TRISAZO ACID DYES

FIELD OF THE INVENTION

[0001] The invention relates to novel trisazo acid dyes, a process for the preparation thereof, and use thereof in a dyeing process or a printing process.

BACKGROUND OF THE INVENTION

[0002] Trisazo acid dyes are known in the art.

[0003] WO 2013/056838 A1 relates to trisazo dyes of the following formula

wherein the residues have the meaning as defined in said document. The dyes are particularly suitable for dyeing fibrous material, which contains or consists of natural or synthetic polyamide, in blue, violet or black shades.

[0004] EP 2 457 955 A1 relates to trisazo dyes of the following formula

wherein the three azo groups are linked by aromatic structures such as benzene and/or naphthalene groups as defined in said document. The dyes are particularly suitable for making paper or paper board in brownish shades.

[0005] EP 0 490 195 A1 relates to an ink comprising at least water, a water-soluble organic solvent and a dye, the dye comprising a solvent represented by the general following formula

wherein the residues have the meaning as defined in said document. The dyes are suitable to be used in ink-jet printing.

[0006] EP 0 422 668 A2 relates to a recording liquid containing a solvent and at least one dye represented by the following formula

wherein A represents a substituted or unsubstituted phenyl or naphthyl group, B represents a substituted or unsubstituted naphthylene group, and C represents a substituted phenyl, pyridyl or pyrimidinyl group as defined in said document, and to an ink-jet recording method employing the recording liquid.

OBJECT OF THE INVENTION

,[0007] There is still an ongoing need for trisazo acid dyes that have improved properties, such as dye levelness (i.e. the uniformity of color shade along the substrate to be dyed), color fastness (light and wet/wash fastness, i.e. the resistance of the color to fading and running when exposed to light and wetness), and build-up behavior. Moreover, there is an ongoing need for blue trisazo dyes, which, when mixed with a red and a yellow dye to give a desired color, can be used in a trichromatic printing or dyeing process.

SUMMARY OF THE INVENTION

[0008] The invention relates to a compound of formula (I)

(I) wherein

R ¹ signifies hydrogen, unbranched C ₁ -C ₆ -alkyl or branched C ₃ -C ₆ -alkyl, SO ₃ Y, or SO ₂ CH ₂ CH ₂ OH, signifies hydrogen, unbranched C ₁ -Ce-alkyl or branched C ₃ -C ₆ -alkyl, SO ₃ Y, SO ₂ CH ₂ CH ₂ OH, or -NHCH ₂ CH ₂ OH,

signify independently from each other hydrogen, unbranched C ₁ -C ₆ -alkyl or branched C ₃ -C ₆ -alkyl, unbranched C ₁ -C ₆ -alkoxy or branched C ₃ -C ₆ -alkoxy, signifies hydrogen or SO ₃ Y,

signifies hydrogen or SO ₃ Y,

signifies hydrogen, unbranched CrC ₆ -alkyl or branched C ₃ -C ₆ -alkyl , phenyl, or unbranched C ₁ -C ₁₂ -alkoxy, or branched C ₃ -C ₁₂ -alkoxy, or NH ₂ ,

signify independently from each other unbranched CrC ₆ -alkyl or branched C ₃ -C6-alkyl, or aryl, or -(CH ₂ ) _n -aryl with n = 1 , 2, 3 or 4; wherein Y signifies H ⁺ or an alkali metal cation, preferably Na ⁺ or K ⁺ ; and

wherein said compound of formula (I) contains at least one SO ₃ Y group.

[0009] In one embodiment, the compound of formula (I) contains two, or three SO ₃ Y- groups, preferably two SO ₃ Y-groups.

[0010] In one embodiment, R ¹ signifies hydrogen or SO ₃ Y or SO ₂ CH ₂ CH ₂ OH.

[0011] In one embodiment, R ² signifies hydrogen, SO ₃ Y or -NHCH ₂ CH ₂ OH.

[0012] In one embodiment, R ³ and R ⁴ signify independently of one another hydrogen, or unbranched C ₁ -C ₄ -alkyl, or branched C ₃ -C ₄ -alkyl.

