AQUEOUS INK COMPOSITIONS

Abstract: An aqueous ink composition characterized in that the composition comprises a tetrakisazo dye represented by the formula wherein A₁ and A₂ represent (wherein m is 0 or 1, n is 0, 1 or 2, and M is H, Na, K, Li or NH₄) and are the same or different, and B₁ and B₂ represent or (wherein Y₁ is COOM, Y₂ is H, Cl, CH₃, OH, OCH₃, COOM or SO₃M, and Z is H, CH₃, t-C₄H₉ or COOM) and are the same or different.

Description: AQUEOUS INK COMPOSITIONS The present invention re3ates to aqueous ink ccmpositions having good stability and high safety for writing, printing and recording. As is well known, aqueous ink compositions for writing implements, etc. are usually solutions of watersoluble dyes in water and glycol solvents. Efforts have been made to fulfill the two conflicting requirements of good stability of the ink in the form of a solution and high water resistance of the ink after writing, with use of suitable additives. While improvements have been race in recent years in paper processing techniques to give increased water resistance to writing, the jet ink printing process, etc. require aqueous inks adapted to have enhanced stability with use of improved dyes which are less susceptible to association. Water-soluble dyes, especially black dyes, heretofore used for aqueous inks for writing implements and the like are polyazo dyes containing l-amino-8-naphthol-3,6disulfonic acid (H acid) as a coupled component. However, the acid coupling of dye components with H acid is lower in reactivity than with other compounds, so that the dye obtained varies greatly in quality from lot to lot. Furthermore, such amino-containing water-soluble polyazo dyes, which are prone to association, have a serious drawback. When formulated into an aqueous ink, the dye initially exhibits good solubility and stability but becomes less stable with time, such that the dye undergoes association in one to two months, resulting in gelation, a rise of viscosity and subsequent precipitation to impair the properties of the ink. Accordingly the above-mentioned conventional watersoluble dyes are almost unusable for jet printing inks which have been introduced into wide use recently and which must retain high stability even when the pH varies slightly. To cvercome the above problems we :e conducted extensive research and found that ap aqueous ink composition having high solution stability can be obtained with use of a tetrakisazo dye represented by the formula EMI2.1 wherein A1 and A2 represent EMI2.2 (wherein rn is O or 1, n is 0, 1 or 2, and M is H, Na, K, Li or NH4) an are the same cr different, and B1 and B2 repesent EMI2.3 EMI3.1 (wherein Y1 is COOM, Y2 is H, C1, CH3, OH, OCH3, COOM or SO3M, and Z is H, CH3, t-C4Hg or COOM) and are the same or different. We have further found that the tetrakisazo dye is negative when tested for mutagenicity by Ames Test and can be formulated into aqueous ink compositions having high safety in addition to high solution stability. Thus, the present invention has been accomplished. The tetrakisezo dye of the present invention represented by the formula (I) is prepared by tetrazotizing 1 ole of 4,4'-diaminostiltene-2,2'-disulfonic acid by a conventional process, coupling the resulting product wlth 2 moles of a compound represented by the formula EMI3.2 wherein m is O or 1, and n is 0, 1 or 2,0r wlth 2 moles of a mixture of compounds of the formula (II), tetrazotizing the resulting disazo dye again, and coupling the resulting compound with 2 moles of at least one compound represented by the formula EMI3.3 wherein Y1 is COOH, m is O or 1, and n is 0, 1 or 2, or of at least one compcund represented by the formula EMI4.1 wherein Y2 is H, C1, CH3, OH, OCH3, COOH or S03H, and Z is H, CH3, t-C4 H9 or COOH, or with 2 moles of a mixture of compounds of the formulae (III) and (IV). The dye obtained is purified with an acid or by salting-out or desalting treatment in usual manner and made into an alkali salt with a suitable amount of alkali, giving a water-soluble dye having good solubility and high safety and retaining good stability for a prolonged period of time. The dye can be modified in color with a known water-soluble dye to obtain the desired color. Examples of useful alkalis are sodium hydroxide, potassium hydroxide, lithium hycIoxide, ammonia water, etc. Examples of compounds represented by the formula (II) are l-aminonaphthalene, l-amino-4-naphthalenesulfonic acid, l-amino-5-naphthalenesulfonic acid, 1-amino-6naphthalenesulfonic acid, l-amino-7-naphthalenesulfonic acid, 1-amino-8-naphthalenesulfonic acid, 2-amino-1-naphthalenesulfonic acid, 5-arino-l-naphthol, l-amino-5-naphthol-7sulfonic acid, l-amino-8-naphthol-4-sulfonic acid, 2-amino5-naphthol-7-sulfonic acid, 2-amino-8-naphthol-6-sulfonic