NEW BISAZO ACID DYES.

Abstract

The present invention relates to novel bisazo compounds of formula (I) (see Formula), a process for preparing the compounds, the use of the compounds in a dyeing or printing process, a process for dyeing or printing a substrate in a trichromatic dyeing or trichromatic printing process with the compounds, and further to colored substrates comprising the compound.

Description

NEW BISAZO ACID DYES FIELD OF INVENTION The invention relates to novel bisazo dyes, a process for preparing them, and their use in a dyeing process or a printing process. BACKGROUND OF THE INVENTION Bisazo dyes are known in the art. Bisazo dyes are a class of organic dyes containing at least two azo groups as chromophoric groups. Bisazo dyes are used in trichromatic dyeing or printing, especially on fibrous substrates made of cellulose or natural or synthetic polyamide. Trichromatic dyeing or printing can utilize all common and known dyeing and printing processes, such as a continuous process, exhaust process, foam dyeing process, and inkjet process. In the trichromatic dyeing process, the composition of three individual dyes produces a desired hue. Typically, the individual dye components are provided in yellow, red, and blue. WO 2010 / 130379 A1 describes a bisazo dye bearing at least one anionic substituent selected from carboxy or sulfo groups. The dye carries a naphthylene group in the vicinity of each azo group. The dyes according to WO 2010 / 130379 A1 are particularly suitable for dyeing or printing fibrous organic substrates in red and violet shades. WO 2010 / 130384 A1 describes a bisazo dye that carries at least one anionic substituent, which may be a sulfo group. The dye carries a pyridone group in the vicinity of each azo group. The dyes according to WO 2010 / 130384 A1 are particularly suitable for dyeing or printing fibrous organic substrates in yellow shades. There is a continuing need for new bisazo dyes suitable for blue dyeing, in particular, suitable as a blue component in trichromatic dyeing / printing providing good properties such as dye uniformity, color fastness and build-up behavior. OBJECT OF THE INVENTION It has therefore been an object of the present invention to provide novel bisazo dyes having improved properties such as dye uniformity (i.e. uniformity of color tone across the substrate to be dyed), color fastness (light and moisture / wash fastness, i.e. resistance of the color to fading and bleeding when exposed to light and moisture) and build-up behavior. BRIEF DESCRIPTION OF THE INVENTION The object is achieved by a bisazo dye according to the invention of the general formula (I) in its free acid, salt or mixed salt form. It has surprisingly been found that the compound of formula (I) has good dyeing characteristics, such as uniformity, light and wet / wash fastness and build-up behaviour, compared to dyes or dye mixtures known in the prior art when applied to substrates, in particular when applied to substrates with a high surface area such as microfibres. The improvement of the compound of formula (I) is achieved in particular during dyeing and printing processes, such as inkjet printing and trichromatic dyeing / printing. In a first aspect, the invention relates to a compound of formula (I) in its free acid, salt or mixed salt form cpfrQnn / Lznz / e / YiAi R1 where R1 means hydrogen or SO3 M, R2 means hydrogen or SO3 M, R3 means hydrogen or SO3 M, R4 means hydrogen or SO3 M, R5 means hydrogen, unsubstituted unbranched Ci-Cs alkyl or unsubstituted branched Cs-Cs alkyl, or substituted unbranched Ci-Cs alkyl or substituted branched Cs-Cs alkyl, substituted or unsubstituted phenyl, or unsubstituted unbranched C1-C12 alkoxy, or unsubstituted branched C3-C12 alkoxy, or substituted unbranched C1-C12 alkoxy, or substituted branched C3-C12 alkoxy, or NH2, R6 and R7 independently of one another represent unsubstituted unbranched O-Cs alkyl or unsubstituted branched Cs-Cs alkyl, or substituted unbranched Ci-Cs alkyl or substituted branched Cs-Cs alkyl, or aryl, or -(CH2)n-aryl with n = 1, 2, 3 or 4, where the aryl radicals may be substituted; with the proviso that the compound of formula (I) contains at least one anionic group, preferably a carboxy or sulfo group, and at least one cation M is selected from hydrogen cation, alkali metal cation, alkaline earth metal cation, ammonium ion and alkylammonium ion or mixtures thereof. In a second aspect the invention relates to a process for preparing a compound of formula (I) wherein the process comprises providing a compound of formula (II) diazotizing the compound of formula (II) and coupling the diazotized compound of formula (II) to the compound of formula (III) cpfrQnn / Lznz / e / YiAi to obtain the resulting amine of formula (IV) R1 diazotizing the compound of formula (IV) and coupling the diazotized compound of formula (IV) onto the compound of formula (V) HN wherein the radicals R1a and R7 are each as defined in at least one of claims 1 to 9. In a third aspect, the invention relates to the use of a compound of formula (I) as defined in at least one embodiment of the first aspect of the invention or prepared according to a process according to a third aspect of the invention in a dyeing process or a printing process, preferably a process for dyeing or printing a substrate. In further embodiments of the third aspect, the invention in particular relates to the use of a compound as defined in 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. In a fourth aspect, the invention relates to a process for dyeing or printing a substrate in a trichromatic dyeing or trichromatic printing process for the manufacture of a colored substrate, wherein the blue component used in the trichromatic dyeing or trichromatic printing process is a compound of formula (I) as defined in at least one embodiment of the first aspect of the invention or prepared according to the second aspect of the invention. 