[0013] In one embodiment, R ⁷ signifies hydrogen, or NH ₂ , or unbranched C ₁ -C ₄ -alkyl, or branched C ₃ -C ₄ -alkyl. Preferably, R ⁷ signifies methyl or ethyl.

[0014] In one embodiment, R ⁸ signifies -(CH ₂ ) _n -phenyl, wherein n = 1 , 2, 3 or 4; or- (CH ₂ ) _n -naphthyl, wherein n = 1 , 2, 3 or 4 . [0015] In one embodiment, R signifies a -(CH ₂ ) _1-2 -phenyl group, or a -(CH ₂ ) _1-2 -phenyl group wherein the phenyl radical is substituted with one SO ₃ Y group or with one nitro group.

[0016] In one embodiment, R ⁹ signifies unbranched C ₁ -C ₄ -alkyl, or branched C ₃ -C ₄ -alkyl.

[0017] In one embodiment,

R signifies hydrogen or SO ₃ Y or SO ₂ CH ₂ CH ₂ OH;

R ² signifies hydrogen, SO ₃ Y or SO ₂ CH ₂ CH ₂ OH or -NHCH ₂ CH ₂ OH;

R ³ and R ⁴ signify independently of each other hydrogen, methyl or methoxy;

R ⁵ signifies hydrogen or SO ₃ Y;

R ⁶ signifies hydrogen or SO ₃ Y;

R ⁷ signifies hydrogen or methyl;

R ⁸ signifies -(CH ₂ ) _n -phenyl or -(CH ₂ ) _n -phenyl substituted with SO ₃ Y, wherein n

= 1 , 2;

R ⁹ signifies methyl or ethyl; with the proviso that R ⁵ and R ⁶ do not both signify SO ₃ Y at the same time.

[0018] In one embodiment, said unbranched C ₁ -C ₆ -alkyl groups or branched C ₃ -C ₆ -alkyl groups as defined with respect to R ¹ , R ² , R ³ or R ⁴ , R ⁷ , or R ⁸ and R ⁹ , or said unbranched C ₁ -C ₆ -alkoxy or branched C ₃ -C ₆ -alkoxy as defined with respect to R ³ and R ⁴ , or said unbranched C ₁ -C ₁₂ -alkoxy or branched C ₃ -C ₁₂ -alkoxy as defined with respect to R ⁷ may independently from one another bear one or more substituents selected from hydroxyl groups or cyano groups.

[0019] In one embodiment, said phenyl group as defined with respect to R ⁷ may be substituted with one or more of C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen or nitro. [0020] The invention further relates to a process for preparing a compound defined in formula (I), wherein the process comprises a compound of formula (II)

being diazotized and coupled onto one equivalent of a compound of formula (III),

the resulting amine of formula (IV)

being diazotized and coupled onto one equivalent of a compound of formula (V)

and the resulting amine of formula (VI)

being diazotized and coupled onto one equivalent of a compound of formula (VII)

wherein the R ¹ to R ⁹ radicals are each as defined with respect to formula (I).

[0021] The invention further relates to the use of a compound as defined in formula (I), or use of a compound prepared according to the process for preparing a compound of formula (I) in a dyeing process or a printing process, preferably a process for dyeing or printing a substrate, in particular a fibrous substrate, preferably of fibrous material comprising or consisting of at least one natural polyamide, preferably selected from wool or silk, or at least one synthetic polyamide, preferably selected from nylon or mixtures thereof.

[0022] In one embodiment, a compound as defined in formula (I), or a compound prepared according to the process for preparing a compound of formula (I) is used as blue component in a trichromatic dyeing or trichromatic printing process.

[0023] The invention further relates to a process for dyeing or printing a substrate, wherein the process is a trichromatic dyeing or trichromatic printing process for the manufacturing of a color-containing substrate, wherein the blue component used in the trichromatic dyeing or trichromatic printing process is a compound as defined in formula (I), or a compound prepared according to the process for preparing a compound of formula (I).

[0024] The invention further relates to a colour-containing substrate prepared according to the process for preparing a compound of formula (I).

[0025] The invention further relates to a dye composition, comprising at least one compound of formula (I), preferably a blue dye, or prepared according to the process according to the invention.

