| CORP. SALE |
1,3,5-TriAzine-2-[S(CH2)2-SO3Na]-4-NH2-6-(Monoazo dye radical) |
| PATENT ASSIGNEE'S COUNTRY | CH |
| UPDATE | 05.00 |
| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | 30.05.00 |
| PATENT TITLE |
Azo dyes and their preparation and use |
| PATENT ABSTRACT |
Azo dyes of formula (4) ##STR1## wherein A, R.sub.4, M and m are as defined in the specification, are excellent dyes for dyeing and printing of cellulose containing materials and especially for the preparation of inks for ink jet printing. |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | 19.11.98 |
| PATENT FOREIGN APPLICATION PRIORITY DATA | This data is not available for free |
| PATENT REFERENCES CITED |
Analytical Report, Photographic Gelatin ST 71, 810 Deutsche Gelatinefabrikin (DGF Stoess), Jun. 1995. Olin Chemical Specialities Specifications-Glycidol Surfactant 10G, Mar. 1989. Ciba-Geigy Speciality Chemicals Data Sheet For Compound 11 in application, Nov. 1995. |
| PATENT CLAIMS |
What is claimed is: 1. Azo dyes of formula (4) ##STR27## wherein A represents NR.sub.3 R.sub.4, wherein R.sub.3 and R.sub.4 independently represent hydrogen; alkyl with 1 to 6 C atoms; substituted alkyl with 2 to 6 C atoms, where the substituents are selected from the group consisting of OH, OCH.sub.3 and COOM; aralkyl; aryl or substituted aryl, where the substituents are selected from the group consisting of COOM, Cl, Br or SO.sub.3 M; or where R.sub.3 and R.sub.4 together form a ring with or without a hetero atom; or represents OR.sub.2 wherein R.sub.2 represents hydrogen or alkyl with 1 to 8 C atoms; m is from 2 to 6; R.sub.1 represents hydrogen or alkyl with 1 to 6 C atoms; M represents hydrogen, a metal cation, ammonium or substituted ammonium, wherein the substituents are selected from the group consisting of alkyl, alkoxyalkyl or hydroxyalkyl each having from 1 to 12 C atoms or phenyl; guanidinium or substituted guanidinium, where the substituent is selected from the group consisting of alkyl with 1 to 12 C atoms or phenyl; and F represents a monoazo or a polyazo dye radical. 2. Dyes according to claim 1, wherein A, m, R.sub.1 and F are as defined in claim 1; and M represents an alkali metal cation. 3. Dyes of formula (20) according to claim 1, ##STR28## wherein A, m, R.sub.1 and M are as defined in claim 1; and B represents one of the following groups ##STR29## wherein R.sub.5, R.sub.6 independently represent hydrogen, alkyl or alkoxy each having from 1 to 4 C atoms, chloro, bromo, carboxy or sulpho; D.sub.1 represents phenyl or phenyl substituted by one or two substituents selected from the group consisting of alkyl, alkoxy, chloro, bromo, carboxy and sulpho, or naphthyl or naphthyl substituted by 1 or 2 sulpho groups; and p.sub.1 is 0 or 1. 4. Dyes of formula (21) according to claim 1, ##STR30## wherein A, m, R.sub.1 and M are as defined in claim 1; B represents one of the following groups ##STR31## wherein R.sub.5, R.sub.6 independently represent hydrogen, alkyl or alkoxy each having from 1 to 4 C atoms, chloro, bromo, carboxy or sulpho; D.sub.1 represents phenyl or phenyl substituted by one or two substituents selected from the group consisting of alkyl, alkoxy, chloro, bromo, carboxy and sulpho, or naphthyl or naphthyl substituted by 1 or 2 sulpho groups; and R.sub.7, R.sub.8 independently represent hydrogen, alkyl or alkoxy or acylamino with up to 3 C atoms. 5. Dyes of formula (22) according to claim 1, ##STR32## wherein A, m, R.sub.1 and M are as defined in claim 1; B represents one of the following groups ##STR33## wherein R.sub.5, R.sub.6 independently represent hydrogen, alkyl or alkoxy each having from 1 to 4 C atoms, chloro, bromo, carboxy or sulpho; D.sub.1 represents phenyl or phenyl substituted by one or two substituents selected from the group consisting of alkyl, alkoxy chloro, bromo, carboxy and sulpho, or naphthyl or naphthyl substituted by 1 or 2 sulpho groups; is 0 or 1; and E represents phenyl or phenyl substituted by one or two substituents selected from the group consisting of alkyl, alkoxy, chloro, bromo, carboxy and sulpho, or naphthyl or naphthyl substituted by one or two substituents selected from the group consisting of sulpho, hydroxy and amino. 