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 a blue component in a trichromatic dyeing or trichromatic printing process. In a fifth aspect, the invention relates to a colored substrate comprising a compound according to at least one of the embodiments of the first aspect of the invention or prepared according to at least one of the embodiments of the second aspect of the invention. cpfrQnn / Lznz / e / YiAi DETAILED DESCRIPTION OF THE INVENTION In a first aspect the invention relates to a compound of formula (I) where R1 means hydrogen or SO3 M, R2 means hydrogen or SO3 M, R3 means hydrogen or SO3 M, R4 means hydrogen or SO3 M, R5 means hydrogen, unsubstituted unbranched C1-C12 alkyl or unsubstituted branched Cs-Cs alkyl, or substituted unbranched C1-C12 alkyl or substituted branched Cs-Cs alkyl, substituted or unsubstituted phenyl, or unsubstituted unbranched C1-C12 alkoxy, or unsubstituted branched C3-C12 alkoxy, or substituted unbranched C1-C12 alkoxy, or substituted branched C3-C12 alkoxy, or NH2, R6 and R7 independently of each other represent unsubstituted unbranched Ci-Ca alkyl or unsubstituted branched Cs-Ca alkyl, or substituted unbranched Ci-Ca alkyl or substituted branched Cs-Ca alkyl, or aryl, or -(CEEjn-aryl with n = 1, 2, 3 or 4, where the aryl radicals may be substituted; with the proviso that the compound of formula (I) contains at least one anionic group, preferably a sulfo group, and at least one cation M is selected from hydrogen cation, alkali metal cation, alkaline earth metal cation, ammonium ion and alkylammonium ion or mixtures thereof. The compound of formula (I) provides blue dyes preferably on polyamide and wool fibers with very good light and moisture fastness. The term “anionic group” means a group capable of forming an anion and a respective counterion in the form of a cation. The SO3M group may be referred to as an anionic group. The SO3M group is capable of forming an SO3 group as an anion. Suitable counterions M+ are preferably H+, or alkali metal ions such as Na+ and K+ ions, or alkaline earth metal ions such as Ca2+ and Mg2+ ions, or ammonium cation, alkylammonium cation, for example, mono-, di-, tri- and tetramethyl or mono-, di-, tri- and tetraethylammonium ammonium cations or mixtures thereof. In the context of this application, the terms “SO3H” or “SO3” are considered to correspond to the term “sulfo” group. In this application, the term “sulfo” is understood to represent equivalently the free acid, salt, or mixed salt form. In the context of the present application, the term "free acid" refers to an anionic group, where H+ forms the counter cation. An example of a free acid is SO3H. Correspondingly, the bisazo dye of formula (I) may be referred to as being in its free acid form if the sulfo groups are in their free acid form. If the counter cation M+ of the anionic group is an alkali or alkaline earth metal cation, or an ammonium or alkylammonium cation, the anionic group can be said to be in its salt form. Correspondingly, the bisazo dye can also be said to be in its salt form. In case the counter cation M+ of the anionic group is formed by a mixture of different cations H+, alkali metal or alkaline earth ion, or ammonium cation or alkylammonium cation, the anionic group and the bisazo dye of formula (I) itself can be said to be in their mixed salt form. The term “alkali metal cation” in the context of the present application encompasses the cations of the elements of group 1 of the periodic table, except hydrogen, i.e. Li+, Na+, K+, Rb+, Cs+ and Fr+. In a preferred embodiment of the present application, the term “alkali metal cation” encompasses the cations of Li+, Na+ and K. The term “alkaline earth metal cation” in the context of the present application encompasses the cations of the elements of group 2 of the periodic table, i.e., Be2+, ​​Mg2+, Ca2+, Sr2+, Ba2+, and Ra2+. In a preferred embodiment of the present application, the term “alkaline earth metal cation” encompasses the cations of Mg2+ and Ca2+. The term “alkylammonium cation” in the context of the present application encompasses a positively charged nitrogen atom carrying four residues in total, wherein at least one residue is an alkyl residue having 1 to 10 carbon atoms and the remaining residues could be hydrogen or alkyl residue having 1 to 10 carbon atoms. As used in the context of the present application, the term “compound” encompasses any single compound or any mixture of two or more compounds of formula (I) as defined herein. Therefore, the term “compound” also encompasses mixtures of two or more compounds of formula (I) that are different with respect to their constitutional structure, their configurational structure and / or with respect to the counter cations. The compound of general formula (I) is constructed from an aminonaphthalene unit which is coupled via diazotization to an additional naphthylene ring and to a 3-N,N-dialkylamino anilide. In the context of the present application, the term "aryl" refers to a monocyclic or polycyclic residue derived from an aromatic hydrocarbon. The aryl residue may be unsubstituted, indicating, in the context of the present application, that the aromatic hydrocarbon residue carries only hydrogen atoms. The aryl residue may be substituted, indicating, in the context of the present application, that the aromatic hydrocarbon residue is substituted with heteroatoms other than hydrogen. Preferred embodiments of the aryl residue are the phenyl and naphthylene groups. The term "phenyl" in the context of the present application indicates an aromatic residue derived from benzene. The phenyl residue may be unsubstituted, indicating, in the context of the present application, that the aromatic hydrocarbon