[0026] In one embodiment, the composition further comprises a yellow and a red dye. [0027] The invention also extends to the following items 1 to 15: 1. Compound of formula (I)

(I) and mixtures thereof wherein

R ¹ signifies hydrogen, unsubstituted unbranched CrC ₆ -alkyl or unsubstituted branched C ₃ -C ₆ -alkyl, or substituted unbranched C ₁ -C ₆ - alkyl or substituted branched C ₃ -C ₆ -alkyl, or SO ₃ Y, or SO2CH ₂ CH ₂ OH,

R ² signifies hydrogen, unsubstituted unbranched CrC ₆ -alkyl or unsubstituted branched C ₃ -C ₆ -alkyl, or substituted unbranched C ₁ -C ₆ - alkyl or substituted branched C ₃ -C ₆ -alkyl, SO ₃ Y, or SO ₂ CH ₂ CH ₂ OH, or -NHCH ₂ CH ₂ OH,

R ³ and R ⁴ signify independently from each other hydrogen, unsubstituted unbranched C ₁ -Ce-alkyl or unsubstituted branched C ₃ -C ₆ -alkyl, or substituted, unbranched C ₁ -C ₆ -alkyl or substituted branched C ₃ -C ₆ -alkyl, unsubstituted unbranched C ₁ -C6-alkoxy or unsubstituted branched C ₃ - C ₆ -alkoxy, or substituted unbranched C ₁ -C ₆ -alkoxy or substituted branched C ₃ -C ₆ -alkoxy,

R ⁵ signifies hydrogen or SO ₃ Y,

R ⁶ signifies hydrogen or SO ₃ Y,

R ⁷ signifies hydrogen, unsubstituted unbranched CrC ₆ -alkyl or unsubstituted branched C ₃ -C ₆ -alkyl, or substituted unbranched C ₁ -C ₆ - alkyl or substituted branched C ₃ -C ₆ -alkyl, substituted or unsubstituted phenyl, or unsubstituted unbranched CrC ₁₂ -alkoxy, or unsubstituted branched C ₃ -C ₁₂ -alkoxy, or substituted unbranched C ₁ -C ₁₂ -alkoxy, or substituted branched C ₃ -C ₁₂ -alkoxy, or NH ₂ ,

R ⁸ and R ⁹ signify independently from each other unsubstituted unbranched C ₁ -C ₆ - alkyl or unsubstituted branched C ₃ -C ₆ -alkyl, or substituted unbranched C ₁ -C ₆ - alkyl or substituted branched C ₃ -C ₆ -alkyl, or aryl, or -(CH ₂ ) _n -aryl with n = 1 , 2, 3 or 4, where the aryl radicals may be substituted; wherein Y signifies H ⁺ or an alkali metal cation, preferably Na ⁺ or K ⁺ ; and wherein said compound of formula (I) contains at least one anionic group. Compound according to item 1 , wherein the compound of formula (I) contains one, or two, or three anionic groups, preferably at least one SO ₃ Y-group, more preferably two SO ₃ Y-groups. Compound according to at least one of the preceding items 1 or 2, wherein R ¹ signifies hydrogen or SO ₃ Y, or SO ₂ CH ₂ CH ₂ OH. Compound according to at least one of the preceding items 1 to 3, wherein R ² signifies hydrogen, SO ₃ Y, or -NHCH ₂ CH ₂ OH. Compound according to at least one of the preceding items 1 to 4, wherein R ³ and R ⁴ signify independently of other hydrogen, or unsubstituted unbranched C ₁ -C ₄ - alkyl, or unsubstituted branched C ₃ -C ₄ -alkyl, or substituted unbranched C ₁ -C ₄ -alkyl, or substituted branched C ₃ -C ₄ -alkyl. Compound according to at least one of the preceding items 1 to 5, wherein R ⁷ signifies hydrogen, or NH ₂ , or unsubstituted unbranched C ₁ -C ₄ -alkyl, or unsubstituted branched C ₃ -C ₄ -alkyl, or substituted unbranched C ₁ -C-4-alkyl, or substituted branched C ₃ -C ₄ -alkyl, preferably methyl or ethyl. Compound according to at least one of the preceding items 1 to 6, wherein R ⁸ signifies substituted or unsubstituted -(CH ₂ ) _n -phenyl, wherein n = 1 , 2, 3 or 4; or substituted or unsubstituted -(CH ₂ ) _n -naphthyl, wherein n = 1 , 2, 3 or 4 . Compound according to at least one of the preceding items 1 to 7, wherein R ⁸ signifies a -(CH ₂ )i-2-phenyl group, or a -(CH ₂ )i-2-phenyl group wherein the phenyl radical is substituted with one SO ₃ Y or with one nitro group. Compound according to at least one of the preceding items 1 to 8, wherein R ⁹ signifies unsubstituted unbranched C ₁ -C ₄ -alkyl, or unsubstituted branched C ₃ -C ₄ - alkyl, or substituted unbranched C ₁ -C ₄ -alkyl, or substituted branched C ₃ -C ₄ -alkyl. Compound according to at least one of the preceding items 1 to 9, wherein

