)</entry><entry>65 : 20 : 15</entry></row><row><entry>522</entry><entry>(I-1)</entry><entry>(II-54)</entry><entry>(Gb-2)</entry><entry>70 : 18 : 12</entry></row><row><entry>523</entry><entry>(I-1)</entry><entry>(II-54)</entry><entry>(Gb-5)</entry><entry>67 : 20 : 13</entry></row><row><entry>524</entry><entry>(I-1)</entry><entry>(II-54)</entry><entry>(Ge-1)</entry><entry>70 : 20 : 10</entry></row><row><entry>525</entry><entry>(I-1)</entry><entry>(II-54)</entry><entry>(Gf-1)</entry><entry>65 : 18 : 17</entry></row><row><entry>526</entry><entry>(I-1)</entry><entry><chemistry id="chem0131" num="0131"><img file="EP1490441B2_D0131.tif" /></chemistry></entry><entry>(Gb-2)</entry><entry>70 : 18 : 12</entry></row><row><entry>527</entry><entry>(I-1)</entry><entry><chemistry id="chem0132" num="0132"><img file="EP1490441B2_D0132.tif" /></chemistry></entry><entry>(Ge-1)</entry><entry>67 : 22 : 11</entry></row><row><entry>528</entry><entry>(I-1)</entry><entry><chemistry id="chem0133" num="0133"><img file="EP1490441B2_D0133.tif" /></chemistry></entry><entry>(Gf-2)</entry><entry>63 : 20 : 17</entry></row><row><entry>529</entry><entry>(I-1)</entry><entry><chemistry id="chem0134" num="0134"><img file="EP1490441B2_D0134.tif" /></chemistry></entry><entry>(Ga-1)</entry><entry>67 : 20 : 1 3</entry></row><row><entry>530</entry><entry>(I-1)</entry><entry>(II-24)</entry><entry>(Ga-2)</entry><entry>65 : 20 : 15</entry></row><row><entry>531</entry><entry>(I-1)</entry><entry>(II-24)</entry><entry>(Gb-2)</entry><entry colsep="1">70 : 18 : 12</entry></row><row><entry>532</entry><entry>(I-1)</entry><entry>(II-24)</entry><entry>(Gb-5)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>533</entry><entry>(I-1)</entry><entry>(II-24)</entry><entry>(Ge-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>534</entry><entry>(I-1)</entry><entry>(II-24)</entry><entry>(Gf-1)</entry><entry colsep="1">66 : 17 : 17</entry></row><row><entry>535</entry><entry>(I-1)</entry><entry><chemistry id="chem0135" num="0135"><img file="EP1490441B2_D0135.tif" /></chemistry></entry><entry>(Ge-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>536</entry><entry>(I-1)</entry><entry><chemistry id="chem0136" num="0136"><img file="EP1490441B2_D0136.tif" /></chemistry></entry><entry>(Gb-2)</entry><entry colsep="1">68 : 20 : 12</entry></row><row><entry>537</entry><entry>(I-1)</entry><entry><chemistry id="chem0137" num="0137"><img file="EP1490441B2_D0137.tif" /></chemistry></entry><entry>(Gf-2)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>538</entry><entry>(I-1)</entry><entry><chemistry id="chem0138" num="0138"><img file="EP1490441B2_D0138.tif" /></chemistry></entry><entry>(Ga-1)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>539</entry><entry>(I-1)</entry><entry><chemistry id="chem0139" num="0139"><img file="EP1490441B2_D0139.tif" /></chemistry></entry><entry>(Gf-1)</entry><entry colsep="1">62 : 22 : 16</entry></row><row><entry>540</entry><entry>(I-1)</entry><entry><chemistry id="chem0140" num="0140"><img file="EP1490441B2_D0140.tif" /></chemistry></entry><entry>(Ga-1)</entry><entry colsep="1">70 : 18 : 12</entry></row><row><entry>541</entry><entry>(I-1)</entry><entry>(II-26)</entry><entry>(Gb-5)</entry><entry colsep="1">68 : 20 : 12</entry></row><row><entry>542</entry><entry>(I-1)</entry><entry>(II-26)</entry><entry>(Ge-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>543</entry><entry>(I-1)</entry><entry>(II-26)</entry><entry>(Gf-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>544</entry><entry>(I-1)</entry><entry><chemistry id="chem0141" num="0141"><img file="EP1490441B2_D0141.tif" /></chemistry></entry><entry>(Ga-1)</entry><entry colsep="1">67 : 18 : 15</entry></row><row><entry>545</entry><entry>(I-1)</entry><entry>(II-27)</entry><entry>(Ga-2)</entry><entry colsep="1">66 : 17 : 17</entry></row><row><entry>546</entry><entry>(I-1)</entry><entry>(II-27)</entry><entry>(Gb-2)</entry><entry colsep="1">73 : 15 : 12</entry></row><row><entry>547</entry><entry>(I-1)</entry><entry>(II-27)</entry><entry>(Gb-5)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>548</entry><entry>(I-1)</entry><entry>(II-27)</entry><entry>(Ge-1)</entry><entry colsep="1">70 : 18 : 12</entry></row><row><entry>549</entry><entry>(I-1)</entry><entry>(II-27)</entry><entry>(Gf-1)</entry><entry colsep="1">67 : 15 : 18</entry></row><row><entry>550</entry><entry>(I-1)</entry><entry><chemistry id="chem0142" num="0142"><img file="EP1490441B2_D0142.tif" /></chemistry></entry><entry>(Ga-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>551</entry><entry>(I-1)</entry><entry>(II-67)</entry><entry>(Ga-2)</entry><entry colsep="1">63 : 20 : 17</entry></row><row><entry>552</entry><entry>(I-1)</entry><entry>(II-67)</entry><entry>(Ga-6)</entry><entry colsep="1">64 : 20 : 16</entry></row><row><entry>553</entry><entry>(I-1)</entry><entry>(II-67)</entry><entry>(Gb-2)</entry><entry colsep="1">63 : 25 : 12</entry></row><row><entry>554</entry><entry>(I-1)</entry><entry>(II-67)</entry><entry>(Gb-5)</entry><entry colsep="1">68 : 20 : 12</entry></row><row><entry>555</entry><entry>(I-1)</entry><entry>(II-67)</entry><entry>(Ge-1)</entry><entry colsep="1">66 : 23 : 11</entry></row><row><entry>556</entry><entry>(I-1)</entry><entry>(II-67)</entry><entry>(Gf-1)</entry><entry colsep="1">60 : 20 : 20</entry></row><row><entry>557</entry><entry>(I-1)</entry><entry><chemistry id="chem0143" num="0143"><img file="EP1490441B2_D0143.tif" /></chemistry></entry><entry>(Ge-1)</entry><entry colsep="1">65 : 25 : 10</entry></row><row><entry>558</entry><entry>(I-1)</entry><entry><chemistry id="chem0144" num="0144"><img file="EP1490441B2_D0144.tif" /></chemistry></entry><entry>(Gb-2)</entry><entry colsep="1">68 : 20 : 12</entry></row><row><entry>559</entry><entry>(I-1)</entry><entry><chemistry id="chem0145" num="0145"><img file="EP1490441B2_D0145.tif" /></chemistry></entry><entry>(Ga-2)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>560</entry><entry>(I-1)</entry><entry><chemistry id="chem0146" num="0146"><img file="EP1490441B2_D0146.tif" /></chemistry></entry><entry>(Ga-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>561</entry><entry>(I-1)</entry><entry>(II-72)</entry><entry>(Gb-5)</entry><entry>68 : 20 : 12</entry></row><row><entry>562</entry><entry>(I-1)</entry><entry>(II-72)</entry><entry>(Ge-1)</entry><entry>70 : 20 : 10</entry></row><row><entry>563</entry><entry>(I-1)</entry><entry>(II-72)</entry><entry>(Gf-2)</entry><entry>63 : 20 : 17</entry></row><row><entry>564</entry><entry>(I-1)</entry><entry><chemistry id="chem0147" num="0147"><img file="EP1490441B2_D0147.tif" /></chemistry></entry><entry><chemistry id="chem0148" num="0148"><img file="EP1490441B2_D0148.tif" /></chemistry></entry><entry>65 : 20 : 15</entry></row><row><entry>565</entry><entry>(I-1)</entry><entry><chemistry id="chem0149" num="0149"><img file="EP1490441B2_D0149.tif" /></chemistry></entry><entry>(Ge-1)</entry><entry>72 : 18 : 10</entry></row><row><entry>566</entry><entry>(I-1)</entry><entry><chemistry id="chem0150" num="0150"><img file="EP1490441B2_D0150.tif" /></chemistry></entry><entry>(Ga-1)</entry><entry>67 : 18 : 15</entry></row><row><entry>567</entry><entry>(I-1)</entry><entry><chemistry id="chem0151" num="0151"><img file="EP1490441B2_D0151.tif" /></chemistry></entry><entry>(Gb-2)</entry><entry>70 : 15 : 15</entry></row><row><entry>568</entry><entry>(I-1)</entry><entry><chemistry id="chem0152" num="0152"><img file="EP1490441B2_D0152.tif" /></chemistry></entry><entry>(Ge-2)</entry><entry>75 : 15 : 10</entry></row><row><entry>569</entry><entry>(I-1)</entry><entry><chemistry id="chem0153" num="0153"><img file="EP1490441B2_D0153.tif" /></chemistry></entry><entry>(Gf-1)</entry><entry>66 : 20 : 14</entry></row><row><entry>570</entry><entry>(I-1)</entry><entry><chemistry id="chem0154" num="0154"><img file="EP1490441B2_D0154.tif" /></chemistry></entry><entry>(Gf-2)</entry><entry>65 : 20 : 15</entry></row><row><entry>571</entry><entry>(I-1)</entry><entry><chemistry id="chem0155" num="0155"><img file="EP1490441B2_D0155.tif" /></chemistry></entry><entry>(Gf-3)</entry><entry>68 : 20 : 12</entry></row><row><entry>572</entry><entry>(I-1)</entry><entry><chemistry id="chem0156" num="0156"><img file="EP1490441B2_D0156.tif" /></chemistry></entry><entry><chemistry id="chem0157" num="0157"><img file="EP1490441B2_D0157.tif" /></chemistry></entry><entry>67 : 18 : 15</entry></row><row><entry>573</entry><entry>(I-1)</entry><entry><chemistry id="chem0158" num="0158"><img file="EP1490441B2_D0158.tif" /></chemistry></entry><entry>(Ga-3)</entry><entry>62 : 20 : 18</entry></row><row><entry>574</entry><entry>(I-1)</entry><entry><chemistry id="chem0159" num="0159"><img file="EP1490441B2_D0159.tif" /></chemistry></entry><entry>(Gb-2)</entry><entry>66 : 22 : 12</entry></row><row><entry>575</entry><entry>(I-1)</entry><entry><chemistry id="chem0160" num="0160"><img file="EP1490441B2_D0160.tif" /></chemistry></entry><entry>(Ga-1)</entry><entry>62 : 23 : 15</entry></row><row><entry>576</entry><entry>(I-1)</entry><entry>(II-86)</entry><entry>(Gb-5)</entry><entry>70 : 20 : 10</entry></row><row><entry>577</entry><entry>(I-1)</entry><entry>(II-86)</entry><entry>(Ge-1)</entry><entry>67 : 22 : 11</entry></row><row><entry>578</entry><entry>(I-1)</entry><entry>(II-86)</entry><entry>(Gf-1)</entry><entry>63 : 20 : 1 7</entry></row><row><entry>579</entry><entry>(I-1)</entry><entry><chemistry id="chem0161" num="0161"><img file="EP1490441B2_D0161.tif" /></chemistry></entry><entry>(Ga-1)</entry><entry>60 : 25 : 15</entry></row><row><entry>580</entry><entry>(I-1)</entry><entry><chemistry id="chem0162" num="0162"><img file="EP1490441B2_D0162.tif" /></chemistry></entry><entry>(Gf-2)</entry><entry>65 : 20 : 15</entry></row><row><entry>581</entry><entry>(I-1)</entry><entry><chemistry id="chem0163" num="0163"><img file="EP1490441B2_D0163.tif" /></chemistry></entry><entry>(Gb-2)</entry><entry>67 : 20 : 13</entry></row><row><entry>582</entry><entry>(I-2)</entry><entry>(II-1)</entry><entry>(Gb-5)</entry><entry>68 : 20 : 12</entry></row><row><entry>583</entry><entry>(I-2)</entry><entry>(II-2)</entry><entry>(Gb-2)</entry><entry>72 : 18 : 10</entry></row><row><entry>584</entry><entry>(I-2)</entry><entry>(II-14)</entry><entry>(Gf-3)</entry><entry>65 : 23 : 12</entry></row><row><entry>585</entry><entry>(I-2)</entry><entry>(II-54)</entry><entry>(Ge-2)</entry><entry>70 : 20 : 10</entry></row><row><entry>586</entry><entry>(I-2)</entry><entry>(II-24)</entry><entry>(Gf-2)</entry><entry>67 : 18 : 15</entry></row><row><entry>587</entry><entry>(I-2)</entry><entry>(II-27)</entry><entry>(Ga-1)</entry><entry>69 : 18 : 13</entry></row><row><entry>588</entry><entry>(I-2)</entry><entry>(II-67)</entry><entry>(Ge-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>589</entry><entry>(I-2)</entry><entry>(II-69)</entry><entry>(Gf-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>590</entry><entry>(I-2)</entry><entry>(II-72)</entry><entry>(Gf-4)</entry><entry colsep="1">66 : 22 : 12</entry></row><row><entry>591</entry><entry>(I-2)</entry><entry>(II-86)</entry><entry>(Ga-3)</entry><entry colsep="1">60 : 20 : 20</entry></row><row><entry>592</entry><entry>(I-3)</entry><entry>(11-3)</entry><entry>(Ge-1)</entry><entry colsep="1">73 : 20 : 7</entry></row><row><entry>593</entry><entry>(I-3)</entry><entry>(II-7)</entry><entry>(Gb-5)</entry><entry colsep="1">69 : 20 : 11</entry></row><row><entry>594</entry><entry>(I-3)</entry><entry>(II-27)</entry><entry>(Gf-2)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>595</entry><entry>(I-3)</entry><entry>(II-86)</entry><entry>(Ga-1)</entry><entry colsep="1">67 : 22 : 11</entry></row><row><entry>596</entry><entry>(I-4)</entry><entry>(II-4)</entry><entry>(Gb-2)</entry><entry colsep="1">72 : 20 : 8</entry></row><row><entry>597</entry><entry>(I-4)</entry><entry>(II-8)</entry><entry>(Gf-2)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>598</entry><entry>(I-4)</entry><entry>(II-17)</entry><entry>(Ge-1)</entry><entry colsep="1">73 : 22 : 5</entry></row><row><entry>599</entry><entry>(I-5)</entry><entry>(II-4)</entry><entry>(Ge-1)</entry><entry colsep="1">72 : 20 : 8</entry></row><row><entry>600</entry><entry>(I-5)</entry><entry>(II-17)</entry><entry>(Gb-2)</entry><entry colsep="1">73 : 20 : 7</entry></row><row><entry>601</entry><entry>(I-6)</entry><entry>(II-1)</entry><entry>(Gb-3)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>602</entry><entry>(I-6)</entry><entry>(II-3)</entry><entry>(Gf-3)</entry><entry