residue carries only hydrogen atoms, i.e., a residue of formula CeHs. The phenyl residue may be substituted, indicating, in the context of the present application, that the aromatic hydrocarbon residue is substituted with heteroatoms other than hydrogen. The term "naphthylene" in the context of the present application indicates an aromatic residue derived from naphthalene, i.e. a compound consisting of two fused benzene rings. The naphthyl residue could be unsubstituted indicating, in the context of the present application, that the aromatic hydrocarbon residue carries only hydrogen atoms, i.e. a residue of formula CwH?. The naphthylene residue could be substituted indicating, in the context of the present application, that the aromatic hydrocarbon residue is substituted with heteroatoms other than hydrogen. The substituents of the substituted aryl are selected from the group of -H, -SO3M, wherein M denotes a counter cation as defined above, linear or branched, unsubstituted or substituted C1-6 alkyl, linear or branched, unsubstituted or substituted C1-6 alkoxy. In the context of the present application, the term “substituted alkyl” or “substituted alkoxy” indicates an alkyl residue or an alkoxy residue that is substituted with heteroatoms other than hydrogen. The substituents of the substituted alkyl and alkoxy groups are selected from the group consisting of halogen, -CN, NH20 -COOM, wherein M denotes a counter cation as defined above. In further embodiments of the first aspect of the invention, the compound of formula (I) contains one, or two, or three or four SO3M groups, preferably the number of sulfo groups in the compound of formula (I) is equal to 2. In one embodiment of the first aspect of the invention, in R5, R6, R7 methyl, ethyl, and propyl are preferred C1-C3 alkyl groups, wherein methyl and ethyl are particularly preferred. In a further embodiment of the first aspect of the invention, in R5methoxy and ethoxy are preferred C1-C2 alkoxy groups, wherein methoxy is particularly preferred. In a further embodiment of the first aspect of the invention, in R6, R7aryl is unsubstituted or substituted phenyl or naphthylene group. In a further embodiment, R1 is attached to the 4-position. The numbers on the naphthylene ring presented in formula (a) shown below will be used to describe the substitution pattern. cpfrQnn / Lznz / e / YiAi In a further embodiment of the first aspect of the invention, R2 is sulfo and is attached to the 5, 6, or 7 position. In further embodiments of the first aspect of the invention, the number of SO3M groups is equal to two, wherein R1 and R4, or R1 and R3, or R2 and R4, or R2 and R3, represent SO3M. In further embodiments of the first aspect of the invention, the number of SO3M groups in the compound of formula (I) is equal to two, wherein R1 and R4 mean SO3M and R1 is at position 4, or where R1 and R3 stand for SO3M and R1 is at position 4, or where R2 and R4 stand for SO3M and R2 is at position 7, or where R2 and R3 stand for SOsM and R2 is on position 7, or where R2 and R4 stand for SO3M and R2 is at position 5, or where R2 and R3 stand for SO3M and R2 is at position 5, or where R1 and R2 mean SO3M and R1 is at position 4, and Rz is at position 6, or where R2 and R4 stand for SOsM and R2 is at position 6, or where R2 and R3 stand for SO3M and R2 is at position 6. In a further embodiment of the first aspect of the invention, in the compound of formula (I) R5 represents unsubstituted unbranched Ci-Cs alkyl. In one embodiment, R5 represents unsubstituted unbranched Ci-Ce alkyl or may represent unsubstituted unbranched C1-C4 alkyl, or unsubstituted methyl, or unsubstituted ethyl, or unsubstituted unbranched propyl, or unsubstituted unbranched butyl, wherein methyl or unsubstituted ethyl are preferred. In a further embodiment of the first aspect of the invention, in the compound of formula (I) R6 and R7 independently denote unsubstituted unbranched C1-C6 alkyl or unsubstituted branched C3-C4 alkyl or substituted unbranched C1-Cs alkyl or substituted branched C3-C4 alkyl. In particular, R6 and R7 may independently denote unsubstituted methyl, or unsubstituted ethyl, or unsubstituted unbranched propyl, or unsubstituted unbranched butyl, or unsubstituted unbranched pentyl, or unsubstituted unbranched hexyl, or substituted methyl, or substituted ethyl, or substituted unbranched propyl, or substituted unbranched butyl, or substituted unbranched pentyl, or substituted unbranched hexyl, or unsubstituted branched propyl, or unsubstituted branched butyl, or substituted branched propyl, or substituted branched butyl. R6 and R7 can mean the same substituents or they can mean different substituents.In particular, R6 represents unsubstituted unbranched C1-C2 alkyl and R7 represents unsubstituted branched C3-C4 alkyl or substituted branched C3-C4 alkyl, and vice versa. Alternatively, R6 represents substituted unbranched C1-C2 alkyl and R7 represents unsubstituted branched C3-C4 alkyl or substituted branched C3-C4 alkyl, and vice versa. In a further embodiment, wherein R5 represents substituted unbranched C1-C12 alkyl or substituted branched Cs-Cs alkyl, substituted phenyl, or substituted unbranched C1-C12 alkoxy, or substituted branched C3-C12 alkoxy, the substituents on R5 represent -OH, -CN or NH2. In a further embodiment, wherein R6 and R7 independently of each other represent substituted unbranched Cs-Cs alkyl or substituted branched Cs-Cs alkyl, or aryl, or -(CH2)naryl with n = 1, 2, 3 or 4, wherein the aryl radical may be substituted, the substituents on R6 and R7 represent -OH, -CN or NHa. In certain embodiments, R6 and R7 may independently of each other represent cyanoethyl or hydroxyethyl. Compounds of formula (I) defined above can be prepared by suitable diazotization and coupling reactions. The diazotization and coupling conditions can