6. Dyes of formula (23) according to claim 1, ##STR34## wherein A, m, R.sub.1 and M are as defined in claim 1; D.sub.2 represents phenyl or phenyl substituted by one or two substituents selected from the group consisting of alkyl, alkoxy, chloro, bromo, carboxy and sulpho, or naphthyl or naphthyl substituted by one or two sulpho groups; and p.sub.2 is 0 or 1. 7. Dyes of formula (24) according to claim 1, ##STR35## wherein A, m, R.sub.1 and M are as defined in claim 1; and R.sub.9 represents hydrogen, alkyl with 1 to 6 C atoms, substituted alkyl with 2 to 6 C atoms, where the substituents are selected from the group consisting of carboxy, hydroxy and sulpho, phenyl or substituted phenyl, where the substituents are selected from the group consisting of methyl, chloro, bromo and sulpho. 8. Dyes of formula (25) according to claim 1, ##STR36## wherein A, m, R.sub.1 and M are as defined in claim 1; R.sub.10 represents CH.sub.3, COOH or NHCOCH.sub.3 ; and R.sub.11, R.sub.12 independently represent hydrogen, chloro, bromo or methyl. 9. Dyes of formula (26) according to claim 1, ##STR37## wherein A, m, R.sub.1 and M are as defined in claim 1; R.sub.13 represents hydrogen, alkyl or alkoxy each having up to 3 C atoms; R.sub.14 represents alkyl with 1 to 8 C atoms, phenyl or phenyl substituted by one or more substituents selected from the group consisting of chloro, bromo, alkyl and alkoxy each having from 1 to 4 C atoms; and p.sub.2 is 0 or 1. 10. Dyes of formula (27) according to claim 1, ##STR38## wherein A, m, R.sub.1 and M are as defined in claim 1; R.sub.15 represents hydrogen, alkyl or alkoxy each having up to 3 C atoms; R.sub.16 represents alkyl with 1 to 8 C atoms, substituted alkyl with 1 to 6 C atoms, where the substituents are selected from the group consisting of COOCH.sub.3, COOH and halogen, phenyl or phenyl substituted by one or more substituents selected from the group consisting of chloro, bromo, alkyl, alkoxy, alkylcarbonylamino and alkylsulphonyl each having from 1 to 4 C atoms, or pyridine; and p.sub.3 is 0 or 1. 11. Dyes of formula (28) according to claim 1, ##STR39## wherein A, m, R.sub.1 and M are as defined in claim 1; D.sub.3 represents phenyl or phenyl substituted by one or two substituents selected from the group consisting of sulpho, chloro, bromo, carboxy, alkyl and alkoxy; and R.sub.17, R.sub.18 independently represent hydrogen, chloro, bromo, ureido, alkyl, alkoxy or acylamino each having up to 3 C atoms. 12. Dyes of formula (29) according to claim 1, ##STR40## wherein A, m, R.sub.1 and M are as defined in claim 1; and R.sub.19 represents hydrogen, alkyl or alkoxy with up to 3 C atoms; R.sub.20 represents hydrogen, alkyl with 1 to 6 C atoms, substituted alkyl with 2 to 6 C atoms, where the substituents are selected from the group consisting of CN, COOH, OH, COOCH.sub.3, COOCH.sub.2 CH.sub.3 and COCH.sub.3, phenyl or substituted phenyl, where the substituents are selected from the group consisting of methyl, chloro and bromo. 13. Dyes of formula (30) according to claim 1, ##STR41## wherein A, m, R.sub.1 and M are as defined in claim 1; R.sub.21, R.sub.22 independently represent hydrogen, chloro, bromo, ureido, alkyl, alkoxy or acylamino each having up to 3 C atoms; and p.sub.4 is 1, 2 or 3 and the SO.sub.3 M group is in positions 1 or 4 or 5 or 6 or 7 or 8, when p.sub.4 is 1; or the SO.sub.3 M groups are in positions 4 and 8 or 5 and 7 or 6 and 8 or 1 and 5, when p.sub.4 is 2; or the SO.sub.3 M groups are in positions 3 and 6 and 8 or 4 and 6 and 8, when p.sub.4 is 3. 14. Dyes according to claim 1, wherein M represents hydrogen, a metal cation, ammonium or substituted ammonium, wherein the substituents are selected from the group consisting of alkyl, alkoxyalkyl or hydroxyalkyl each having from 1 to 12 C atoms or phenyl; quanidinium or substituted quanidinium, where the substituent is selected from the group consisting of alkyl with 1 to 12 C atoms or phenyl; M is from 2 to 4; R.sub.1 represents hydrogen; and F represents a monoazo or polyazo dye radical. 