DYES FOR INK JET PRINTING

Abstract: There is described a new yellow dye which can be used in an aqueous composition in an ink-jet printing process.

Description: Dves for ink iet printing Field of the invention The present invention relates to dyes and aqueous ink composition compris¬ ing these dyes for ink jet printing processes. Ink jet printing systems generally are of two types: continuous stream and drop-on-demand. In continuous stream Ink jet systems, Ink is emitted in a con¬ tinuous stream under pressure through an orifice or nozzle. The stream is per¬ turbed, causing It to break up into droplets at a fixed distance from the ori¬ fice. At the break up point, the droplets are charged in accordance with digital data signals and (Dossed through an electrostatic field which adjusts the trajectory of each droplet in order to direct It to a waste ink collecting vessel (e. g. for recirculation) or a specific location on a recording medium. In drop-on-demand systems, a droplet is expelled from an orifice to a position on a recording medium In accordance with digital data signals. A droplet is not formed or expelled unless It is to be placed on the recording medium. The most important part of an ink used in ink jet printing are the dyes. Al¬ though a number of dyes have been proposed none has been produced which meets all the requirements of a modern printing process. Background of the invention Reactive dyes with incorporated 1 ,3,5-triazine structural elements are com¬ mon in textile printing and have also been proposed for ink jet printing. Such dyes are for several reasons in general not too well suited for this application. The reactive groups are not very stable over prolonged periods in aqueous solutions. Dyes containing such reactive groups are moreover, due to their potential health risk, less suitable for handling in a non industrial environment. Reactive dyes of this kind have been described in EP 559 * 331 (B. Lamble et al). In particular dyes of the following structural formulas have been de¬ scribed: EP 559'331 (dye l) (1) EP 559 * 331 (dye 5) (2) These dyes are however still inadequate when used in aqueous inks of mod¬ em ink jet printers. In particular printers of the continuous-stream type are highly demanding as far as physical properties of the inks are concerned. Particularly critical Is the storage stability of the inks without forming degrada- tion products prone to clog the nozzles of the printer. Printers are today able to print images of high density rapidly. Therefore highly concentrated inks are needed in order to avoid the jetting of high water volumes onto the receiving layer. These high concentrations should ideally, for environmental reasons, be achieved without the use of organic cosolvents. Such inks can only be pre¬ pared with dyes having a particularly high water solubility. Dyes of the above mentioned structures which are the state of the art, are in general not soluble or stable enough to satisfy the required demanding con¬ ditions. It is the aim of this invention to provide dyes with the required high water solubility. Description of the invention This invention relates to azo dyes of the formula (3) (3) wherein: Rl is selected from hydrogen or an aliphatic radical having from 1 to 6 C atoms; n is 2, 3 or 4; R3, R4 are independently selected from hydrogen, alkyl or alkoxy or acyl- amino containing up to 3 C atoms; SUBSTiηjTF SHFFT ^ i ϋ F rø X is NR5R6 where R5 and R<5 are independently selected from hydrogen, alky I from 1 to 6 C atoms, substituted alkyl having 2 to ό C atoms where the sub- stituents are selected from OH, OCH3, COOM, SO3M; aralkyl; unsub- stituted aryl or an aryl substituted by COOM or SO3M; R5 and R$ may form a ring without or with inclusion of a hetero atom; or X is SR7 in which R7 is an unsubstituted alkyl from 1 to 6 C atoms; sub¬ stituted alkyl having 2 to 6 C atoms where the substituents are se¬ lected from OH, OCH3, COOM, SO3M; or X Is ORβ in which Re is hydrogen or an aliphatic radical having from 1 to 6 C atoms; m is 1 , 2 or 3 and the substitution pattern is selected from 4,8/ 5,7/ 6,8/ 3,6,8 or 4,6,8. In a case where m is 1 , SO3M may also be in position 1 or 4 to 8; M is hydrogen, a metal atom, an ammonium or ammonium substi¬ tuted with alkyl, alkoxyalkyl and hydroxyalkyl each having 1 to 12 C atoms. The azo dyes of the present invention comprise no reactive groups. They are of particular use in inks used for ink-jet printing because of their high water solubility. Dye synthesis One method of preparing dyes of the present invention is by: (i) Reacting a compound of formula (4) (4) with cyanuric chloride under conditions such that one chlorine atom of the triazine Is displaced by the monoazo compound of formula (4), then (ii) reacting the mono-substituted dichloro-triazine with a compound of formula (5) HN(CH 2 ^Sθ 3 R (5) under conditions such that a second atom of chlorine is displaced by the compound of formula (5) and reacting finally (iii) the di-substituted triazine with a compound XH under conditions that the third chlorine atom is displaced by X. Where X is a compound of formula 5, the second and third chlorine atoms of the triazine nucleus may be displaced simultaneously. The present invention is illustrated by the following example: Exαmole 1 Preparation of the compound No.100 (Na-salt) stage 1 62.2 g (0,126 mol) monoazo compound of Formula (6) (6) (prepared as described in USP 3'264'109) was added to water (200 ml) and the pH adjusted to 9.5 by addition of 30 % sodium hydroxide solution. A solution of cyanuric chloride (25.4 g, 0,138 mol) in ethyl acetate (90 ml) was added maintaining the pH at 8.2-8.5 and the temperature at 20-25 °C. After 30 minutes a solution of 2-aminoethanesulfonic acid (20.4 g, 0,138 mol) in wa¬ ter (30 ml) and 30 % sodium hydroxide solution (22 g) was added to the reac¬ tion mixture while maintaining the pH at 9-9.5 and the temperature at 30°C. The reaction mixture was stirred for 6 hours at this temperature and pH and then the product was filtered. stage 2 The wet product (200 g) from stage 1 was added to a mixture of water (300 ml) and 30% sodium hydroxide solution (36 g). The reaction mixture was heated to 90 °C for 6 hours and cooled to room temperature. Acetic acid (8.5 ml) was added to obtain a pH value of 7.5 followed by an addition of methanol (340 ml). The solid was collected by filtration, washed with metha- nol (150 ml), dried in vacuum at 60 °C to yield the yellow dye (85 g) of for¬ mula 100. In an analogous manner using appropriate starting materials the dyes de¬ scribed in Tables 1 to 3 can be obtained. Table 1 The dyes of the general formula: were made wherein the substltuents are: Compound SO3M X M λ max (nm) No. positions in H2θ 100 4.8 OH Na 398 101 4, 8 SCH2CH2OH Na 404 102 4, 8 SCH 2 COONa Na 408 103 4, 8 N(CH2CH 2 OH)2 Na 409 104 4, 8 NHCH2CH2SO3K K 405 105 4, 8 OCH2CH3 Na 406 106 5, 7 OH Na 393 Table 2 The dyes of the general formula: were made wherein the substituents are: Compound SO3M X M λ max (nm) No. positions in H2θ 201 4, 8 OH Na 394 202 4, 8 SCH2CH2OH Na 394 203 4. 8 SCH2COONa Na 398 Table 3 The dyes of the general formula: were made wherein the substituents are: Compound SO3M X M λ max (nm) No. positions in H2θ 301 4, 8 OH Na 378 Example 2 The dyes of the present Invention are specially adapted for the preparation of inks. Inks for ink jet printing are well known. These inks consist in essence of a liquid vehicle dissolved therein a dye. The liquid vehicle of the inks employed for the printing consists in general of water or a mixture of water and a misci- ble organic solvent such as C1-C4 alkanols, alkylene glycols such as dKpropylene glycol), di(ethylene glycol), polyols such as 1 ,5-pentanediol. gycerol, 1 ,2,6-trihydroxyhexane, nitrogen-containing solvents such as 2- pyrrolidinone , N-methyl-2-pyrrolidinone , 1 -<2-hydroxyethyl)-2-pyrrolidinone , 1 ,3-dimethy--2-imidazolidinone, 1.1,3,3-tetramethylurea or sulfur containing solvents such as organosulfoxides, sulfolane and the like. The non water parts of the printing ink generally serve as humefactant, cosol- vent. viscosity regulating agent, ink penetration additive, levelling agent or drying agent. In addition aqueous inks may contain miscellaneous known additives like vis¬ cosity modifiers, such as cellulose derivatives and other water-soluble resins, various kinds of surfactants, surface tension modifiers, optical brighteners, UV absorbers, light stabilisers, biocides and pH conditioners, such as buffers. Inks for use in ink jet recording of the type based on continuous-stream usually contain an inorganic salt as electrolyte, such as sodium/ammonium/lithium halogenides or sulphate. This description of inks is for illustration only and is not to be considered as limit¬ ing the invention. The present invention in so far as it relates to inks is further illustrated with ref¬ erence to the following examples in which all parts and percentages are by weight. Inks were prepared, using the dyes 100 to 102, as described above, accord¬ ing to the following recipe: dye 6 parts glycerol 20 parts water 74 parts The inks were prepared by dissolving the ingredients and filtering the solution under pressure through a Millipore filter (0.5 micron). The inks were tested and shown to satisfy all the requirements specifying a us¬ able ink. In particular they were shown to meet the following criteria: (1 ) Physical properties of the ink. such as viscosity, conductivity and surface tension, are each within a defined range. (2) All dyes have good solubility in the ink medium to give solutions having good stability which do not plug the fine ejecting orifices. (3) The recording agent gives images of sufficient optical density. (4) The ink does not change physical properties or deposit solid matter during storage. (5) Printing can be performed without a restriction on the nature of sub ¬ strate. (6) The ink exhibits α high rate of fixation. (7) The ink gives images of good resistance to water, light and abrasion. Example 3 The solubilities of the dyes according to the invention were determined as follows: An excess of dye was heated at 50°C in water with stirring for one hour. The mixture was then cooled down to 20 ° C and filtered, and the dye content of the clear solution was determined spectroscopically. The results obtained are shown in table 4. Table 4 dye No solubility On g per 100 ml) 100 31 101 40 102 54 dye 1 11 dye 5 17 The dyes 1 and 5 are known from EP 559 * 331 es heretofore set forth. The results in table 4 show the significantly higher solubility of the dyes accord¬ ing to the invention compared to dyes of the prior art.