be chosen by analogy with conventional diazotization and coupling reactions. Therefore, a second aspect of the invention relates to a process for preparing a compound of formula (I) wherein the process comprises providing a compound of formula (II) crfrQnn / Lznz / e / YiAi diazotizing the compound of formula (II) and coupling the diazotized compound of formula (II) onto the compound of formula (III), to obtain the resulting amine of formula (IV) R1 diazotizing the compound of formula (IV) and coupling the diazotized compound of formula (IV) to the compound of formula (V) (V) wherein R1a and R7 are each as defined in any of the embodiments according to the first aspect of the invention. In one embodiment of the second aspect of the invention, the diazotization is carried out at 10°C to +10°C, preferably at -5°C to +10°C. The diazotized amine is then allowed to react with the corresponding coupling component, preferably in aqueous solution. The compound of formula (I) can be isolated from the reaction medium by conventional processes, for example by salification with an alkali metal salt, filtration and drying, if appropriate under reduced pressure and at elevated temperature. Depending on the reaction and / or isolation conditions, the compound of formula (I) may be obtained in its free acid, salt, or as a mixed salt form containing, for example, one or more M+ cations selected from alkali metal cations, for example, sodium ion, or an ammonium ion or alkylammonium cation, for example, mono-, di-, or trimethyl or ethylammonium cations. The compound may be converted by conventional techniques from the free acid to a salt or a mixed salt, or vice versa, or from one salt form to another. If desired, the compound of formula (I) may be further purified by diafiltration, in which case unwanted salts and synthesis by-products are separated from the crude compound of formula (I). The removal of unwanted salts and synthesis by-products and partial removal of water from the crude solution of the compound of formula (I) can be carried out by means of a semipermeable membrane by applying a pressure, whereby the compound of formula (I) is obtained without the unwanted salts and synthesis by-products as a solution and, if necessary, as a solid body in a conventional manner. In a third aspect, the invention therefore relates to the use of a compound of formula (I) as defined in any of the embodiments of the first aspect of the invention or prepared according to the second aspect of the invention in a dyeing process or a printing process, in particular a trichromatic dyeing / printing process, preferably a process for dyeing or printing a substrate. The term “substrate” as used herein encompasses all substrates of natural or synthetic origin. The substrate may be present in the form of a textile (i.e. material comprising or consisting of natural or synthetic polyamides such as wool, silk and all types of nylon, cellulose or cotton), or in the form of a plastic article. The term “substrate” also encompasses hydroxy- or nitrogen-containing materials. In preferred embodiments, the substrate is a plastic object, preferably a 3D printed plastic object, or a fibrous substrate, preferably a 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. The substrate to be dyed may be in the form of yarn, woven fabric, cloth, or loop-knit rug, for example. Fully woven dyeing is even perfectly possible on delicate substrates; examples include lamb's wool, cashmere, alpaca, and mohair. The dyes of the invention are particularly useful for dyeing fine denier fibers (microfibers). cpfrQnn / Lznz / e / YiAi Additional examples of the form / appearance of the substrate are yarn, woven fabric, loop-knit woven fabric carpet comprising or consisting of an organic substrate, for example, natural or synthetic polyamides (for example wool, silk and all types of nylon), polyurethanes, cellulose as well as hydrophobic and non-absorbent substrates, for example plastics, metal and glass. Substrates for dyeing may also be leather and fibrous materials, comprising natural or synthetic polyamides and, in particular, natural or regenerated cellulose such as cotton, spun rayon and viscose. In one embodiment, the dyeing substrates are textiles comprising cotton. Suitable substrates that can be dyed using the compound of formula (I), in particular for printing, are paper, plastic, textiles, metal, glass, or an overhead projector slide. Suitable plastic objects that can be dyed using the compound of formula (I) can be formed by any traditional methods known in the art, such as molding methods. Furthermore, the plastic object can be formed by newly developed methods, such as 3D printing methods. Commonly known 3D printing methods are, for example, binder jetting, triple jetting (also known as PolyJet, MultiJet), stereolithography (SLA), digital light processing (DLP), multijet printing, fused deposition modeling (FDM), selective heat sintering (SHS), selective laser sintering (SLS), laminated object manufacturing (LOM), wax deposition modeling (WDM), three-dimensional inkjet printing (3DP), thermoplastic extrusion, soft bend printing, selective deposition lamination, hybrid CNC, fused filament fabrication (FFF). Dyeing is carried out according to known processes. The term “exhaustion dyeing process” as used herein is to be understood as a process in which the dye is gradually transferred from a relatively large volume dye bath to the organic substrate whereby it is dyed over a relatively long period of time (see A Review of Textile Dyeing Processes, Perkins W. S, 1991. Textile Chemist & Colorist vol. 23(8) 23-27). Preference is given to dyeing in the exhaustion process at a temperature of 30 to 140°C. The dyeing process can be carried out in temperature ranges from 40 to 100°C, or 50 to 80°C; in other embodiments, temperature