15. Process for the preparation of azo dyes according to claim 1, wherein (i) a compound of formula (5) ##STR42## where R.sub.1 and F are as defined in claim 1, are reacted with a compound of formula (6) ##STR43## where R.sub.3 and R.sub.4 are as defined in claim 1, under conditions where one of the chlorine atoms of the dichlorotriazine of formula (5) is replaced by the compound of formula (6); or a compound of formula (7) ##STR44## where R.sub.1 and F are as defined in claim 1, is reacted with a compound of formula (8) ##STR45## where R.sub.2 is as defined in claim 1, under conditions that one of the chlorine atoms of the dichlorotriazine of formula (8) is replaced by the compound of formula (7), and (ii) the disubstituted triazine is reacted with a compound of formula (9) ##STR46## where m is as defined in claim 1, under conditions that the third chlorine atom of the triazine ring is replaced by the compound of formula (9). 16. Process for dyeing cellulose containing material, paper, cotton, viscose, leather and wool by applying thereto an azo dye according to anyone of claims 1 to 14. 17. Liquid dye preparations comprising a dye or a mixture of dyes according to anyone of claims 1 to 14. 18. Inks for ink jet printing comprising a dye or a mixture of dyes according to anyone of claims 1 to 14. |
| PATENT DESCRIPTION |
FIELD OF THE INVENTION This invention relates to novel azo dyes and their salts, a method of their preparation and their use in dying and printing operations. It relates also to liquid dye preparations containing these dyes, particularly to aqueous inks for ink jet printing. BACKGROUND OF THE INVENTION Ink jet printing processes are of two types, continuous stream and drop-on-demand. In continuous stream ink jet printing systems, ink is emitted in a continuous stream under pressure through a nozzle. The stream is perturbed, causing it to break up into droplets at a fixed distance from the nozzle. At the break-up point, the drop-lets are charged in accordance with digital data signals and passed through an electric static field which adjusts the trajectory of each droplet in order to direct it to a gutter for recirculation or to a specific location on a recording medium. In the non-continuous process, or the so called "drop-on-demand" systems, a droplet is expelled from a nozzle to a position on a recording medium in accordance with digital data signals. A droplet is not formed and expelled unless it is to be placed on the recording medium. The most important part of an ink for ink jet printing are the dyes. Although a number of dyes have been proposed none meets all the requirements of a modern printing process. Reactive dyes with incorporated 1,3,5-triazine structural elements are common in textile printing. They have also been proposed as dyes for ink jet printing. For several reasons these dyes are not very suitable for this application. The reactive groups are not very stable over prolonged periods in aqueous solutions. Furthermore, dyes containing such reactive groups are due to their potential health risk, less suitable for handling in a non-chemical environment, where ink jet printing is normally done. Dyes of different structures not containing reactive groups have been described for example in the patents U.S. Pat. No. 4,771,129, U.S. Pat. No. 4,780,532, U.S. Pat. No. 4,968,784, U.S. Pat. No. 4,975,118, U.S. Pat. No. 4,997,919 and U.S. Pat. No. 5,118,737 as well as in the patent applications JP 5-171,053, EP 0,187,520, EP 0,194,885 and EP 0,755,984 as being suitable dyes for inks for ink jet printing. The azo dye of formula (1) ##STR2## has been described in patent application EP 0,187,520 (example 4). This dye and similar dyes described therein, however, are not soluble enough for their intended use in inks for modern ink jet printers. The azo dye of formula (2) ##STR3## has been described in patent application EP 0,755,984 (dye 100). The very high water solubility of the azo dye of formula (2) and of similar dyes has been attributed to the introduction of the structural element (3) ##STR4## wherein R represents hydrogen or alkyl with 1 to 6 C atoms; M represents hydrogen, a metal cation or a substituted ammonium cation wherein the substituent is selected from the group consisting of alkyl, alkoxyalkyl or hydroxyalkyl each having from 1 to 12 C atoms; and n and m independently of each other have a value from 2 to 6. Dyes having the structural element (3) mentioned above however show the disadvantage that they are not very stable against hydrolysis and that therefore inks containing such dyes are not stable when stored over long periods of time. They therefore do not satisfy all the required demands when used in recording liquids for ink jet printing. Dyes used for such recording liquids have to show a good solubility in the essentially aqueous ink liquid, they have to penetrate into the recording medium and should not show dye aggregation on the surface of the recording medium ("bronzing"). They need to provide printed images having high optical density, good water fastness and excellent light fastness. They need to be stable in the ink even when the recording liquid is stored for a long time under adverse conditions. Various types of compositions have been proposed as inks for ink jet printing. Typical inks comprise one or more dyes, water, organic cosolvents and other additives. The inks have to meet the following criteria: (1) The ink gives high quality images on any type of recording medium. (2) The ink gives printed images exhibiting excellent water fastness. (3) The ink gives printed images exhibiting excellent light fastness. (4) The ink gives printed images exhibiting excellent smudge behavior. (5) The ink does not clog jetting nozzles even when these are kept uncapped while recording is suspended. (6) The ink can be stored for long periods of time without deterioration of its quality. (7) The values of the physical properties of the inks as viscosity, conductivity and surface tension are all within defined ranges. (8) The ink has to be non toxic, not flammable and safe. DESCRIPTION OF THE INVENTION This invention relates to novel azo dyes showing high solubility and excellent stability against hydrolysis in aqueous recording liquids especially for ink jet printing. Printed images containing these dyes according to the invention show high optical density, excellent water fastness, excellent light fastness and excellent smudge behavior. Another object of the present invention is the provision of recording liquids especially for ink jet printing, showing high quality images on any type of recording medium as plain or coated paper, coated or uncoated, opaque or transparent synthetic materials. A further object of the present invention is to provide recording liquids satisfying also all the other requirements mentioned above. The present invention relates to novel azo dyes of general formula (4) showing very high solubility and at the same time excellent stability against hydrolysis, ##STR5## wherein A represents NR.sub.3 R.sub.4, wherein R.sub.3 and R.sub.4 independently represent hydrogen; alkyl with 1 to 6 C atoms; substituted alkyl with 2 to 6 C atoms, where the substituents are selected from the group consisting of OH, OCH.sub.3 and COOM; aralkyl; aryl or substituted aryl, where the substituents are selected from the group consisting of COOM, Cl, Br or SO.sub.3 M; or where R.sub.3 and R.sub.4 together form a ring with or without a hetero atom; or represents OR.sub.2 wherein R.sub.2 represents hydrogen or alkyl with 1 to 8 C atoms; m is from 2to 6; R.sub.1 represents hydrogen or alkyl with 1 to 6 C atoms; M represents hydrogen, a metal cation, ammonium or substituted ammonium, wherein the substituents are selected from the group consisting of alkyl, alkoxyalkyl or hydroxyalkyl each having from 1 to 12 C atoms or phenyl; guanidinium or substituted guanidinium, where the substituent is selected from the