colsep="1">67 : 22 : 11</entry></row><row><entry>603</entry><entry>(I-6)</entry><entry>(II-24)</entry><entry>(Ge-1)</entry><entry colsep="1">72 : 20 : 8</entry></row><row><entry>604</entry><entry>(I-6)</entry><entry>(II-27)</entry><entry>(Gb-5)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>605</entry><entry>(I-6)</entry><entry>(11-67)</entry><entry>(Ga-3)</entry><entry colsep="1">66 : 17 : 17</entry></row><row><entry>606</entry><entry>(I-6)</entry><entry>(II-72)</entry><entry>(Gf-4)</entry><entry colsep="1">63 : 22 : 15</entry></row><row><entry>607</entry><entry>(I-6)</entry><entry>(II-41)</entry><entry>(Gc-4)</entry><entry colsep="1">67 : 22 : 11</entry></row><row><entry>608</entry><entry>(I-7)</entry><entry>(II-1)</entry><entry>(Ge-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>609</entry><entry>(I-7)</entry><entry>(II-2)</entry><entry>(Gb-2)</entry><entry colsep="1">73 : 18 : 9</entry></row><row><entry>610</entry><entry>(I-7)</entry><entry>(II-3)</entry><entry>(Gf-1)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>611</entry><entry>(I-7)</entry><entry>(II-7)</entry><entry>(Gb-5)</entry><entry colsep="1">66 : 21 : 13</entry></row><row><entry>612</entry><entry>(I-7)</entry><entry>(II-26)</entry><entry>(Gf-4)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>613</entry><entry>(I-7)</entry><entry>(II-67)</entry><entry>(Ga-1)</entry><entry colsep="1">67 : 22 : 11</entry></row><row><entry>614</entry><entry>(I-7)</entry><entry>(II-72)</entry><entry>(Gf-3)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>615</entry><entry><chemistry id="chem0164" num="0164"><img file="EP1490441B2_D0164.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(Gb-5)</entry><entry colsep="1">68 : 20 : 12</entry></row><row><entry>616</entry><entry>(I-24)</entry><entry>(II-2)</entry><entry>(Gb-2)</entry><entry colsep="1">67 : 22 : 11</entry></row><row><entry>617</entry><entry>(I-24)</entry><entry>(II-3)</entry><entry>(Ga-1)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>618</entry><entry>(I-24)</entry><entry>(II-7)</entry><entry>(Gf-2)</entry><entry colsep="1">66 : 17 : 17</entry></row><row><entry>619</entry><entry>(I-24)</entry><entry>(II-67)</entry><entry>(Ge-1)</entry><entry colsep="1">70 : 22 : 8</entry></row><row><entry>620</entry><entry><chemistry id="chem0165" num="0165"><img file="EP1490441B2_D0165.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(Ge-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>621</entry><entry>(I-9)</entry><entry>(II-2)</entry><entry>(Gf-2)</entry><entry>65 : 20 : 15</entry></row><row><entry>622</entry><entry>(I-9)</entry><entry>(II-3)</entry><entry>(Ga-1)</entry><entry>67 : 22 : 11</entry></row><row><entry>623</entry><entry>(I-9)</entry><entry>(II-7)</entry><entry>(Gb-5)</entry><entry>67 : 20 : 13</entry></row><row><entry>624</entry><entry>(I-9)</entry><entry>(II-67)</entry><entry>(Gb-2)</entry><entry>68 : 22 : 10</entry></row><row><entry>625</entry><entry><chemistry id="chem0166" num="0166"><img file="EP1490441B2_D0166.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(Gb-5)</entry><entry>68 : 20 : 12</entry></row><row><entry>626</entry><entry>(I-10)</entry><entry>(II-2)</entry><entry>(Gb-2)</entry><entry>69 : 20 : 11</entry></row><row><entry>627</entry><entry>(I-10)</entry><entry>(II-3)</entry><entry>(Ga-1)</entry><entry>67 : 22 : 11</entry></row><row><entry>628</entry><entry>(I-10)</entry><entry>(II-7)</entry><entry>(Gf-2)</entry><entry>66 : 18 : 16</entry></row><row><entry>629</entry><entry>(I-10)</entry><entry>(II-67)</entry><entry>(Ge-1)</entry><entry>70 : 20 : 10</entry></row><row><entry>630</entry><entry><chemistry id="chem0167" num="0167"><img file="EP1490441B2_D0167.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(Ge-1)</entry><entry>72 : 20 : 8</entry></row><row><entry>631</entry><entry>(I-11)</entry><entry>(II-2)</entry><entry>(Gf-1)</entry><entry>66 : 20 : 14</entry></row><row><entry>632</entry><entry>(I-11)</entry><entry>(II-3)</entry><entry>(Ga-1)</entry><entry>68 : 20 : 12</entry></row><row><entry>633</entry><entry>(I-11)</entry><entry>(II-7)</entry><entry>(Gb-2)</entry><entry>72 : 18 : 10</entry></row><row><entry>634</entry><entry>(I-11)</entry><entry>(II-67)</entry><entry>(Gb-5)</entry><entry>67 : 20 : 13</entry></row><row><entry>635</entry><entry>(I-12)</entry><entry>(II-3)</entry><entry>(Ge-1)</entry><entry>70 : 23 : 7</entry></row><row><entry>636</entry><entry>(I-12)</entry><entry>(II-7)</entry><entry>(Gb-2)</entry><entry>70 : 20 : 10</entry></row><row><entry>637</entry><entry>(I-12)</entry><entry>(II-27)</entry><entry>(Gf-1)</entry><entry>67 : 20 : 13</entry></row><row><entry>638</entry><entry>(I-12)</entry><entry>(II-86)</entry><entry>(Ga-1)</entry><entry>68 : 22 : 10</entry></row><row><entry>639</entry><entry><chemistry id="chem0168" num="0168"><img file="EP1490441B2_D0168.tif" /></chemistry></entry><entry>(II-8)</entry><entry>(Ge-1)</entry><entry>72 : 20 : 8</entry></row><row><entry>640</entry><entry>(I-13)</entry><entry>(II-17)</entry><entry>(Gb-2)</entry><entry>70 : 20 : 10</entry></row><row><entry>641</entry><entry>(I-13)</entry><entry>(II-67)</entry><entry>(Gf-2)</entry><entry>66 : 20 : 14</entry></row><row><entry>642</entry><entry><chemistry id="chem0169" num="0169"><img file="EP1490441B2_D0169.tif" /></chemistry></entry><entry>(II-4)</entry><entry>(Gb-2)</entry><entry>70 : 20 : 10</entry></row><row><entry>643</entry><entry>(I-14)</entry><entry>(II-8)</entry><entry>(Gf-1)</entry><entry>68 : 20 : 12</entry></row><row><entry>644</entry><entry>(I-14)</entry><entry>(II-17)</entry><entry>(Ge-1)</entry><entry>72 : 20 : 8</entry></row><row><entry>645</entry><entry><chemistry id="chem0170" num="0170"><img file="EP1490441B2_D0170.