ranges from 80 to 120°C, or from 80 to 100°C may be used, depending on the thermal softening behavior of the plastic article. The liquor ratio is in the range from 3:1 to 40:1. In a further embodiment, the dyeing process may be a continuous dyeing process. The term "continuous dyeing process," as used herein, is to be understood as a process in which the substrate to be dyed is continuously fed into a dye bath. Examples of a continuous dyeing process are the steam pad process or the dry pad process. In one embodiment, the compound of formula (I), in its free acid, salt or mixed salt form, is particularly suitable for printing fibrous material consisting of natural or synthetic polyamide in violet to black shades. The compound of formula (I) and its salts are also suitable for producing inkjet printing inks and for using these inkjet printing inks for printing substrates such as plastic objects, in particular 3D printed plastic objects, or fibrous material consisting of natural or synthetic polyamide or cellulose (paper, for example). In a fourth aspect, therefore, the invention relates to a process for dyeing or printing a substrate in a trichromatic dyeing or trichromatic printing process for the manufacture of a colored substrate, wherein the blue or violet component used in the trichromatic dyeing or trichromatic printing process is a compound of formula (I) as defined in any of the embodiments of the first aspect of the invention, or prepared according to any of the embodiments of the second aspect of the invention. In a fifth aspect, the invention relates to a colored substrate comprising a compound of formula (I) according to any of the embodiments of the first aspect of the invention, or prepared according to any of the embodiments of the second aspect of the invention. In preferred embodiments, the substrate is selected from cellulose, preferably paper, or natural polyamide, preferably wool or silk, or synthetic polyamide, preferably nylon. The compound of formula (I) according to the present invention in its free acid, salt or mixed salt form is highly compatible with known acid dyes. Accordingly, the compound of formula (I) can be used alone in a dyeing or printing process or also as a component in a combined tone 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 of the dye bath on the substrate. The compound of formula (I) of the present invention can in particular be used together with certain other dyes having suitable chromophores. The combined dyes obtained have a similar fastness compared to dyes with the individual dye. The ratio in which the dyes are present in a combined tone dyeing or printing composition is dictated by the hue to be obtained. The compound of formula (I), as indicated above, is very useful for dyeing natural and synthetic polyamides, i.e., wool, silk, and all types of nylon, and plastic objects, particularly 3D-printed plastic objects, each of which produces dyes with a high level of fastness, especially good light fastness and good moisture fastness (washing, alkaline perspiration). The compound of formula (I) in its free acid, salt, or mixed salt form has a high exhaustion rate. The ability of the compound of formula (I) in its free acid, salt, or mixed salt form to accumulate is also very good. The tone dyes on the identified substrates are of excellent quality. Furthermore, all dyes have a consistent hue under artificial light. Furthermore, the fastness to settling and boiling is good. A decisive advantage of the compounds of formula (I) according to the invention is that they are metal-free and provide highly homogeneous dyes. In the context of the present application, the term "metal" refers to centered metals that are bound by coordinative bonds to the dye compounds. These dyes are referred to as metal complex dyes. However, within the meaning of the present application, the term "metal-free" does not extend to alkali metal or alkaline earth metal ions, as exemplified throughout the present application. The compounds of formula (I) according to the invention can also be used as blue components in trichromatic dyeing or printing. Trichromatic dyeing or printing can be carried out using all conventional and known dyeing and printing processes, such as, for example, the continuous process, the exhaust process, the foam dyeing process, and the inkjet process. cpfrQnn / Lznz / e / YiAi The blue component, as described above, may consist of a single component or a mixture of different individual blue components according to formula (I). Preference is given to double and triple combinations. The present invention is further illustrated by the following preferred examples or embodiments thereof, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention. In the following examples, unless otherwise indicated, parts and percentages are by weight and temperatures are reported in degrees Celsius. EXAMPLES Preparation Example 1 111.6 parts of 1-aminonaphthalene-4-sulfonic acid were mixed with 750 parts of water. The pH of the resulting suspension was adjusted to 9.5 to 10 by the addition of 0.5 parts by volume of 30% aqueous sodium hydroxide and stirred for a period of 30 minutes. 