acid, l-amino-8-naphthol-2,4-disulfonic acid, l-amino-8- naphthol-3,6-disulfonic acid, l-amino-8-naphthol-4, 6- disulfonic acid, etc. Examples of compounds represented by the formula (III) are l-naphthol, l-naphthol-4-sulfonic acid, l-naphthol-5sulfonic acid, l-naphthol-8-sulfonic acid, 2-naphthol, 2-naphthol-6-sulfonic acid, 2-naphthol-3,6-disulfonic acid, 2-naphthol-3-carboxylic acid, etc. Examples of compounds represented by the formula (IV) are phenol, 4-chiorophenol, resorcinol, phenol-4sulfonic acid, o-cresol, salicylic acid, sulfosalicylic acid, 2-t-butyl-4-hydroxyarsole, etc. Given beloW are examples of tetrakisazo dyes of the invention reprcsented by the formula (I) and obtained by the above process. EMI6.1 EMI7.1 EMI8.1 EMI9.1 EMI10.1 EMI11.1 EMI12.1 EMI13.1 The solvents which are desirable for preparing ink compositions of this invention are water, and solvents which are miscible with Cater to thoroughly dissolve the foregoing dyes, activators and other additives, have suitable hygroscopicity and are capable of suitably controlling evaporation of the composition. Examples of such solvents are ethylene glycol, diethylene glycol, thiodiglycol and other glycol solvents, alcohol solvents, cellosolve solvents, carbitol solvents and pyrrolidone solvents. Examples of useful additives are alkanolamines, and anionic, nonionic or a-,.photeric activators. Depending on the use contemplated, disinfectants, corrosion ribitors, seclestering agents, etc. are also usable. W°len required, natural or snthetic water-soluble resins are also usable in admixture with the dye of the formula (I). The proportion of the coloring agent to be in.orporated into the present ink composition comprising such ingredients, which is variable with the contemplated use, is suitably 1 to 20%. The aqueous ink composition thus prepared according to the invention is comparable to those comprising conventional polyazo dyes in color density, has good stability for a prolonged period of time, is free of the rise of viscosity and is most suited for writing implements, jet printing, recorders, etc. Examples of the present invention are given below wherein "dye No." refers to the tetrakisazo dye of the same dye number according to the invention already mentioned. In the examples, the parts are all by weight. Example 1 Dye No. 4 (M = Na) 10 parts Ethylene glycol 10 parts Diethylene glycol 10 parts Propylene glycol 5 parts Disinfectant 0.3 part Activator 0.2 part Distilled water 64.5 parts The mixture of above ingredients was heated at 60 to 700 C to prepared a solution, which was then filtered with industrial filter paer to obtain a black ink composition. The ink composition was placed into a marking pen container and tested for writing. The ink flowed out from the pen tip always smoothly without any interruption to produce written images in a distinct color. The composition was allowed to stand at rcom temperature for more than 6 months and then checked. The composition was found to be stable and was filterable satisfactorily when tested with a l-micron membrane filter. Example 2 An :ny. composition was prepared in the same manner as in Example 1 except that 10 parts of dye No. 17 (M = Li) was used in place of the dye used in Example 1. Example 3 Dye No. 8 (M = NH4) 10 parts Ethylene glycol 10 parts Diethylerie glycol 10 parts Thiodigl.col 5 parts Triethanolamine 2 parts Disinfectant 0.3 part Activator 0.2 part Distilled water 62.5 parts The above ingredients ere nade into an ink composition in the same manner as in Example 1. Example 4 An ink composition was prepared in the same manner as in Example 3 except that 10 parts of dye No. 11 (M = Na) was used in place of the dye used in Example 3. Example 5 An ink composition was prepared in the same manner as in Example 3 except that 10 parts of dye No. 19 (M = Na) was used in place of the dye used in Example 3. Comparative Example 1 An ink composition was prepared in the same manner as in Example 1 or 2 except that 10 parts of C.I. Direct Black 19, purified by desalting, was used in place of the dye used in Example 1 or 2. Comparative Example 2 An ink composition was prepared in the same manner as in Example 3, 4 or 5 except that 10 parts of C.I. Direct Black 154, purified by desalting, was used in place of the dye used in Example 3, 4 or 5, Comparative Examnle 3 A black ink having high safety was prepared in the same manner as in Example 1 or 2 except that the dye used in Example 1 or 2 was replaced b te following dyes. C.I. Food Yeliow 3 5.5 parts C.I. Food Violet 2 1.5 parts C.I. Food Blue 2 3 parts When triethanolamine was added to the ink, a color change occurred. Table 1 shows the properties of the writing inks prepared in the foregoing Examples and Comparative Examples. The