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(Gb-1)</entry><entry>70 : 20 : 10</entry></row><row><entry>646</entry><entry>(I-15)</entry><entry>(II-3)</entry><entry>(Gf-3)</entry><entry>66 : 22 : 12</entry></row><row><entry>647</entry><entry>(I-15)</entry><entry>(II-20)</entry><entry>(Ge-1)</entry><entry colsep="1">72 : 20 : 8</entry></row><row><entry>648</entry><entry>(I-15)</entry><entry>(II-27)</entry><entry>(Gb-1)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>649</entry><entry>(I-15)</entry><entry>(II-67)</entry><entry>(Ga-3)</entry><entry colsep="1">66 : 18 : 16</entry></row><row><entry>650</entry><entry>(I-15)</entry><entry>(II-72)</entry><entry>(Gf-4)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>651</entry><entry>(I-15)</entry><entry>(II-81)</entry><entry>(Gf-3)</entry><entry colsep="1">68 : 20 : 12</entry></row><row><entry>652</entry><entry>(I-15)</entry><entry>(II-41)</entry><entry>(Gc-4)</entry><entry colsep="1">70 : 18 : 12</entry></row><row><entry>653</entry><entry><chemistry id="chem0171" num="0171"><img file="EP1490441B2_D0171.tif" /></chemistry></entry><entry>(I-1)</entry><entry>(Ge-1)</entry><entry colsep="1">72 : 20 : 8</entry></row><row><entry>654</entry><entry>(I-16)</entry><entry>(II-2)</entry><entry>(Gb-2)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>655</entry><entry>(I-16)</entry><entry>(II-3)</entry><entry>(Ga-1)</entry><entry colsep="1">68 : 20 : 1 2</entry></row><row><entry>656</entry><entry>(I-16)</entry><entry>(II-7)</entry><entry>(Gb-5)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>657</entry><entry>(I-16)</entry><entry>(II-67)</entry><entry>(Gf-1)</entry><entry colsep="1">66 : 17 : 17</entry></row><row><entry>658</entry><entry><chemistry id="chem0172" num="0172"><img file="EP1490441B2_D0172.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(Gb-5)</entry><entry colsep="1">71 : 18 : 11</entry></row><row><entry>659</entry><entry>(I-17)</entry><entry>(II-2)</entry><entry>(Gb-2)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>660</entry><entry>(I-17)</entry><entry>(II-3)</entry><entry>(Ga-1)</entry><entry colsep="1">70 : 18 : 12</entry></row><row><entry>661</entry><entry>(I-17)</entry><entry>(II-7)</entry><entry>(Gf-2)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>662</entry><entry>(I-17)</entry><entry>(II-67)</entry><entry>(Ge-1)</entry><entry colsep="1">72 : 18 : 10</entry></row><row><entry>663</entry><entry><chemistry id="chem0173" num="0173"><img file="EP1490441B2_D0173.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(Gb-5)</entry><entry colsep="1">67 : 20 : 1 3</entry></row><row><entry>664</entry><entry>(I-18)</entry><entry>(II-2)</entry><entry>(Gb-2)</entry><entry colsep="1">68 : 20 : 12</entry></row><row><entry>665</entry><entry>(I-18)</entry><entry>(II-3)</entry><entry>(Ga-1)</entry><entry colsep="1">68 : 18 : 14</entry></row><row><entry>666</entry><entry>(I-18)</entry><entry>(II-7)</entry><entry>(Gf-1)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>667</entry><entry>(I-18)</entry><entry>(II-67)</entry><entry>(Ge-1)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>668</entry><entry><chemistry id="chem0174" num="0174"><img file="EP1490441B2_D0174.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(Ge-1)</entry><entry colsep="1">68 : 22 : 10</entry></row><row><entry>669</entry><entry>(I-19)</entry><entry>(II-2)</entry><entry>(Gb-2)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>670</entry><entry>(I-19)</entry><entry>(II-3)</entry><entry>(Gf-1)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>671</entry><entry>(I-19)</entry><entry>(II-7)</entry><entry>(Ga-2)</entry><entry colsep="1">66 : 22 : 12</entry></row><row><entry>672</entry><entry>(I-19)</entry><entry>(II-14)</entry><entry>(Gf-4)</entry><entry colsep="1">65 : 22 : 13</entry></row><row><entry>673</entry><entry>(I-19)</entry><entry>(II-26)</entry><entry>(Gf-3)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>674</entry><entry>(I-19)</entry><entry>(II-67)</entry><entry>(Ga-1)</entry><entry colsep="1">68 : 20 : 12</entry></row><row><entry>675</entry><entry>(I-19)</entry><entry>(II-72)</entry><entry>(Gd-2)</entry><entry colsep="1">67 : 22 : 11</entry></row><row><entry>676</entry><entry><chemistry id="chem0175" num="0175"><img file="EP1490441B2_D0175.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(Ge-1)</entry><entry colsep="1">67 : 22 : 11</entry></row><row><entry>677</entry><entry>(I-20)</entry><entry>(II-2)</entry><entry>(Gf-1)</entry><entry colsep="1">65 : 20 : 1 5</entry></row><row><entry>678</entry><entry>(I-20)</entry><entry>(II-3)</entry><entry>(Ga-1)</entry><entry colsep="1">68 : 20 : 12</entry></row><row><entry>679</entry><entry>(I-20)</entry><entry>(II-7)</entry><entry>(Gb-2)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>680</entry><entry>(I-20)</entry><entry>(II-67)</entry><entry>(Gb-5)</entry><entry colsep="1">66 : 22 : 12</entry></row><row><entry>681</entry><entry>(I-20)</entry><entry>(II-80)</entry><entry>(Ga-2)</entry><entry colsep="1">65 : 20 : 15</entry></row><row><entry>682</entry><entry><chemistry id="chem0176" num="0176"><img file="EP1490441B2_D0176.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(Gb-5)</entry><entry colsep="1">68 : 20 : 12</entry></row><row><entry>683</entry><entry>(I-21)</entry><entry>(II-2)</entry><entry>(Gf-2)</entry><entry colsep="1">66 : 20 : 14</entry></row><row><entry>684</entry><entry>(I-21)</entry><entry>(II-3)</entry><entry>(Ga-1)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>685</entry><entry>(I-21)</entry><entry>(II-7)</entry><entry>(Gb-2)</entry><entry colsep="1">67 : 22 : 11</entry></row><row><entry>686</entry><entry>(I-21)</entry><entry>(II-67)</entry><entry>(Ge-1)</entry><entry colsep="1">68 : 22 : 10</entry></row><row><entry>687</entry><entry><chemistry id="chem0177" num="0177"><img file="EP1490441B2_D0177.tif" /></chemistry></entry><entry>(II-1)</entry><entry>(Ge-1)</entry><entry colsep="1">72 : 20 : 8</entry></row><row><entry>688</entry><entry>(I-22)</entry><entry>(II-2)</entry><entry>(Gf-1)</entry><entry colsep="1">67 : 20 : 13</entry></row><row><entry>689</entry><entry>(I-22)</entry><entry>(II-3)</entry><entry>(Ga-1)</entry><entry colsep="1">68 : 20 : 12</entry></row><row><entry>690</entry><entry>(I-22)</entry><entry>(II-7)</entry><entry>(Gb-2)</entry><entry colsep="1">70 : 20 : 10</entry></row><row><entry>691</entry><entry>(I-22)</entry><entry>(II-67)</entry><entry>(Ge-2)</entry><entry colsep="1">67 : 22 : 11</entry></row><row><entry>692</entry><entry>(I-22)</entry><entry>(II-80)</entry><entry>(Gd-1)</entry><entry colsep="1">65 : 20 : 15</entry></row></tbody></tgroup></table></tables>