Claims: CLAIMS: 1. An αzo dye of formula (3) (3) wherein Rl is selected from hydrogen or an aliphatic radical having from 1 to 6 C atoms; n is 2.3 or 4; R3. 4 are independently selected from hydrogen, alkyl or alkoxy or acylamino containing up to 3 C atoms; is NR5R5 where R5 and R^ are independently selected from hydrogen, alkyl from lto 6 C atoms, C2 to C6 substituted alkyl where the sub¬ stituents are selected from OH. OCH3, COOM, SO3M or an aryl substituted by COOM, SO3M or R^ t R form a ring without or with inclusion of a hetero atom; or X is SR7 in which R7 is an unsubstituted alkyl from 1 to 6 C atoms, alkyl having 2 to6 C atoms substituted by OH, OCH3, COOM. SO3M; or X is ORβ in which Rs is hydrogen or an aliphatic radical having from 1 to 6 C atoms; m is 1 , 2 or 3 and the substitution pattern Is selected from 4,8/ 5,7/ 6.8/ 3.6,8 or 4,6.8. In a case where m is 1 , -SO3M may also be in position 1 or 4 to 8; M is hydrogen, a metal atom, an ammonium or ammonium sub¬ stituted with alkyl, alkoxyalkyl and hydroxyalkyl each having 1 to 12 C atoms. 2. An azo dye according to claim 1 where R] is hydrogen and where X, R3 to RQ. n, m, M and the substitution pattern in the naphthaline ring are as set forth in claim 1. 3. An azo dye according to claim 2 where n is 2 or 3 R$ t R4 are as set forth in claim 1; R5 R< are independently selected from hydrogen, Cl to Co alkyl, C2 to C6 substituted alkyl where the substituents are selected from OH, CH3, COOM, SO3M or R5 R$ form a 5- or 6- membered ring without or with inclusion of a hetero atom; or X is SR7 where R7 is α C2 to C4 substituted αlkyi where the sub¬ stituents are selected from OH. OCH3, COOM. SO3M; X is ORβ where RQ is hydrogen, CH3 or CH2CH3; M is as in claim 2; and m is 2 and the substitution pattern in the naphthaline part is 4,8 or 6,8 or 5,7. 4. An azo dye according to claim 3 where R3. R4 are independently selected from hydrogen. OCH3. OCH2CH3. CH3. CH2CH3 or HNCOCH3; X is NR5R6 where R5 and R^ are as set forth in claim 3; or X is S-CCH 2 ) q -OH, S-(CH2) q -COOM or S-(CH 2 ) q -Sθ3M where q is 1 to 6; or X is OR8 where Re is as set forth in claim 3; M is hydrogen, alkali metal atom, ammonium, ammonium sub¬ stituted with Cl to C2 alkyl or with CH2CH2OH; m is 2 and the substitution pattern in the naphthaline part of the dye is 4.8 or 6,8 or 5,7. 5. An αzo dye according to the formula 7 (7) where R3, R4 are Independently selected from hydrogen, CH3, OCH3 or NHCOCH3; Rδ is hydrogen, CH3 or CH2CH3; and M is as set forth in claim 4. An azo dye according to formula 8 (8) where R3, R4 are as set forth in claim 5; R5, R_ are independently selected from hydrogen, CH3, CH2CH2OH or CH2CH2SO3M; and M is as set forth in claim 4. An azo dye according to formula 9 (9) where R3, 4 are as se * forth in claim 5 R7 is selected from CH2CH2OH. CH2COOM or CH2CH2CH2SO3M; and M is as set forth in claim 4. 8. An ink comprising at least one dye as described in anyone of claims 1 to 7. 9. An ink which contains in addition to a dye or dyes as claimed in any¬ one of claims 1 to 7 one or more other dyes or additives.

Inventors: BAETTIG KURT, JAN GERALD, BAETTIG, KURT, JAN, GERALD
Applicants: BAETTIG KURT, ILFORD AG, JAN GERALD, MATTHEWS RICHARD NORDAN, BAETTIG, KURT, JAN, GERALD, MATTHEWS, RICHARD, NORDAN
Application year: 1996
Main classification: C09B43
IPC codes: C07D251, C09B43, C09D11