R ¹ signifies hydrogen or SO ₃ Y or SO ₂ CH ₂ CH ₂ OH;

R ² signifies hydrogen, SO ₃ Y, or SO ₂ CH ₂ CH ₂ OH or -NHCH ₂ CH ₂ OH;

R ³ and R ⁴ signify independently of each other hydrogen, methyl or methoxy;

R ⁵ signifies hydrogen or SO ₃ Y;

R ⁶ signifies hydrogen or SO ₃ Y;

R ⁷ signifies hydrogen or methyl;

R ⁸ signifies -(CH ₂ ) _n -phenyl or -(CH ₂ ) _n -phenyl substituted with SO ₃ Y, wherein n = 1 , 2;

R ⁹ signifies methyl or ethyl; with the proviso that R ⁵ and R ⁶ do not both signify SO ₃ Y at the same time. A process for preparing a compound according to at least one of the preceding items 1 to 10, wherein the process comprises a compound of formula (II)

being diazotized and coupled onto one equivalent of a compound of formula (III),

the resulting amine of formula (IV)

being diazotized and coupled onto one equivalent of a compound of formula (V)

and the resulting amine of formula (VI)

being diazotized and coupled onto one equivalent of a compound of formula (VII)

wherein the R ¹ to R ⁹ radicals are each as defined in at least one of the preceding claims 1 to 10.

Use of a compound according to at least one of the preceding items 1 to 10, or use of a compound prepared according to the process of item 11 in a dyeing process or a printing process, preferably a process for dyeing or printing a substrate, in particular a fibrous substrate, preferably of fibrous material comprising or consisting of at least one natural polyamide, preferably selected from wool or silk, or at least one synthetic polyamide, preferably selected from nylon or mixtures thereof.

13. Use according to item 12, wherein a compound according to at least one of the preceding items 1 to 10, or a compound prepared according to the process of item 1 1 , is used as blue component in a trichromatic dyeing or trichromatic printing process.

14. Process for dyeing or printing a substrate, wherein the process is a trichromatic dyeing or trichromatic printing process for the manufacturing of a color-containing substrate, wherein the blue component used in the trichromatic dyeing or trichromatic printing process is a compound according to at least one of the preceding items 1 to 10, or a compound prepared according to the process of item 11.

15. Colour-containing substrate prepared according to the process according to item 14.

DETAILED DESCRIPTION OF THE INVENTION

[0028] The SO ₃ Y group in the compound of formula (I) may be termed as an anionic group. This group is capable of forming a S0 ₃ - group as an anion. Suitable counterions Y ⁺ are preferably H ⁺ , or alkali metal ions such as Na ⁺ and K ⁺ ions, or earth alkali metal ions such as Ca ²⁺ and Mg ²⁺ ions, or ammonia cation.

[0029] Although the compounds of formula (I) may contain more than one or two SO ₃ Y groups, it is preferred that said compounds contain two SO ₃ Y groups. [0030] In one embodiment, said unbranched C ₁ -C ₆ -alkyl groups or branched C ₃ -C ₆ -alkyl groups as defined with respect to R ¹ , R ² , R ³ or R ⁴ , or R ⁷ , or R ⁸ and R ⁹ , or said unbranched d-C6-alkoxy or branched C ₃ -C ₆ -alkoxy as defined with respect to R ³ and R ⁴ , or said unbranched C ₁ -C ₁₂ -alkoxy, or branched C ₃ -C ₁₂ -alkoxy as defined with respect to

R ⁷ may independently from one another bear one or more substituents selected from hydroxyl groups, cyano groups, amino groups, nitro groups, halogen groups or aryl groups, preferably phenyl groups.