Further dye mixtures according to Example 468 or 469

0100<tables id="tabl0008" num="0008"><table frame="all"><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="16mm" /><colspec colnum="2" colname="col2" colwidth="34mm" /><colspec colnum="3" colname="col3" colwidth="35mm" /><colspec colnum="4" colname="col4" colwidth="50mm" /><colspec colnum="5" colname="col5" colwidth="33mm" colsep="0" /><thead><row><entry valign="top">example</entry><entry valign="top">Dye according to general formula (I)</entry><entry valign="top">Dye according to general formula (II)</entry><entry valign="top">Dye according to formula (G)</entry><entry valign="top">Ratio (I) :( II) :( G)</entry></row></thead><tbody><row><entry>693</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry><chemistry id="chem0178" num="0178"><img file="EP1490441B2_D0178.tif" /></chemistry></entry><entry>72 : 18 : 10</entry></row><row><entry>694</entry><entry>(I-1)</entry><entry>(II-2)</entry><entry><chemistry id="chem0179" num="0179"><img file="EP1490441B2_D0179.tif" /></chemistry></entry><entry>68 : 21 : 11</entry></row><row><entry>695</entry><entry>(I-1)</entry><entry>(II-7)</entry><entry><chemistry id="chem0180" num="0180"><img file="EP1490441B2_D0180.tif" /></chemistry></entry><entry>70 : 20 : 10</entry></row><row><entry>696</entry><entry>(I-1)</entry><entry>(II-54)</entry><entry><chemistry id="chem0181" num="0181"><img file="EP1490441B2_D0181.tif" /></chemistry></entry><entry>70 : 18 : 12</entry></row><row><entry>697</entry><entry>(I-1)</entry><entry>(II-26)</entry><entry>(Ga-9)</entry><entry>72 : 17 : 11</entry></row><row><entry>698</entry><entry>(I-1)</entry><entry>(II-77)</entry><entry>(Ga-7)</entry><entry>73 : 18 : 9</entry></row><row><entry>699</entry><entry>(I-2)</entry><entry>(II-1)</entry><entry>(Ga-7)</entry><entry>72 : 18 : 10</entry></row><row><entry>700</entry><entry>(I-2)</entry><entry>(II-2)</entry><entry>(Ga-7)</entry><entry>68 : 21 : 11</entry></row><row><entry>701</entry><entry>(I-2)</entry><entry>(II-7)</entry><entry>(Ga-9)</entry><entry>70 : 20 : 10</entry></row><row><entry>702</entry><entry>(I-2)</entry><entry>(II-54)</entry><entry>(Ga-10)</entry><entry>70 : 18 : 12</entry></row><row><entry>703</entry><entry>(I-2)</entry><entry>(II-26)</entry><entry>(Ga-9)</entry><entry>72 : 17 : 11</entry></row><row><entry>704</entry><entry>(I-2)</entry><entry>(II-77)</entry><entry>(Ga-7)</entry><entry>73 : 18 : 9</entry></row><row><entry>705</entry><entry>(I-4)</entry><entry>(II-1)</entry><entry>(Ga-7)</entry><entry>72 : 18 : 10</entry></row><row><entry>706</entry><entry>(I-4)</entry><entry>(II-2)</entry><entry>(Ga-8)</entry><entry>68 : 21 : 11</entry></row><row><entry>707</entry><entry>(I-4)</entry><entry>(II-7)</entry><entry>(Ga-9)</entry><entry>70 : 20 : 10</entry></row><row><entry>708</entry><entry>(I-4)</entry><entry>(II-54)</entry><entry>(Ga-10)</entry><entry>70 : 18 : 12</entry></row><row><entry>709</entry><entry>(I-4)</entry><entry>(II-26)</entry><entry>(Ga-9)</entry><entry>72 : 17 : 11</entry></row><row><entry>710</entry><entry>(I-4)</entry><entry>(II-77)</entry><entry>(Ga-7)</entry><entry>73 : 18 : 9</entry></row><row><entry>711</entry><entry>(I-7)</entry><entry>(II-1)</entry><entry>(Ga-7)</entry><entry>72 : 18 : 10</entry></row><row><entry>712</entry><entry>(I-7)</entry><entry>(II-2)</entry><entry>(Ga-8)</entry><entry>68 : 21 : 11</entry></row><row><entry>713</entry><entry>(I-7)</entry><entry>(II-7)</entry><entry>(Ga-9)</entry><entry>70 : 20 : 10</entry></row><row><entry>714</entry><entry>(I-7)</entry><entry>(II-54)</entry><entry>(Ga-10)</entry><entry>70 : 18 : 12</entry></row><row><entry>715</entry><entry>(I-7)</entry><entry>(II-26)</entry><entry>(Ga-9)</entry><entry>72 : 17 : 11</entry></row><row><entry>716</entry><entry>(I-7)</entry><entry>(II-77)</entry><entry>(Ga-7)</entry><entry>73 : 18 : 9</entry></row></tbody></tgroup></table></tables>

Dye mixtures according to Example 473

0101<tables id="tabl0009" num="0009"><table frame="all"><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="16mm" /><colspec colnum="2" colname="col2" colwidth="38mm" /><colspec colnum="3" colname="col3" colwidth="40mm" /><colspec colnum="4" colname="col4" colwidth="40mm" /><colspec colnum="5" colname="col5" colwidth="33mm" /><thead><row><entry valign="top">example</entry><entry valign="top">Dye according to general formula (I)</entry><entry valign="top">Dye according to general formula (11)</entry><entry valign="top">Dye according to general formula (G)</entry><entry valign="top">Ratio (I) :( II) :( G)</entry></row></thead><tbody><row><entry>717</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry>(Gf-2)</entry><entry>65 : 20 : 1 5</entry></row><row><entry>718</entry><entry>(I-2)</entry><entry>(II-3)</entry><entry>(Ge-1)</entry><entry>70 : 20 : 10</entry></row><row><entry>719</entry><entry>(I-6)</entry><entry>(II-41)</entry><entry>(Gf-3)</entry><entry>67 : 22 : 11</entry></row><row><entry>720</entry><entry>(I-7)</entry><entry>(II-14)</entry><entry>(Gd-2)</entry><entry>65 : 22 : 13</entry></row><row><entry>721</entry><entry>(I-24)</entry><entry>(II-15)</entry><entry>(Gf-1)</entry><entry>67 : 20 : 13</entry></row><row><entry>722</entry><entry>(I-9)</entry><entry>(II-17)</entry><entry>(Ga-3)</entry><entry>67 : 18 : 15</entry></row><row><entry>723</entry><entry>(I-10)</entry><entry>(11-54)</entry><entry>(Ga-4)</entry><entry>66 : 22 : 12</entry></row><row><entry>724</entry><entry>(I-16)</entry><entry>(II-83)</entry><entry>(Ga-2)</entry><entry>65 : 20 : 15</entry></row><row><entry>725</entry><entry>(I-17)</entry><entry>(II-85)</entry><entry>(Gb-5)</entry><entry>67 : 20 : 13</entry></row><row><entry>726</entry><entry>(I-18)</entry><entry>(II-76)</entry><entry>(Gb-3)</entry><entry>70 : 17 : 13</entry></row><row><entry>727</entry><entry>(I-20)</entry><entry>(II-77)</entry><entry>(Gf-3)</entry><entry>70 : 15 : 15</entry></row><row><entry>728</entry><entry>(I-21)</entry><entry>(II-38)</entry><entry>(Gd-1)</entry><entry>65 : 20 : 15</entry></row></tbody></tgroup></table></tables>