group consisting of alkyl with 1 to 12 C atoms or phenyl; and F represents a monoazo or a polyazo dye radical. The compounds of general formula (4) may be in the free acid form or in the form of inorganic or organic salts thereof. Preferably they are in the form of salts with cations such as alkali metal or ammonium or guanidinium, wherein the ammonium or guanidinium cation may be substituted. Examples of such substituted ammonium cations are 2-hydroxyethylammonium, bis-(2-hydroxyethyl)-ammonium, tris-(2-hydroxyethyl)-ammonium, bis-(2-hydroxyethyl)-methyl-ammonium, tris-[2-(2-methoxyethoxy)-ethyl]-ammonium, 8-hydroxy-3,6-dioxaoctylammonium and tetraalkylammonium as for example tetramethylammonium or tetrabutylammonium. Diphenylguanidinium is an example of a substituted guanidinium cation. The invention does not only cover pure dyes of formula (4), but also mixtures of these compounds. Especially preferred are dyes wherein the dye radical F has the following structural formulas: ##STR6## wherein M is as defined above; B represents one of the following groups ##STR7## wherein R.sub.5, R.sub.6 independently represent hydrogen, alkyl or alkoxy each having from 1 to 4 C atoms, chloro, bromo, carboxy or sulpho; D.sub.1 represents phenyl or phenyl substituted by one or two substituents selected from the group consisting of alkyl, alkoxy, chloro, bromo, carboxy and sulpho, or naphthyl or naphthyl substituted by 1 or 2 sulpho groups; and p.sub.1 is 0 or 1; or ##STR8## wherein D.sub.1 and B are as defined above; and R.sub.7, R.sub.8 independently represent hydrogen, alkyl or alkoxy or acylamino with up to 3 C atoms; or ##STR9## wherein M, D.sub.1, B and p.sub.1 are as defined above; and E represents phenyl or phenyl substituted by one or two substituents selected from the group consisting of alkyl, alkoxy, chloro, bromo, carboxy and sulpho, or naphthyl or naphthyl substituted by one or two substituents selected from the group consisting of sulpho, hydroxy and amino; or ##STR10## wherein M is as defined above; D.sub.2 represents phenyl or phenyl substituted by one or two substituents selected from the group consisting of alkyl, alkoxy, chloro, bromo, carboxy and sulpho, or naphthyl or naphthyl substituted by one or two sulpho groups; and p.sub.2 is 0 or 1; or ##STR11## wherein M is as defined above; and R.sub.9 represents hydrogen, alkyl with 1 to 6 C atoms, substituted alkyl with 2 to 6 C atoms, where the substituents are selected from the group consisting of carboxy, hydroxy and sulpho, phenyl or substituted phenyl, where the substituents are selected from the group consisting of methyl, chloro, bromo and sulpho; or ##STR12## wherein M is as defined above; R.sub.10 represents CH.sub.3, COOH or NHCOCH.sub.3 ; and R.sub.11, R.sub.12 independently represent hydrogen, chloro, bromo or methyl; or ##STR13## wherein M is as defined above; R.sub.13 represents hydrogen, alkyl or alkoxy each having up to 3 C atoms; R.sub.14 represents alkyl with 1 to 8 C atoms, phenyl or phenyl substituted by one or more substituents selected from the group consisting of chloro, bromo, alkyl and alkoxy each having from 1 to 4 C atoms; and p.sub.2 is 0 or 1; ##STR14## wherein M is as defined above; R.sub.15 represents hydrogen, alkyl or alkoxy each having up to 3 C atoms; R.sub.16 represents alkyl with 1 to 8 C atoms, substituted alkyl with 1 to 6 C atoms, where the substituents are selected from the group consisting of COOCH.sub.3, COOH and halogen, phenyl or phenyl substituted by one or more substituents selected from the group consisting of chloro, bromo, alkyl, alkoxy, alkylcarbonylamino and alkylsulphonyl each having from 1 to 4 C atoms, or pyridine; and p.sub.3 is 0 or 1; or ##STR15## wherein D.sub.3 represents phenyl or phenyl substituted by one or two substituents selected from the group consisting of sulpho, chloro, bromo, carboxy, alkyl and alkoxy; and R.sub.17, R.sub.18 independently represent hydrogen, chloro, bromo, ureido, alkyl, alkoxy or acylamino each having up to 3 C atoms; or ##STR16## wherein M is as defined