[0031] Preferably, the substituents of the branched C ₃ -C ₆ -alkyl groups or unbranched C _1- C ₆ -alkyl groups and of the unbranched C ₁ -C ₆ -alkoxy groups or branched C ₃ -C ₆ -alkoxy groups are hydroxyl groups, cyano groups, amino groups, nitro groups, halogen groups or aryl groups, preferably phenyl groups.

[0032] Methyl, ethyl, propyl are preferred C ₁ -C ₃ alkyl groups, wherein methyl and ethyl are particularly preferred. Methoxy and ethoxy are preferred C-1-C2 alkoxy groups, wherein methoxy is particularly preferred.

[0033] Preferably, aryl is phenyl or naphthyl.

[0034] In one embodiment, said phenyl group as defined with respect to R ⁷ may be substituted with one or more of C ₁ -C ₄ -alkyl groups, C^C^-alkoxy groups, halogen or nitro groups.

[0035] Thus, in the meaning of the invention, terms such as "unbranched CrCe-alkyl, branched C ₃ -C ₆ -alkyl, unbranched C^-Cs-alkoxy, branched Cs-Ce-alkoxy, unbranched C _r C ₁₂ -alkoxy, or branched C ₃ -C ₁₂ -alkoxy, phenyl ¹ include both the respective unsubstituted groups as well as the groups bearing the substituents defined herein. [0036] The compounds of the above-defined formula (I) may be prepared by suitable diazotation and coupling reactions. Diazotization and coupling conditions can be chosen by analogy with customary diazotization and coupling reactions.

[0037] For diazotization, for example, the particular amine is cooled down to 0 - 10 °C, preferably to 0 - 5 °C, and diazotized by addition of nitrosylsulfuric acid or sodium nitrite. Thereafter, the diazotized amine is allowed to react with the corresponding coupling component, preferably in aqueous solution.

[0038] The dyes of formula (I) can be isolated from the reaction medium by conventional processes, for example by salting out with an alkali metal salt, filtering and drying, if appropriate under reduced pressure and at elevated temperature.

[0039] Depending on the reaction and/or isolation conditions, the dyes of formula (I) can be obtained as free acid, as salt or as mixed salt which contains, for example, one or more cations selected from alkali metal ions, for example the sodium ion, or an ammonium ion or alkylammonium cation, for example mono-, di- or trimethyl- or - ethylammonium cations. The dye can be converted by conventional techniques from the free acid into a salt or into a mixed salt, or vice versa, or from one salt form into another. If desired, the dyes can be further purified by diafiltration, in which case undesired salts and synthesis by-products are separated off from the crude anionic dye.

[0040] The removal of undesired salts and synthesis by-products and partial removal of water from the crude dye solution can be carried out by means of a semipermeable membrane by applying a pressure, whereby the dye is obtained without the undesired salts and synthesis by-products as a solution, and, if necessary, as a solid body in a conventional manner. [0041] The dyes of formula (I) and their salts are particularly suitable for dyeing or printing fibrous material consisting of natural or synthetic polyamide in violet to black shades. The dyes of formula (I) and their salts are suitable for producing ink-jet printing inks and for using these ink-jet printing inks to print fibrous material which consists of natural or synthetic polyamide or cellulose (paper for example).

[0042] The invention accordingly provides from another aspect for the use of the dyes of formula (I), their salts and mixtures for dyeing and/or printing fibrous materials containing or consisting of natural or synthetic polyamides. A further aspect is the production of ink- jet printing inks and their use for printing fibrous materials containing or consisting of natural or synthetic polyamides.

[0043] Dyeing is carried out as per known processes. Preference is given to dyeing in the exhaust process at a temperature of 30 to 140 °C, more preferably 80 to 120 °C, and most preferably at a temperature of 80 to 100 °C, and at a liquor ratio in the range from 3:1 to 40:1.