Dye mixtures according to Example 474

0102<tables id="tabl0010" num="0010"><table frame="all"><tgroup cols="4"><colspec colnum="1" colname="col1" colwidth="16mm" /><colspec colnum="2" colname="col2" colwidth="45mm" /><colspec colnum="3" colname="col3" colwidth="45mm" /><colspec colnum="4" colname="col4" colwidth="28mm" /><thead><row><entry valign="top">example</entry><entry valign="top">Dye according to general formula (I)</entry><entry valign="top">Dye according to general formula (II)</entry><entry valign="top">Ratio (I) :( II)</entry></row></thead><tbody><row><entry>729</entry><entry>(I-3)</entry><entry>(II-1)</entry><entry>70 : 30</entry></row><row><entry>730</entry><entry>(I-3)</entry><entry>(II-2)</entry><entry>67 : 33</entry></row><row><entry>731</entry><entry>(I-3)</entry><entry>(II-54)</entry><entry>70 : 30</entry></row><row><entry>732</entry><entry>(I-3)</entry><entry>(II-24)</entry><entry>75 : 25</entry></row><row><entry>733</entry><entry>(I-3)</entry><entry>(II-26)</entry><entry>70 : 30</entry></row><row><entry>734</entry><entry>(I-3)</entry><entry>(II-67)</entry><entry>72 : 28</entry></row><row><entry>735</entry><entry>(I-3)</entry><entry>(II-69)</entry><entry>75 : 25</entry></row><row><entry>736</entry><entry>(I-3)</entry><entry>(II-72)</entry><entry>68 : 32</entry></row><row><entry>737</entry><entry>(I-4)</entry><entry>(II-1)</entry><entry>67 : 33</entry></row><row><entry>738</entry><entry>(I-4)</entry><entry>(II-2)</entry><entry>65 : 35</entry></row><row><entry>739</entry><entry>(I-4)</entry><entry>(II-3)</entry><entry>75 : 25</entry></row><row><entry>740</entry><entry>(I-4)</entry><entry>(II-14)</entry><entry>68 : 32</entry></row><row><entry>741</entry><entry>(I-4)</entry><entry>(II-54)</entry><entry>70 : 30</entry></row><row><entry>742</entry><entry>(I-4)</entry><entry>(II-24)</entry><entry>76 : 24</entry></row><row><entry>743</entry><entry>(I-4)</entry><entry>(II-26)</entry><entry>72 : 28</entry></row><row><entry>744</entry><entry>(I-4)</entry><entry>(II-27)</entry><entry>77 : 23</entry></row><row><entry>745</entry><entry>(I-4)</entry><entry>(II-67)</entry><entry>73 : 27</entry></row><row><entry>746</entry><entry>(I-4)</entry><entry>(II-69)</entry><entry>70 : 30</entry></row><row><entry>747</entry><entry>(I-4)</entry><entry>(II-72)</entry><entry>70 : 30</entry></row><row><entry>748</entry><entry>(I-4)</entry><entry>(II-86)</entry><entry>80 : 20</entry></row><row><entry>749</entry><entry>(I-5)</entry><entry>(II-1)</entry><entry>70 : 30</entry></row><row><entry>750</entry><entry>(I-5)</entry><entry>(II-2)</entry><entry>67 : 33</entry></row><row><entry>751</entry><entry>(I-5)</entry><entry>(II-3)</entry><entry>72 : 28</entry></row><row><entry>752</entry><entry>(I-5)</entry><entry>(II-7)</entry><entry>70 : 30</entry></row><row><entry>753</entry><entry>(I-5)</entry><entry>(II-14)</entry><entry>66 : 34</entry></row><row><entry>754</entry><entry>(I-5)</entry><entry>(II-54)</entry><entry>68 : 32</entry></row><row><entry>755</entry><entry>(I-5)</entry><entry>(II-24)</entry><entry>75 : 25</entry></row><row><entry>756</entry><entry>(I-5)</entry><entry>(II-26)</entry><entry>73 : 27</entry></row><row><entry>757</entry><entry>(I-5)</entry><entry>(II-27)</entry><entry>75 : 25</entry></row><row><entry>758</entry><entry>(I-5)</entry><entry>(II-67)</entry><entry>72 : 28</entry></row><row><entry>759</entry><entry>(I-5)</entry><entry>(II-69)</entry><entry>70 : 30</entry></row><row><entry>760</entry><entry>(I-5)</entry><entry>(II-72)</entry><entry colsep="0">70 : 30</entry></row><row><entry>761</entry><entry>(I-12)</entry><entry>(II-54)</entry><entry colsep="0">70 : 30</entry></row><row><entry>762</entry><entry>(I-12)</entry><entry>(II-26)</entry><entry colsep="0">75 : 25</entry></row><row><entry>763</entry><entry>(I-12)</entry><entry>(II-69)</entry><entry colsep="0">68 : 32</entry></row><row><entry>764</entry><entry>(I-13)</entry><entry>(II-1)</entry><entry colsep="0">75 : 25</entry></row><row><entry>765</entry><entry>(I-13)</entry><entry>(II-2)</entry><entry colsep="0">67 : 33</entry></row><row><entry>766</entry><entry>(I-13)</entry><entry>(II-3)</entry><entry colsep="0">70 : 30</entry></row><row><entry>767</entry><entry>(I-13)</entry><entry>(II-7)</entry><entry colsep="0">72 : 28</entry></row><row><entry>768</entry><entry>(I-13)</entry><entry>(II-14)</entry><entry colsep="0">65 : 35</entry></row><row><entry>769</entry><entry>(I-13)</entry><entry>(II-54)</entry><entry colsep="0">68 : 32</entry></row><row><entry>770</entry><entry>(I-13)</entry><entry>(II-24)</entry><entry colsep="0">73 : 27</entry></row><row><entry>771</entry><entry>(I-13)</entry><entry>(II-26)</entry><entry colsep="0">72 : 28</entry></row><row><entry>772</entry><entry>(I-13)</entry><entry>(II-27)</entry><entry colsep="0">75 : 25</entry></row><row><entry>773</entry><entry>(I-13)</entry><entry>(II-67)</entry><entry colsep="0">70 : 30</entry></row><row><entry>774</entry><entry>(I-13)</entry><entry>(II-69)</entry><entry colsep="0">68 : 32</entry></row><row><entry>775</entry><entry>(I-13)</entry><entry>(II-72)</entry><entry colsep="0">70 : 30</entry></row><row><entry>776</entry><entry>(I-14)</entry><entry>(II-1)</entry><entry colsep="0">72 : 28</entry></row><row><entry>777</entry><entry>(I-14)</entry><entry>(II-2)</entry><entry colsep="0">68 : 32</entry></row><row><entry>778</entry><entry>(I-14)</entry><entry>(II-3)</entry><entry colsep="0">72 : 28</entry></row><row><entry>779</entry><entry>(I-14)</entry><entry>(II-7)</entry><entry colsep="0">70 : 30</entry></row><row><entry>780</entry><entry>(I-14)</entry><entry>(II-14)</entry><entry colsep="0">66 : 34</entry></row><row><entry>781</entry><entry>(I-14)</entry><entry>(II-54)</entry><entry colsep="0">70 : 30</entry></row><row><entry>782</entry><entry>(I-14)</entry><entry>(II-24)</entry><entry colsep="0">75 : 25</entry></row><row><entry>783</entry><entry>(I-14)</entry><entry>(II-26)</entry><entry colsep="0">72 : 28</entry></row><row><entry>784</entry><entry>(I-14)</entry><entry>(II-27)</entry><entry colsep="0">74 : 26</entry></row><row><entry>785</entry><entry>(I-14)</entry><entry>(II-67)</entry><entry colsep="0">72 : 28</entry></row><row><entry>786</entry><entry>(I-14)</entry><entry>(II-69)</entry><entry colsep="0">68 : 32</entry></row><row><entry>787</entry><entry>(I-14)</entry><entry>(II-72)</entry><entry colsep="0">72 : 28</entry></row><row><entry>788</entry><entry>(I-14)</entry><entry>(II-86)</entry><entry colsep="0">75 : 25</entry></row></tbody></tgroup></table></tables>

Dye mixtures according to Example 475

0103<tables id="tabl0011" num="0011"><table frame="all"><tgroup cols="4"><colspec colnum="1" colname="col1" colwidth="16mm" /><colspec colnum="2" colname="col2" colwidth="45mm" /><colspec colnum="3" colname="col3" colwidth="45mm" /><colspec colnum="4" colname="col4" colwidth="28mm" /><thead><row><entry valign="top">example</entry><entry valign="top">Dye according to general formula (I)</entry><entry valign="top">Dye according to general formula (II)</entry><entry valign="top">Ratio (I) :( II)</entry></row></thead><tbody><row><entry>789</entry><entry>(I-4)</entry><entry>(II-4)</entry><entry>70 : 30</entry></row><row><entry>790</entry><entry>(I-5)</entry><entry>(II-17)</entry><entry>75 : 25</entry></row><row><entry>791</entry><entry>(I-12)</entry><entry>(II-1)</entry><entry>73 : 27</entry></row><row><entry>792</entry><entry>(I-12)</entry><entry>(II-2)</entry><entry>70 : 30</entry></row><row><entry>793</entry><entry>(I-12)</entry><entry>(II-24)</entry><entry>72 : 28</entry></row><row><entry>794</entry><entry>(I-12)</entry><entry>(II-67)</entry><entry>73 : 27</entry></row><row><entry>795</entry><entry>(I-12)</entry><entry>(II-72)</entry><entry>72 : 28</entry></row><row><entry>796</entry><entry>(I-12)</entry><entry>(II-45)</entry><entry>65 : 35</entry></row><row><entry>797</entry><entry>(I-13)</entry><entry>(II-4)</entry><entry>75 : 25</entry></row><row><entry>798</entry><entry>(I-14)</entry><entry>(II-17)</entry><entry>77 : 23</entry></row></tbody></tgroup></table></tables>