90.6 parts by volume of a 40% sodium nitrite solution were added at 20°C to 25°C in a dropwise manner over a period of 30 minutes. The resulting suspension was then added dropwise within 60 to 90 minutes into a beaker charged with 500 parts of water, 500 parts of ice, and 127 parts by volume of approximately 30% aqueous hydrochloric acid. The temperature was maintained during the addition within the range of -5°C to +10°C by adding ice. After the diazotization was complete, the excess sodium nitrite was destroyed with amidosulfonic acid. 111.6 parts of 1-aminonaphthalene-6-sulfonic acid were suspended in 850 parts of water. The suspension was adjusted to a pH of 3 to 3.5 with hydrochloric acid. The diazo suspension was then added over a period of 90 to 120 minutes with vigorous stirring. During the addition, the pH was maintained at approximately 3.5 by the measured addition of sodium carbonate solution. After the coupling reaction is completed, the resulting compound of formula (VI) HO3S was salted with sodium chloride, filtered and dried at 50°C under reduced pressure. A suspension of 131.2 parts of 3-N,N-diethylamino-1-acetanilide in 400 parts of water was mixed with a diazonium salt solution prepared in a conventional manner from 228.8 parts of the amino azo compound (VI) and 69.9 parts by volume of 40% sodium nitrite solution at 0 to 5°C. After the coupling was completed, the resulting dye of formula (VII) cpfrQnn / Lznz / e / YiAi It was salted with sodium chloride, filtered and dried at 50°C under reduced pressure. On wool and especially on polyamide fibres it produces blue dyes that have good light and moisture fastness properties with an absorption maximum of Xmax = 599 nm, measured via UV-VIS spectrometry. Preparation Examples 2 to 58 The following table lists the compounds of formula (I) prepared according to the method described in Preparation Example 1 using the corresponding starting materials. These compounds provide blue dyes on polyamide and wool fibers with very good light and moisture fastness. Ejemplo R1 R2 R3 R4 R5 R6 R7 7max, absorción 2 4-SOsH H H -SO3H -ch3 -CH2CH3 -CH2CH3 600 3 4-SO3H H -SO3H H ch3 -ch2ch2ch2ch3 -ch2ch2ch2ch3 604 4 4-SO3H H H -SOsH ch3 -ch2ch2ch2ch3 -ch2ch2ch2ch3 604 5 4>Η H -SO3H H ch3 -(CH2)5CH3 -(CH2)5CH3 606 6 4-SO3H H H -SO3H -ch3 -(CH2)sCH3 -(CH2)5CH3 605 7 4-SO3H H -SO3H H -ch3 -(CH2)4CH3 -(CH2)4CH3 604 8 4-SO3H H H -SO3H -ch3 -(CH2)4CH3 -(CH2)4CH3 604 9 4-SO3H H -SO3H H ch3 -ch2ch2ch3 -ch2ch2ch3 602 10 4-SO3H H H -SO3H -ch3 -ch2ch2ch3 CH2CH2CH3 603 11 4-SO3H H -SO3H H -ch2ch3 -ch2ch2ch2ch3 -CH2CH2CH2CH3 605 12 4-SO3H H H SO3H -ch2ch3 -ch2ch2ch2ch3 -CH2CH2CH2CH3 604 13 4-SO3H H H -SO3H ch3 -ch2ch2oh -CH2CH2OH 601 14 4-SO3H H H -SO3H -ch2ch3 -ch2ch2oh CH2CH2OH 600 15 4-SO3H H -SO3H H ch3 -ch2ch2oh CH2CH2CN 599 16 4-SO3H H -SO3H H ch3 -CH2CH(CH3)2 CH2CH(CH3)2 604 17 H 7-SO3H H -SO3H ch3 -ch2ch2ch2ch3 -CH2CH2CH2CH3 589 > & h c h c c o 4 1 t Ejemplo R1 R2 R3 R4 R5 R6 R7 7max, absorción 18 H 7-SO3H H -SO3H CH3 -CH2CH3 -CH2CH3 590 19 H 7-SO3H -SO3H H CH3 -CH2CH2CH2CH3 -CH2CH2CH2CH3 590 20 H 7-SO3H H -SOsH CH3 -ch2ch2ch2ch3 -CH2CH2CH2CH3 589 21 H 7-SO3H -SO3H H CH3 -(CH2)5CH3 -(CH2)5CH3 588 22 H 7-SO3H H -SO3H -ch3 -(CH2)sCH3 -(CH2)5CH3 588 23 H 7-SO3H H -SO3H ch3 CH2CH2CH3 CH2CH2CH3 587 24 H 7-SO3H -SO3H H -CH2CH3 -CH2CH2CH2CH3 -CH2CH2CH2CH3 589 25 H 7-SO3H -SO3H H -ch3 -CH2CH2OH CH2CH2CN 586 26 H 5-SO3H H -SO3H -ch3 -CH2CH3 -CH2CH3 598 27 H 5-SO3H -SO3H H -ch2ch3 -CH2CH3 -CH2CH3 599 28 H 5-SO3H -SO3H H -ch3 -CH2CH2CH2CH3 -CH2CH2CH2CH3 602 29 H 5-SO3H H -SO3H -ch3 -CH2CH2CH2CH3 -CH2CH2CH2CH3 602 30 H 5-SO3H -SO3H H -ch3 -(CH2)5CH3 -(CH2)5CH3 603 31 H 5-SO3H H SO3H -ch3 -(CH2)5CH3 -(CH2)5CH3 604 32 H 5-SO3H H -SO3H ch3 -(CH2)4CH3 -(CH2)4CH3 604 33 H 5-SO3H -SO3H H ch3 CH2CH2CH3 -CH2CH2CH3 601 > & h c h c c o 4 1 t Ejemplo R1 R2 R3 R4 R5 R6 R7 7max, absorción 34 H 5-SO3H H -SO3H ch3 CH2CH2CH3 -ch2ch2ch3 602 35 H 5-SO3H -SO3H H -CH2CH3 -CH2CH2CH2CH3 -CH2CH2CH2CH3 603 36 H 5-SO3H H -SOsH ch3 ch2ch2oh ch2ch2oh 605 37 H 5-SO3H H -SOsH -ch2ch3 CH2CH2OH -ch2ch2oh 604 38 H 5-SO3H -SO3H H ch3 -CH2CH2OH -CH2CH2CN 601 39 H 5-SO3H -SO3H H ch3 -CH2CH(CH3)2 CH2CH(CH3)2 603 40 4-SO3H 6-SO3H H H ch3 ch2ch3 -ch2ch3 599 41 4-SO3H 6-SO3H H H ch3 -ch2ch2ch2ch3 -ch2ch2ch2ch3 602 42 4-SO3H 6-SO3H H H ch3 -(OH2)5CH3 -(CH2)5CH3 604 43 4-SO3H 6-SO3H H H ch3 -(CH2)4CH3 -(CH2)4CH3 604 44 4-SO3H 6-SO3H H H ch3 -ch2ch2ch3 -ch2ch2ch3 603 45 4-SO3H 6-SO3H H H ch2ch3 -CH2CH2CH2CH3 -ch2ch2ch2ch3 605 46 4-SO3H 6-SO3H H H ch3 ch2ch2oh -ch2ch2oh 603 47 4-SO3H 6-SO3H H H ch3 -CH2CH2OH -CH2CH2CN 601 48 4-SO3H 6-SO3H H H ch3 -CH2CH(CH3)2 CH2CH(CH3)2 604 49 H 6-SO3H -SO3H H ch2ch3 ch2ch3 ch2ch3 589 > & h c h c c o 4 1 t Ejemplo R1 R2 R3 R4 R5 R6 R7 7max, absorción 50 H 6-SO3H -SO3H H ch3 -CH2CH2CH2CH3 -CH2CH2CH2CH3 590 51 H 6-SO3H H -SO3H ch3 -CH2CH2CH2CH3 -ch2ch2ch2ch3 590 52 H 6-SO3H -SO3H H ch3 -(CH2)5CH3 -(CH2)5CH3 589 53 H 6-SO3H H -SOsH ch3 -CH2CH2CH2CH3 -ch2ch2ch2ch3 588 54 H 6-SO3H -SO3H H -ch2ch3 -ch2ch2ch2ch3 -ch2ch2ch2ch3 588 55 H 6-SO3H H -SO3H ch2ch3 -ch2ch2ch2ch3 -ch2ch2ch2ch3 587 56 H 6-SO3H H -SO3H ch3 ch2ch2oh ch2ch2oh 589 57 H 6-SO3H H -SO3H -CH2CH3 -CH2CH2OH ch2ch2oh 588 58 H 6-SO3H -SO3H H ch3 CH2CH2OH -ch2ch2cn 587 > & h c h c c o 4 1 t Ejemplo de Aplicación A A 40°C dyebath consisting of 2,000 parts water, 1 part of a weakly active cation matching agent based on an ethoxylated aminopropyl fatty acid amide and having affinity for the dye, 0.25 parts of the dye of Preparation Example 1 and adjusted to pH 5 with 1 to 2 parts of 40% aqueous acetic acid was introduced with 100 parts of nylon 6 fabric. After 10 minutes at 40°C, the dyebath was heated to 98°C at a rate of 1°C per minute and then allowed to boil for 45 to 60 minutes. It was then cooled to 70°C over a period of 15 minutes. The dye was removed from the bath, rinsed with hot water and then with cold water, and dried. The result obtained was a blue polyamide dye that has good fastness to light and moisture. Application Example B A dyebath at 40°C, consisting of 2,000 parts of water, 1 part of a weakly active cation-matching agent based on an ethoxylated aminopropyl fatty acid amide and having affinity for the dye, 0.3 parts of the dye of Preparation Example 1 and adjusted to pH 5.5 with 1-2 parts of 40% acetic acid, was introduced with 100 parts of nylon 6,6 fabric. After 10 minutes at 40°C, the dyebath was heated to 120°C at a rate of 1.5°C per minute and then left at this temperature for 15-25 minutes. It was then cooled