[0044] The substrate to be dyed can be present in the form of yarn, woven fabric, loop- forming knitted fabric or carpet, for example. Fully fashioned dyeings are even perfectly possible on delicate substrates, examples being lamb-wool, cashmere, alpaca and mohair. The dyes of the invention are particularly useful for dyeing fine-denier fibres (microfibres).

[0045] The dyes according to the present invention and their salts are highly compatible with known acid dyes. Accordingly, the dyes of formula (I), their salts or mixtures can be used alone in a dyeing or printing process or else as a component in a combination shade dyeing or printing composition together with other acid dyes of the same class, i.e. with acid dyes possessing comparable dyeing properties, such as for example fastness properties and exhaustion rates from the dye bath onto the substrate. The dyes of the present invention can be used in particular together with certain other dyes having suitable chromophores. The ratio in which the dyes are present in a combination shade dyeing or printing composition is dictated by the hue to be obtained.

[0046] The novel dyes of formula (I), as stated above, are very useful for dyeing natural and synthetic polyamides, i.e. wool, silk and all nylon types, on each of which dyeings having a high fastness level, especially good light fastness and good wet fastness (washing, alkaline perspiration) are obtained. The dyes of formula (I) and their salts have a high rate of exhaustion. The ability of the dyes of formula (I) and their salt to build up is likewise very good. On-tone dyeings on the identified substrates are of outstanding quality. All dyeings moreover have a constant hue under artificial light. Furthermore, the fastness to decating and boiling is good.

[0047] One decisive advantage of the novel dyes is that they are metal free and provide very homogeneous dyeings.

[0048] The compounds according to the invention can be used as an individual dye or, owing to their good compatibility, else as a combination element with other dyes of the same class having comparable dyeing properties, for example with regard to general fastness, exhaustion value, etc. The obtained combination dyeings have similar fastness compared to dyeings with the individual dye.

[0049] The dyes of formula (I) according to the invention can also be used as blue components in trichromatic dyeing or printing. Trichromatic dyeing or printing can utilize all customary and known dyeing and printing processes, such as, for example, the continuous process, exhaustion process, foam dyeing process and ink-jet process.

[0050] The composition of the individual dye components in the trichromatic dye mixture used in the process of the invention depends on the desired hue. A brown hue, for example, preferably utilizes 20 - 40% by weight of a yellow component, 40 - 60% by weight of an orange or red component and 10 - 20% by weight of the blue component according to the invention.

[0051] The blue component can, as described above, consist of a single component or of a mixture of different blue individual components conforming to formula (I). Preference is given to double and triple combinations.

[0052] Thus, the invention further relates to a dye composition, comprising at least one compound of formula (I), preferably wherein the compound is a blue dye.

[0053] In one embodiment, the composition further comprises a yellow and a red dye.

[0054] In the following examples, parts and percentages are by weight and temperatures are reported in degrees Celsius.

EXAMPLES

Preparation Example 1

[0055] 34.6 parts of 1-aminobenzene-3-sulfonic acid were introduced into a mixture of 100 parts of ice and 25 parts by volume of approximately 30% strength aqueous hydrochloric acid and stirred for a period of about 30 minutes. At 0 to 5 °C, then, 35 parts by volume of a 40% strength sodium nitrite solution were added in a dropwise manner within a period of 30 minutes. The temperature was maintained at 0 to 5 °C during the addition by addition of ice. After the diazotization had ended, excess sodium nitrite was destroyed with amidosulfonic acid. [0056] 24.6 parts of p-xylidene were suspended in 300 parts of water. The suspension was adjusted to a p _H of 9-9.5 with sodium carbonate. The diazo suspension was then added in the course of a period of 30 minutes with vigorous stirring. During the addition, the PH was maintained at about 9 by metered addition of sodium carbonate solution.

[0057] After the coupling reaction had ended, 50 parts by volume of approximately 30% strength aqueous hydrochloric acid were added and stirred in for a period of about 30 minutes. The resulting compound of the formula (VIII)

was salted out with sodium chloride, filtered off and dried at 50 °C under reduced pressure.