Dye mixtures according to Example 476

0104<tables id="tabl0012" num="0012"><table frame="all"><tgroup cols="5"><colspec colnum="1" colname="col1" colwidth="16mm" /><colspec colnum="2" colname="col2" colwidth="38mm" /><colspec colnum="3" colname="col3" colwidth="40mm" /><colspec colnum="4" colname="col4" colwidth="40mm" /><colspec colnum="5" colname="col5" colwidth="33mm" /><thead><row><entry valign="top">example</entry><entry valign="top">Dye according to general formula (I)</entry><entry valign="top">Dye according to general formula (II)</entry><entry valign="top">Dye according to general formula (G)</entry><entry valign="top">Ratio (I) :( II) :( G)</entry></row></thead><tbody><row><entry>799</entry><entry>(I-1)</entry><entry>(II-24)</entry><entry>(Gf-2)</entry><entry>66 : 20 : 14</entry></row><row><entry>800</entry><entry>(I-1)</entry><entry>(II-67)</entry><entry>(Gb-5)</entry><entry>67 : 20 : 13</entry></row><row><entry>801</entry><entry>(I-1)</entry><entry>(II-72)</entry><entry>(Gf-1)</entry><entry>65 : 20 : 15</entry></row><row><entry>802</entry><entry>(I-1)</entry><entry>(II-45)</entry><entry>(Ga-3)</entry><entry>60 : 25 : 15</entry></row><row><entry>803</entry><entry>(I-2)</entry><entry>(II-57)</entry><entry>(Ge-1)</entry><entry>70 : 20 : 10</entry></row><row><entry>804</entry><entry>(I-2)</entry><entry>(II-62)</entry><entry>(Ga-1)</entry><entry>65 : 22 : 13</entry></row><row><entry>805</entry><entry>(I-2)</entry><entry>(II-27)</entry><entry>(Gb-2)</entry><entry>70 : 20 : 10</entry></row><row><entry>806</entry><entry>(I-2)</entry><entry>(II-35)</entry><entry>(Gf-1)</entry><entry>66 : 20 : 14</entry></row><row><entry>807</entry><entry>(I-7)</entry><entry>(II-63)</entry><entry>(Ge-1)</entry><entry>70 : 22 : 8</entry></row><row><entry>808</entry><entry>(I-7)</entry><entry>(II-26)</entry><entry>(Gb-2)</entry><entry>70 : 20 : 10</entry></row><row><entry>809</entry><entry>(I-7)</entry><entry>(II-31)</entry><entry>(Gd-2)</entry><entry>67 : 20 : 13</entry></row><row><entry>810</entry><entry>(I-7)</entry><entry>(II-47)</entry><entry>(Gb-1)</entry><entry>65 : 25 : 10</entry></row><row><entry>811</entry><entry>(I-24)</entry><entry>(II-20)</entry><entry>(Ga-2)</entry><entry>65 : 20 : 15</entry></row><row><entry>812</entry><entry>(I-24)</entry><entry>(II-60)</entry><entry>(Gf-1)</entry><entry>67 : 18 : 15</entry></row><row><entry>813</entry><entry>(I-24)</entry><entry>(II-25)</entry><entry>(Gf-3)</entry><entry>66 : 20 : 14</entry></row><row><entry>814</entry><entry>(I-24)</entry><entry>(II-68)</entry><entry>(Gb-2)</entry><entry>67 : 22 : 11</entry></row><row><entry>815</entry><entry>(I-24)</entry><entry>(II-73)</entry><entry>(Gd-2)</entry><entry>65 : 18 : 17</entry></row><row><entry>816</entry><entry>(I-9)</entry><entry>(II-8)</entry><entry>(Gf-1)</entry><entry>65 : 20 : 15</entry></row><row><entry>817</entry><entry>(I-10)</entry><entry>(II-59)</entry><entry>(Gb-2)</entry><entry>67 : 22 : 11</entry></row><row><entry>818</entry><entry>(I-10)</entry><entry>(II-69)</entry><entry>(Ga-1)</entry><entry>65 : 23 : 12</entry></row><row><entry>819</entry><entry>(1-10)</entry><entry>(II-74)</entry><entry>(Ga-2)</entry><entry>67 : 20 : 13</entry></row></tbody></tgroup></table></tables>

Example 1187

010570 Parts of an electrolyte-containing dye powder which contains the navy blue disazo dye of the formula (I-1) in a 70% proportion, 8 parts of an electrolyte-containing dye powder which contains the scarlet disazo dye of the formula (II-2) in a 75% proportion, 12 Parts of an electrolyte-containing dye powder which contains the orange-colored azo dye of the formula (III-21) in an 80% proportion and 10 parts of an electrolyte-containing dye powder, which contains the yellow azo dye of the formula (Ga-1) in a 75% proportion, are dissolved in 700 parts of water and the dye solution obtained is adjusted to pH 5.5-6.5. Evaporation of this dye solution gives a dye mixture which produces deep black dyeings and prints on cotton under the dyeing conditions customary for reactive dyes.

0106Alternatively, the dye solution obtained can also be buffered at pH 5.5-6 by adding a phosphate buffer and adjusted as a liquid brand of certain strength by further dilution or concentration.

Example 1188

0107An aqueous solution prepared analogously to Example 2, the three dyes (I-1), (II-2) and (III-1) in a ratio of 65: 15: 10, is mixed with 10 parts of an electrolyte-containing dye powder which contains the orange-colored azo dye of the formula (III-21) contains 80%, added and the resulting dye solution adjusted to pH 5.5-6.5. Evaporation of this dye solution gives a dye mixture which produces deep black dyeings and prints on cotton under the dyeing conditions customary for reactive dyes.

Example 1189

0108An aqueous solution prepared analogously to Example 2, the three dyes (I-1), (II-1) and (III-1) in a ratio of 66: 17: 7, is mixed with 10 parts of an electrolyte-containing dye powder which contains the yellow azo dye of the formula Contains (Ga-1) in a 75% proportion, added and the resulting dye solution is adjusted to pH 5.5-6.5. Evaporation of this dye solution gives a dye mixture which produces deep black dyeings and prints on cotton under the dyeing conditions customary for reactive dyes.

Further dye mixtures according to Example 1187

0109<tables id="tabl0013" num="0013"><table frame="all"><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="16mm" /><colspec colnum="2" colname="col2" colwidth="26mm" /><colspec colnum="3" colname="col3" colwidth="27mm" /><colspec colnum="4" colname="col4" colwidth="28mm" /><colspec colnum="5" colname="col5" colwidth="49mm" /><colspec colnum="6" colname="col6" colwidth="22mm" colsep="0" /><thead><row><entry valign="top">example</entry><entry valign="top">Dye according to general formula (I)</entry><entry valign="top">Dye according to general formula (II)</entry><entry valign="top">Dye according to general formula (III)</entry><entry valign="top">Dye according to formula (G)</entry><entry valign="top">relationship</entry></row></thead><tbody><row><entry>1190</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry>(III-21)</entry><entry>(Ga-1)</entry><entry colsep="1">70:10:10:10</entry></row><row><entry>1191</entry><entry>(I-1)</entry><entry>(II-2)</entry><entry>(III-22)</entry><entry><chemistry id="chem0182" num="0182"><img file="EP1490441B2_D0182.tif" /></chemistry></entry><entry>66:12:10:12</entry></row><row><entry>1193</entry><entry>(I-1)</entry><entry>(II-7)</entry><entry>(III-24)</entry><entry><chemistry id="chem0183" num="0183"><img file="EP1490441B2_D0183.tif" /></chemistry></entry><entry>68:8:10:14</entry></row><row><entry>1194</entry><entry>(I-1)</entry><entry>(II-24)</entry><entry>(III-27)</entry><entry><chemistry id="chem0184" num="0184"><img file="EP1490441B2_D0184.tif" /></chemistry></entry><entry>67:11:12:10</entry></row><row><entry>1195</entry><entry>(I-1)</entry><entry>(II-26)</entry><entry>(III-21)</entry><entry><chemistry id="chem0185" num="0185"><img file="EP1490441B2_D0185.tif" /></chemistry></entry><entry>70:12:10:8</entry></row><row><entry>1197</entry><entry>(I-1)</entry><entry>(II-37)</entry><entry>(III-24)</entry><entry><chemistry id="chem0186" num="0186"><img file="EP1490441B2_D0186.tif" /></chemistry></entry><entry>70:10:10:10</entry></row><row><entry>1199</entry><entry>(I-1)</entry><entry>(II-45)</entry><entry>(III-22)</entry><entry><chemistry id="chem0187" num="0187"><img file="EP1490441B2_D0187.tif" /></chemistry></entry><entry>60:15:10:15</entry></row></tbody></tgroup></table></tables>