to 70°C over a period of 25 minutes. The dye was removed from the dyebath, rinsed with hot water and then with cold water, and dried. The result obtained was a blue polyamide dye with good uniformity and that has good light fastness and moisture fastness. Application Example C A dyebath at 40°C, consisting of 4,000 parts of water, 1 part of a weakly amphoteric leveling agent based on an ethoxylated, sulfated fatty acid amide having affinity for the dye, 0.4 parts of the dye from Preparation Example 1 and adjusted to pH 5 with 1-2 parts of 40% acetic acid, was introduced with 100 parts of wool fabric. After 10 minutes at 40°C, the dyebath was heated to boiling at a rate of 1°C per minute and then allowed to boil for 40-60 minutes. It was then cooled to 70°C over a period of 20 minutes. The dye was removed from the bath, rinsed with hot water and then with cold water, and dried. The result obtained was a blue wool dyeing having good light fastness and moisture fastness. Application Example D 100 parts of a nylon 6 woven material were filled with a liquor at 50°C consisting of parts of the dye of Preparation Example 1, 100 parts of urea, 100 parts of a non-ionic solubiliser based on butyldiglycol, 15-20 parts of acetic acid (to adjust the pn to 4), 100 parts of a weakly active cation-matching agent based on an ethoxylated aminopropyl fatty acid amide and having affinity for the dye, and 810-815 parts water (to prepare up to 1000 parts filling liquor). The impregnated material was rolled and allowed to remain in a steam chamber under saturated steam conditions of 85 to 98°C for a period of 3 to 6 hours for fixation. The dye was then rinsed with hot and cold water and dried. The resulting dyed blue nylon exhibiting good uniformity throughout the piece and good light and moisture fastness. Application Example E A textile cut pile sheet material composed of nylon 6 and having a synthetic base fabric was filled with a liquor containing per 1,000 parts of dye of Preparation Example 1 parts of a commercially available thickener based on carob flour ether parts of a nonionic ethylene oxide adduct of a higher alkylphenol part of 60% acetic acid. This was followed by printing with a paste containing the following components per 1,000 parts: parts of a commercially available alkoxylated fatty alkylamine parts of a commercially available thickener based on carob flour ether. The print was fixed for six minutes in saturated steam at 100°C, rinsed, and dried. The resulting print was a uniformly colored cover material with a blue and white pattern. Application Example F A dyebath at 40°C consisting of 2,000 parts of water, 1 part of a weakly active cation matching agent which is based on an ethoxylated aminopropyl fatty acid amide and has affinity for the dye, 0.2 parts of the red dye of Example 8 of WO 2002 / 46318, 1.5 parts of a commercially available preparation of Acid Yellow Cl 236 (Nylosan Yellow FL) and 0.5 parts of the blue dye of Preparation Example 1 which was adjusted to pH 5 with 1-2 parts of 40% acetic acid, was introduced with 100 parts of woven nylon 6,6. After a period of 10 minutes at 40°C, the dyebath was heated to 98°C at a rate of 1°C per minute and then allowed to boil for 45 to 60 minutes. This was followed by cooling to 70°C for a period of 15 minutes. The dye was removed from the bath, rinsed with hot water and then cold water, and dried.The result obtained was a uniform grey polyamide dye that had good light fastness and moisture fastness. Application Examples A to F were also carried out with the dyes according to Preparation Examples 2 to 58 with equally good results. cpfrQnn / Lznz / e / YiAi Application Example G Three parts of the dye according to Preparation Example 3 were dissolved in 82 parts of demineralized water and 15 parts of diethylene glycol at 60°C. Cooling to room temperature produced a blue printing ink that is well suited for inkjet printing on paper or polyamide and wool textiles. Application Example G was also carried out with dyes according to preparation examples 1, 2 and 4 to 58 with equally good results. Application Example H A dyebath consisting of 1,000 parts of water, 80 parts of calcined Glauber's salt, 1 part of sodium nitrobenzene-3-sulfonate, and 1 part of the dye from Preparation Example 1 was heated to 80°C over the course of 10 minutes. Then, 100 parts of mercerized cotton were added. This was followed by dyeing at 80°C for a period of 5 minutes and then heating to 95°C over the course of 15 minutes. After a period of 10 minutes at 95°C, 3 parts of sodium carbonate were added, followed by an additional 7 parts of sodium carbonate after a period of 20 minutes and a further 10 parts of sodium carbonate after a period of 30 minutes at 95°C. Dyeing was then continued at 95°C for a period of 60 minutes. The dyed material was then removed from the dye bath and rinsed with demineralized running water for 3 minutes.This was followed by two washes for a period of 10 minutes in 5,000 parts of boiling demineralized water, and a subsequent rinse with demineralized running water at 60°C for a period of 3 minutes and with cold tap water for a period of one minute. Drying left a bright blue cotton dye that had good wet fastness. Application Example J 0.2 parts of the dye from Preparation Example 1 were dissolved in 100 parts of hot water, and the solution was cooled to room temperature. This solution was added to 100 parts of chemically bleached sulfite pulp beaten into 2,000 parts of water in a Hollander. After a 15-minute mixing period, the material was sized with rosin size and aluminum sulfate in a conventional manner. The paper produced from this material had a blue shade with good wet fastness. Application Examples H and J were also carried out with the dyes according to Preparation Examples 2 to 58 with equally good results.