stability, viscosity change and filterability (with use of l-micron membrane filter) listed were determined after allowing the inks to stand at room temperature for 6 months. Table 1 Example Comparative Example 1, 2 3, 4, 5 1 2 3 Reddish Bluish Reddish Yellowish Bluish Color black black black black black Solubility A A B B A Stability A A D D A Viscosity A A D D A change filterability A A D D A Water C C A B D resistance Fastness to B B A A D light Note: A: Very good B: Good C: Slightly poor D: Very poor Example 6 Dye No. 5 (M = Na) 5 parts Diethylene glycol 11 parts Triethanolamine 2 parts Disinfectant 0.2 part Distilled water 81.8 parts The above ingredients were thoroughly mixed together at 30 to 40 C to obtain a solution, which was then purified by filtration with a membrane filter 0.8 micron in ore size, affording a bluish black jet printing ink. The ink obtained had high stability as a solution, caused no clogging and produced prints in a distinct color by jet printing. The prints produced with use of the ink on water-resistant paper (e.g. TJ-MATCOAT M8 (brand name) and IJ-M-BW (brand name) manufactured by Mitsubishi Paper Mills, Ltd.) had good resistance to water. Example 7 A bluish black ink composition was prepared in the same manner as in Example 6 except that 5 parts of dye No. 18 (M = Na) was used in place of the dye used in Example 6. The ccmposition obtained was comparable to the one obtained in Example 6 in properties. Example 8 Dye No. 10 (M = Na) 5 parts Triethylene glycol 10 parts Thiodiglycol 2 parts N-Methylpyrrol i done 1 part Disinfectant 0.2 part Distilled water 81.8 parts The above ingredients were treated in the same manner as in Example 6 to obtain a reddish black jet printing ink. The ink had high stability as a solution, caused no clogging and produced prints of good water resistance with use of coated paper. Example 9 A reddish black ink composition was prepared in the same manner as in Example 8 except that 5 parts of dye No. 20 (M = Na) was used in place of the dye used in Example 8. The composition was comparable to the one obtained in Example 8 in properties. Example 10 Dye No. 14 (M = Na) 5 parts l < -Methylpyrrolidone 11 parts Diethylene glycol 2 parts Triethanolamine 1 part Disinfectant 0.2 part Distilled water 80.8 parts The above ingredients were treated in the same manner as in Example 6 to obtain a reddish black jet printing ink. The ink had high stability as a solution, caused no clogging and produced prints of good water resistance with use of coated paper. Comparative Example 4 A reddish black ink was prepared in the same manner as in Example 6 or 7 except that 5 parts of C.I. Direct Black 19, purified by desalting, was used in place of the dye used in Example 6 or 7. Although the ink produced prints of good water resistance on usual record paper, the ink c-ced clogging during a long period of use Comparative Example 5 A yellowish black ink was prepared in the same manner as in Example 8 or 9 except that i parts of C.I. Direct Black 154, purified by desalting, was used in place of the dye used in Example 8 or 9. The ink caused clogging during use for a long period of time although giving prints of good water resistance on usual record paper. Examples 11 - 24 Ink compositions were prepare in the same manner as in Example 6 with the exception of using 5 parts of the dyes of the invention listed in Table 2 below, in place of dye No. 5. Table 2 also shows the stab City cf the inks and the colors of prints produced with uUe of the inks on coated paper by jet printing. The inks were tested for stability by filtration with a 0.8-micron membrane filter after allowing the ink to stand at room temperature for 6 months. Table 2 Example Dye Stability Color No. M 11 1 Na Good Dark blue 12 2 Na " Light blue 13 3 Na " Dark blue 14 6 NH4 " Medium blue 15 7 Li " Reddish black 16 9 Na " Reddish black 17 12 Na " Reddish black 18 13 K " Black 19 15 Na " Reddish black 20 16 Na " Bluish black 21 21 NH4 " Medium blue 22 22 Na " Reddish black 23 23 Li " Reddish black 24 24 Na n Reddish black Corp. Ex. 4 Precipitation Reddish black 5 " Yellowish black

Claims: What is claimed is: An aqueous ink composition characterized in that the composition comprises a tetrakisazo dye represented by the formula EMI23.1 wherein A1 and A2 represent EMI23.2 (wherein m is O or 1, n is 0, 1 or 2, and M is H, Na, K, Li or NH4) and are the same or different, and R1 and B2 represent EMI23.3 EMI23.4 (wherein Y1 is COOM, Y2 is H, Cl, CH3, OH, OCH3, COON or S03M, and Z is H, CH3, t-C4Hg or COOM) and are the same or different.

Inventors: MATSUBARA, SADAHIKO ORIENT CHEM. IND. LTD., SENSHU, HISASHI
Applicants: ORIENT CHEMICAL INDUSTRIES, LTD.
Application year: 1984
Main classification: C09D11
IPC codes: C09D11