Further dye mixtures according to Example 1188

0110<tables id="tabl0014" num="0014"><table frame="all"><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="16mm" /><colspec colnum="2" colname="col2" colwidth="31mm" /><colspec colnum="3" colname="col3" colwidth="32mm" /><colspec colnum="4" colname="col4" colwidth="33mm" /><colspec colnum="5" colname="col5" colwidth="33mm" /><colspec colnum="6" colname="col6" colwidth="22mm" /><thead><row><entry valign="top">example</entry><entry valign="top">Dye according to general formula (I)</entry><entry valign="top">Dye according to general formula (II)</entry><entry valign="top">Dye according to general formula (III)</entry><entry valign="top">Dye according to formula (III)</entry><entry valign="top">relationship</entry></row></thead><tbody><row><entry>1203</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry>(III-21)</entry><entry>(III-7)</entry><entry>70:10:10:10</entry></row><row><entry>1204</entry><entry>(I-1)</entry><entry>(II-2)</entry><entry>(III-22)</entry><entry>(III-1)</entry><entry>66:12:12:10</entry></row><row><entry>1206</entry><entry>(I-1)</entry><entry>(II-7)</entry><entry>(III-24)</entry><entry>(III-8)</entry><entry>68:10:10:12</entry></row><row><entry>1207</entry><entry>(I-1)</entry><entry>(II-24)</entry><entry>(III-27)</entry><entry>(III-4)</entry><entry>65:11:12:12</entry></row><row><entry>1208</entry><entry>(I-1)</entry><entry>(II-26)</entry><entry>(III-21)</entry><entry>(III-10)</entry><entry>70:12:10:8</entry></row><row><entry>1210</entry><entry>(I-1)</entry><entry>(II-37)</entry><entry>(III-24)</entry><entry>(III-7)</entry><entry>70:10:10:10</entry></row><row><entry>1212</entry><entry>(I-1)</entry><entry>(II-45)</entry><entry>(III-22)</entry><entry>(III-2)</entry><entry>60:15:10:15</entry></row></tbody></tgroup></table></tables>

Further dye mixtures according to Example 1189

0111<tables id="tabl0015" num="0015"><table frame="all"><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="16mm" /><colspec colnum="2" colname="col2" colwidth="31mm" /><colspec colnum="3" colname="col3" colwidth="32mm" /><colspec colnum="4" colname="col4" colwidth="33mm" /><colspec colnum="5" colname="col5" colwidth="33mm" /><colspec colnum="6" colname="col6" colwidth="22mm" /><thead><row><entry valign="top">example</entry><entry valign="top">Dye according to general formula (I)</entry><entry valign="top">Dye according to general formula (II)</entry><entry valign="top">Dye according to general formula (III)</entry><entry valign="top">Dye according to formula (G)</entry><entry valign="top">relationship</entry></row></thead><tbody><row><entry>1216</entry><entry>(I-1)</entry><entry>(II-1)</entry><entry>(III-7)</entry><entry>(Ga-2)</entry><entry>67:10:11:12</entry></row><row><entry>1217</entry><entry>(I-1)</entry><entry>(II-2)</entry><entry>(III-1)</entry><entry>(Ga-1)</entry><entry>67:12:10:11</entry></row><row><entry>1219</entry><entry>(I-1)</entry><entry>(II-7)</entry><entry>(III-8)</entry><entry>(Gf-1)</entry><entry>67:8:10:15</entry></row><row><entry>1220</entry><entry>(I-1)</entry><entry>(II-24)</entry><entry>(III-4)</entry><entry>(Ge-1)</entry><entry>67:11:12:10</entry></row><row><entry>1221</entry><entry>(I-1)</entry><entry>(II-26)</entry><entry>(III-10)</entry><entry>(Gf-3)</entry><entry>69:12:10:9</entry></row><row><entry>1223</entry><entry>(I-1)</entry><entry>(II-37)</entry><entry>(III-7)</entry><entry>(Ga-7)</entry><entry colsep="0">70:10:10:10</entry></row><row><entry>1225</entry><entry>(I-1)</entry><entry>(II-45)</entry><entry>(III-2)</entry><entry>(Ga-6)</entry><entry colsep="0">60:15:10:15</entry></row></tbody></tgroup></table></tables>

Application example 1

01122nd Parts of a dye mixture obtained according to Examples 1 - 7, 9, 449, 468 - 481, 1187 - 1189 and 50 parts of sodium chloride are dissolved in 999 parts of water and 5 parts of sodium carbonate, 0.7 parts of sodium hydroxide (in the form of a 32.5% aqueous solution) and optionally 1 part of a wetting agent. 100 g of a cotton fabric are added to this dye bath. The temperature of the dyebath is first kept at 25 ° C. for 10 minutes, then raised to the final temperature (40-80 ° C.) in 30 minutes and this temperature is held for a further 60-90 minutes. The dyed goods are then rinsed with drinking water for 2 minutes and then with E-water for 5 minutes. The dyed goods are neutralized at 40 ° C in 1000 parts of an aqueous solution containing 1 part of a 50% acetic acid for 10 minutes. It is rinsed with deionized water at 70 ° C. and then soaped at the boil for 15 minutes with a detergent, rinsed again and dried. A strong navy to gray color with very good fastness properties is obtained.

Example of use 2

01136 Parts of a dye mixture obtained according to Examples 1-7, 9, 449, 468-481, 1187-1189 and 50 parts of sodium chloride are dissolved in 998 parts of water and 7 parts of sodium carbonate, 2 parts of sodium hydroxide (in the form of a 32.5% aqueous solution Solution) and optionally 1 part of a wetting agent. 100 g of a cotton fabric are added to this dye bath. The further processing takes place as indicated in application example 1. A deep black color is obtained with very good fastness properties.

Example of use 3

01142nd Parts of one according to Example 9, 128, 129, 132, 137, 138, 141, 143, 145, 275, 276, 279, 284, 285, 288, 290, 292, 436 or 444, 477, 601-607, 645- 652, 719, obtained dye mixture are dissolved in 999 parts of water and 5 parts of sodium carbonate, 0.7 parts of sodium hydroxide (in the form of a 32.5% aqueous solution) and optionally 1 part of a wetting agent. 100 g of a cotton fabric are added to this dye bath. The further processing takes place as indicated in application example 1. A strong navy to gray color with very good fastness properties is obtained.

Example of use 4

01154th Parts of one according to Example 9, 128, 129, 132, 137, 138, 141, 143, 145, 275, 276, 279, 284, 285, 288, 290, 292, 436 or 444, 477, 601-607, 645- 652, 719, dye mixture obtained and 5 parts of sodium chloride are dissolved in 999 parts of water, 7 parts of sodium carbonate, 0.7 part of sodium hydroxide (in the form of a 32.5% aqueous solution) and optionally 1 part of a wetting agent. 100 g of a cotton fabric are added to this dye bath. The further processing takes place as indicated in application example 1. A strong gray-blue to black coloration with very good fastness properties is obtained.

Application example 5

01168th Parts of one according to Example 9, 128, 129, 132, 137, 138, 141, 143, 145, 275, 276, 279, 284, 285, 288, 290, 292, 436 or 444, 477, 601-607, 645- 652, 719, dye mixture obtained and 10 parts of sodium chloride are dissolved in 997 parts of water, 10 parts of sodium carbonate, 1.3 parts of sodium hydroxide (in the form of a 32.5% aqueous solution) and optionally 1 part of a wetting agent. 100 g of a cotton fabric are added to this dye bath. The further processing takes place as indicated in application example 1. A deep black color is obtained with very good fastness properties.