[0058] A suspension of 44.7 parts of 1-aminonaphthalene-6-sulfonic acid in 250 parts of water was admixed with a diazonium salt solution prepared in a conventional manner from 44.7 parts of the amino azo compound (VIII) and 56.5 parts by volume of 40% sodium nitrite solution at 0 to 5 °C. After coupling had ended, the resulting amino dye of the formula (IX)

was left in suspension and diazotized again as described above. The diazonium salt solution thus obtained was added within a period of 30 minutes to a solution of 59.0 parts of 3-N-ethyl-N-benzylamino-1-methylbenzene in 150 parts by volume of water with stirring. During the addition, the p _H was maintained between 4 and 4.5 by metered addition of sodium carbonate solution. After the coupling reaction has ended, the PH is adjusted to about 7.5 and the resulting dye of the following formula

is salted out with sodium chloride, filtered off and dried at 50 °C at reduced pressure. On wool and especially on polyamide fibers it produces blue dyeings having good light and wet fastness properties (lambda(max) (λ _max ) = 596 nm).

Preparation Examples 2 to 100

[0059] The following table contains dyes of the general formula (I) prepared similarly to the method described in Preparation Example 1 by using the corresponding starting materials. These dyes provide blue dyeings on polyamide fibers and wool with very good light and wet fastness.

(I)

Application Example A

[0061] A dye bath at 40 °C, consisting of 2,000 parts of water, 1 part of a weakly cation- active levelling agent which is based on an ethoxylated aminopropyl fatty acid amide and which has affinity for dye, 0.25 part of the dye of Preparation Example 1 and adjusted to a p _H of 5 with 1-2 parts of 40% aqueous acetic acid is entered with 100 parts of nylon-6 fabric. After 10 minutes at 40 °C, the dye bath is heated to 98 °C at a rate of 1 °C per minute and then left at the boil for 45-60 minutes. Thereafter it is cooled down to 70 °C over a period of 15 minutes. The dyeing is removed from the bath, rinsed with hot and then with cold water and dried. The result obtained is a blue polyamide dyeing possessing good light and wet fastness.

Application Example B

[0062] A dye bath at 40 °C, consisting of 2,000 parts of water, 1 part of a weakly cation- active levelling agent which is based on an ethoxylated aminopropyl fatty acid amide and which has affinity for dye, 0.3 part of the dye of Preparation Example 1 and adjusted to a p _H of 5.5 with 1-2 parts of 40% acetic acid is entered with 100 parts of nylon-6,6 fabric. After 10 minutes at 40 °C, the dye bath is heated to 120 °C at a rate of 1.5 °C per minute and then left at this temperature for 15-25 minutes. Thereafter it is cooled down to 70 °C over a period of 25 minutes. The dyeing is removed from the dye bath, rinsed with hot and then with cold water and dried. The result obtained is a blue polyamide dyeing with good levelness and having good light fastness and wet fastness.

Application Example C

[0063] A dye bath at 40 °C, consisting of 4,000 parts of water, 1 part of a weakly amphoteric levelling agent which is based on a sulfated, ethoxylated fatty acid amide and which has affinity for dye, 0.4 part of the dye of Preparation Example 1 and adjusted to p _H 5 with 1-2 parts of 40% acetic acid is entered with 100 parts of wool fabric. After 10 minutes at 40 °C, the dye bath is heated to boiling at a rate of 1 °C per minute and then left at the boil for 40-60 minutes. Thereafter it is cooled down to 70 °C over a period of 20 minutes. The dyeing is removed from the bath, rinsed with hot and then with cold water and dried. The result obtained is a blue wool dyeing possessing good light fastness and wet fastness.

Application Example D

[0064] 100 parts of a woven nylon-6 material are padded with a 50 °C liquor consisting of 40 parts of the dye of Preparation Example 1 ,

100 parts of urea,

20 parts of a nonionic solubilizer based on butyldiglycol,

15-20 parts of acetic acid (to adjust the p _H to 4),

10 parts of a weakly cation-active levelling agent which is based on an ethoxylated aminopropyl fatty acid amide and has affinity for dye, and

810-815 parts of water (to make up to 1 ,000 parts of padding liquor).