Claims

1. A compound of formula (I), in its free acid, salt, or mixed salt form R1 cpfrQnn / Lznz / e / YiAi wherein R1 means hydrogen or M SO3, R2 means hydrogen or M SO3, R3 means hydrogen or M SO3, R4 means hydrogen or M SO3, R5 means hydrogen, unbranched unsubstituted Ci-Ca alkyl or unbranched unsubstituted Cs-Cs alkyl, or unbranched substituted Ci-Cs alkyl or branched substituted Cs-Ce alkyl, substituted or unsubstituted phenyl, or unbranched unsubstituted C1-C12 alkoxy, or branched unsubstituted C3-C12 alkoxy, or unbranched substituted C1-C12 alkoxy, or branched substituted C3-C12 alkoxy, or NH2, R6 and R7 independently mean O-Cs alkyl unsubstituted branched or unsubstituted branched Cs-Cs alkyl, or substituted unbranched Cs-Cs alkyl or substituted branched Cs-Cs alkyl, or unsubstituted aryl, or -(CH2)n-aryl substituted with n = 1, 2, 3 or 4,provided that the compound of formula (I) contains at least one anionic group, preferably a carboxy or sulfo group, and at least one cation M is selected from hydrogen cation, alkali metal cation, alkaline earth metal cation, ammonium cation, and alkylammonium cation, or mixtures thereof.

2. Compound according to claim 1, characterized in that R1 is SOsM and is attached to position 4.

3. Compound according to claim 1 or 2, characterized in that R2 is SO3M and is attached to position 5, 6 or 7.

4. Compound according to at least one of claims 1 to 3, characterized in that the number of SO3M groups present in the compound of formula (I) is equal to 1, 2, 3, or 4; preferably, the number of SO3M groups is equal to 2.

5. Compound according to at least one of claims 1 to 4, characterized in that in the compound of formula (I) the number of SO3M groups is equal to 2 and wherein R1 and R4, or R1 and R3, or R2 and R4, or R2 and R3 mean SO3M.

6. Compound according to claim 5, characterized in that R1 and R4 mean SO3M and R1 is in position 4, or in that R1 and R3 mean SO3M and R1 is in position 4, or in that R2 and R4 mean SO3M and R2 is in position 7, or in that R2 and R3 mean SOsM and R2 is in position 7, or in that R2 and R4 mean SO3M and R2 is in position 5, or in that R2 and R3 mean SO3M and R2 is in position 5, or in that R1 and R2 mean SO3M and R1 is in position 4, and R2 is in position 6, or in that R2 and R4 mean SO3M and R2 is in position 6, or in that R2 and R3 mean SO3M and R2 is in position 6.

7. Compound according to at least one of claims 1 to 6, characterized in that Rs means unsubstituted branched Ci-Csno alkyl, preferably methyl or ethyl.

8. Compound according to at least one of claims 1 to 7, characterized in that R6 and R7 mean, independently of each other, unbranched unsubstituted Ci-Ce alkyl or unbranched unsubstituted C3-C4 alkyl, or substituted unbranched Ci-Ce alkyl or substituted branched C3-C4 alkyl.

9. Compound according to at least one of claims 1 to 8, characterized in that the substituents at R5, R6 and R7 are selected from the hydroxyl group or cyano group, or from the hydroxyl group and cyano group.

10. Process for preparing a compound of formula (I), characterized in that the process comprises providing a compound of formula (II), diazotizing the compound of formula (II) and coupling the diazotized compound of formula (II) to the compound of formula (III) to obtain the resulting amine of formula (IV), diazotizing the compound of formula (IV) and coupling the diazotized compound of formula (IV) onto the compound of formula (V), wherein the radicals R1 to R7 are each in accordance with at least one of claims 1 to 9.

11. Process according to claim 10, characterized in that the diazotization is carried out from -10°C to +10°C, preferably -5°C to +10°C.

12. Use of a compound of formula (I) according to at least one of claims 1 to 9 or prepared according to a process according to claims 10 or 11, in a dyeing process or a printing process, preferably a process for dyeing or printing a substrate.

13. Use of a compound according to claim 12, as a blue or violet component in a three-color dyeing or printing process.

14. Process for dyeing or printing a substrate in a trichromatic dyeing or trichromatic printing process for the manufacture of a colored substrate, characterized in that the blue component used in the trichromatic dyeing or trichromatic printing process is a compound of formula (I) according to at least one of claims 1 to 9 or prepared according to claims 10 or 11.

15. A colored substrate, characterized in that it comprises a compound according to at least one of claims 1 to 9, or prepared according to a process according to claims 10 or 11.