above; R.sub.19 represents hydrogen, alkyl or alkoxy with up to 3 C atoms; and R.sub.20 represents hydrogen, alkyl with 1 to 6 C atoms, substituted alkyl with 2 to 6 C atoms, where the substituents are selected from the group consisting of CN, COOH, OH, COOCH.sub.3, COOCH.sub.2 CH.sub.3 and COCH.sub.3, phenyl or substituted phenyl, where the substituents are selected from the group consisting of methyl, chloro and bromo; or ##STR17## wherein M is as defined above; R.sub.21, R.sub.22 independently represent hydrogen, chloro, bromo, ureido, alkyl, alkoxy or acylamino each having up to 3 C atoms; and p.sub.4 is 1, 2 or 3 and the SO.sub.3 M group is in positions 1 or 4 or 5 or 6 or 7 or 8, when p.sub.4 is 1; or the SO.sub.3 M groups are in positions 4 and 8 or 5 and 7 or 6 and 8 or 1 and 5, when p.sub.4 is 2; or the SO.sub.3 M groups are in positions 3 and 6 and 8 or 4 and 6 and 8, when p.sub.4 is 3. The following dyes are examples of dyes of formula (4) where F is a monoazo radical: ##STR18## The following dyes are examples of dyes of formula (4) where F is a polyazo radical: ##STR19## The invention further claims a process for the preparation of the azo dyes of formula (4) characterized in that (i) a compound of formula (5) ##STR20## wherein R.sub.1 and F are as defined above, is reacted with a compound of formula (6) ##STR21## wherein R.sub.3 and R.sub.4 are as defined above, under conditions that one of the chlorine atoms of the dichlorotriazine of formula (5) is replaced by the compound of formula (6); or a compound of formula (7) ##STR22## wherein R.sub.1 and F are as defined above, is reacted with a compound of formula (8) ##STR23## wherein R.sub.2 is as defined above, under conditions that one of the chlorine atoms of the dichlorotriazine of formula (8) is replaced by the compound of formula (7); and (ii) the disubstituted triazine is reacted with a compound of formula (9) ##STR24## wherein m is as defined above, under conditions that the third chlorine atom of the triazine ring is replaced by the compound of formula (9). The dyes of formula (4) according to the invention are used to dye cellulose containing materials, paper, cotton and viscose as well as leather and wool to provide dyed material with good water and light fastness. Methods well known in the textile and paper industries for dyeing with substantive dyes may be used with the dyes according to our invention, preferably for the bulk or surface treatment of sized or unsized paper. The dyes may also be used in the dyeing of yarns and piece goods of cotton, viscose and linen by the exhaustion process from a long liquor or in continuous processes. The invention furthermore relates to liquid dye preparations comprising at least one dye of general formula (4). The use of such liquid dye preparations is preferred for paper dyeing. Such stable, liquid, preferably aqueous, and concentrated dye preparations may be obtained by using methods well known in the art, preferably by dissolving in suitable solvents. The possibility of preparation of such stable aqueous concentrated preparations in the course of dye synthesis itself, without intermediate isolation of the dye, is of particular advantage. Dyes or mixtures of dyes of formula (4) are excellent dyes for the preparation of recording liquids for ink jet printing. A suitable ink comprises one or more compounds according to the invention in a liquid aqueous medium. The ink contains from 0.5 to 20% by weight, preferably from 0.5 to 5% by weight, of this or these compounds, based on the total weight of the ink. The liquid medium is preferably water or a mixture comprising water and water soluble or water miscible organic solvents. Suitable solvents are given for example in U.S. Pat. Nos. 4,626,284, 4,703,113, 4,963,189 and in Patent Applications GB 2,289,473, EP 0,425,150 and EP 0,597,672. The present invention will be illustrated in more detail by the following examples without limiting the scope of the claimed compounds in any way. |
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