[0065] The material thus impregnated is rolled up and left to dwell in a steaming chamber under saturated steam conditions at 85-98 °C for a period of 3-6 hours for fixation. The dyeing is then rinsed with hot and cold water and dried. The result obtained is a blue nylon dyeing having good levelness in the piece and good light fastness and wet fastness.

Application Example E

[0066] A textile cut pile sheet material composed of nylon-6 and having a synthetic base fabric is padded with a liquor containing per 1 ,000 parts

1 part of dye of Preparation Example 1

4 parts of a commercially available thickener based on carob flour ether

2 parts of a nonionic ethylene oxide adduct of a higher alkylphenol 1 part of 60% acetic acid.

[0067] This is followed by printing with a paste which contains the following components per 1 ,000 parts:

20 parts of commercially available alkoxylated fatty alkylamine

20 parts of a commercially available thickener based on carob flour ether.

The print is fixed for a period of 6 minutes in saturated steam at 100 °C, rinsed and dried.

The result obtained is a level-colored cover material having a blue and white pattern.

Application Example F

[0068] A dye bath at 40 °C consisting of 2,000 parts of water, 1 part of a weakly cation- active levelling agent which is based on an ethoxylated aminopropyl fatty acid amide and has affinity for dye, 0.2 part of the red dye of Example 8 of WO2002/46318, 1.5 parts of a commercially available preparation of C.I. Acid Yellow 236 (Nylosan Yellow F-L) and 0.5 part of the blue dye of Preparation Example 1 which is adjusted to p _H 5 with 1 -2 parts of 40% acetic acid is entered with 100 parts of woven nylon-6,6 fabric. After a period of 10 minutes at 40 °C, the dye bath is heated to 98 °C at a rate of 1 °C per minute and then left at the boil for 45 to 60 minutes. This is followed by cooling down to 70 °C over a period of 15 minutes. The dyeing is removed from the bath, rinsed with hot and then with cold water and dried. The result obtained is a level gray polyamide dyeing having good light fastness and wet fastness.

[0069] Application examples A to F were also carried out with dyes according to Preparation Examples 2 to 100 with equally good results. Application example G

[0070] 3 parts of the dye according to Preparation Example 3 are dissolved in 82 parts of demineralized water and 15 parts of diethylene glycol at 60 °C. Cooling down to room temperature gives a blue printing ink which is very highly suitable for ink jet printing on paper or polyamide and wool textiles.

[0071] Application Example G was also carried out with dyes according to preparation examples 1 , 2 and 4 to 100 with equally good results.

Application Example H

[0072] A dye bath consisting of 1 ,000 parts of water, 80 parts of calcined Glauber salt, 1 part of sodium nitrobenzene-3-sulfonate and 1 part of dye from Preparation Example 1 is heated to 80 °C in the course of 10 minutes. Then, 100 parts of mercerized cotton are added. This is followed by dyeing at 80 °C for a period of 5 minutes and then heating to 95 °C in the course of 15 minutes. After a period of 10 minutes at 95 °C, 3 parts of sodium carbonate are added, followed by a further 7 parts of sodium carbonate after a period of 20 minutes and another 10 parts of sodium carbonate after a period of 30 minutes at 95 °C. Dyeing is subsequently continued at 95 °C for a period of 60 minutes. The dyed material is then removed from the dye bath and rinsed in running demineralized water for 3 minutes. This is followed by two washes for a period of 10 minutes in 5,000 parts of boiling demineralized water at a time and subsequent rinsing in running demineralized water at 60 °C for a period of 3 minutes and with cold tap water for a period of one minute. Drying leaves a brilliant blue cotton dyeing having good wet fastness. Application Example J

[0073] 0.2 parts of the dye of Preparation Example 1 are dissolved in 100 parts of hot water and the solution is cooled down to room temperature. This solution is added to 100 parts of chemically bleached sulfite pulp beaten in 2,000 parts of water in a hollander. After a period of 15 minutes of commixing the stuff is sized with resin size and aluminum sulfate in a conventional manner. Paper produced from this stuff has a blue shade with good wet fastness.

[0074] Application Examples H and J were also carried out with dyes according to Preparation Examples 2 to 100 with equally good results.