Method of manufacturing reactive composition and ink for high stability

Abstract

The present invention provides a method of manufacturing a reactive composition: (a) dissolving 2-[(4-aminophenyl)sulfonyl]ethanesulfonic acid in water to form a solution; (b) introducing excess nitrite or excess nitrous acid and the solution into an acid solution to form a diazonium salt; (c) adding 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid to react with the diazonium salt; (d) adding 7-acetamido-4-hydroxy-2-naphthalenesulfonic acid to react with the diazonium salt; (e) adding a first alkaline substance to adjust a pH value; (f) adding a second alkaline substance to adjust the pH value; (g) adding a third alkaline substance to control the pH value; (h) adding an acidic substance to adjust the pH value; and (i) adding an additive agent to obtain the reactive composition, wherein the additive agent is acetic acid, sodium hydroxide, acetate, sulfonic acid buffering agent, or a combination thereof.

Claims

1. A method of manufacturing a reactive composition, comprising: (a) dissolving 2-[(4-aminophenyl) sulfonyl]ethanesulfonic acid into water to form a solution; (b) introducing excess nitrite or nitrous acid and the solution into hydrochloric acid to form a diazonium salt; (c) adding 4-amino-5-hydroxy-2,7-naphthalenedisulfonic acid to react with the diazonium salt; (d) adding 7-acetamido-4-hydroxy-2-naphthalenesulfonic acid to react with the diazonium salt; (e) adding a first alkaline substance to adjust a pH value, wherein the first alkaline substance is sodium bicarbonate and the pH value is adjusted to 2.0-2.2; (f) adding a second alkaline substance to adjust the pH value, wherein the second alkaline substance is sodium carbonate and the pH value is adjusted to 5.2-5.5; (g) adding a third alkaline substance to control the pH value, wherein the third alkaline substance is sodium hydroxide and the pH value is controlled no more than 11; (h) adding an acidic substance to adjust the pH value, wherein the acidic substance is hydrochloric acid and the pH value is adjusted to 6.0-6.5; and (i) adding an additive agent to obtain the reactive composition, wherein a reaction temperature of the step (b) is lower than 5 C., wherein the additive agent is acetic acid, sodium hydroxide, acetate, sulfonic acid buffering agent, or a combination thereof.

2. The reactive composition of claim 1, wherein a pH value of the reactive composition is ranged 6.5-7.5.

3. The reactive composition of claim 1, further comprising desalination is performed by filtration, and a membrane separation technology is used to concentrate to a solid content of 10 wt. %, thereby obtaining a refined product of the reactive composition.

4. A method of manufacturing a reactive ink, comprising: (a) providing a reactive composition made by the method of claim 1; and (b) mixing an antibacterial agent, a surfactant, ethylene glycol, 1,2-propanediol, glycerin, caprolactam, diethylene glycol, a sulfonic acid buffering agent or a combination thereof with the reactive composition to form the reactive ink.

5. The method of manufacturing a reactive ink of claim 4, wherein a pH value of the reactive ink is ranged 7.0-8.0.

6. The method of manufacturing a reactive ink of claim 4, wherein a concentration of free chloride ion and free sulfate ion are respectively lower than 50 ppm.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The drawing illustrates the Table 5 of the embodiment in the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(2) Reference will now be made in detail to the exemplary embodiments of the present invention. Therefore, it is to be understood that the foregoing is illustrative of exemplary embodiments and is not to be construed as limited to the specific embodiments disclosed, and that modifications to the disclosed exemplary embodiments, as well as other exemplary embodiments, are intended to be included within the scope of the appended claims. These embodiments are provided so that this invention will be thorough and complete, and will fully convey the inventive concept to those skilled in the art.

(3) For convenience, certain terms employed in the specification, examples and appended claims are collected here. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of the ordinary skill in the art to which this invention belongs. In addition, unless otherwise specified, the percentage of additive agent (%) in the embodiments refers to weight percentage.

(4) The inventive concept, however, may be embodied in various different forms, and should not be construed as being limited only to the illustrated embodiments. Rather, these embodiments are provided as examples, to convey the inventive concept to one skilled in the art. Accordingly, known processes, elements, and techniques are not described with respect to some of the embodiments. It should be noted that although the following embodiments are prepared using C.I. reactive black No. 5 dye for ink preparation, the effect of the substance is not intended to limit the scope of the present invention. Generally, all reactive dyes or all reactive compositions selected from the color index can be used in the present invention.

(5) The singular forms a, and, and the are used herein to include plural referents unless the context clearly dictates otherwise.

(6) The following descriptions are provided to elucidate a method of manufacturing reactive composition and ink for high stability and to aid it of skilled in the art in practicing this invention. These embodiments are merely exemplary embodiments and in no way to be considered to limit the scope of the invention in any manner.

Material and Method

(7) (a) 76.99 g of 2-[(4-aminophenyl)sulfonyl]ethanesulfonic acid (vinyl sulfone parabase ester, Cas. 2494-89-5) (100% basis, 0.2740 mol) was added to 100 ml of water and 100 g of ice, then mixed for 4 hours.

(8) (b) 19.1 g of sodium nitrite (NaNO.sub.2, 100% basis, 0.277 mol) was dissolved in 50 ml of water. Wherein the main purpose of this step is to use excessive nitrous acid or nitrite to diazotize the para-vinyl sulfide ester.

(9) (c) 50 g of ice was added to the para-vinyl sulfide ester solution prepared in step (a) to lower the temperature close to 0 C. An acidic solution was also added, which includes but is not limited to inorganic acids, such as 10 g of hydrochloric acid (0.274 mol). The sodium nitrite solution prepared in step (b) was added within 15 minutes, and the temperature is controlled under 5 C. to generate diazonium salt and remaining nitrite. The molar ratio between the nitrite and the para-vinyl sulfide ester is about 1.02:11.05:1. During the process, it was repeatedly tested with Congo red test strips and dark blue was presented. After that, a small amount of sulfamic acid (Casamic 5329-14-6) was used to remove the remaining sodium nitrite to stop the reactivity of the remaining sodium nitrite. The process was tested with potassium iodide starch test paper and light blue was presented, indicating that nitrite has been completely removed.

(10) (d) 34.1 g of 4-amino-5-naphthol-2,7-disulfonic acid (H-acid, Cas no. 5460-09-3) (100% basis, 0.1 mole) was added to diazonium salt prepared in the step (c) and the temperature was raised to 13-14 C.; wherein the molar ratio of the diazonium salt and H acid is about 1.01:11.03:1.

(11) (e) 19.04 g of 7-acetamido-4-hydroxy-2-naphthalenesulfonic acid (acetoxy-J-acid, Cas no. 6334-97-0) was added into 50 ml of water and stirred for 1 hour; wherein the molar ratio of the diazonium salt and the J acid is about 1.01:11.03:1.

(12) (f) About 50 g of ice was added into the solution obtained in step (d), and the acetyl-J-acid solution obtained in step (e) was added to react with the remaining diazonium salt, and the temperature was controlled at 5-8 C. Next, a first alkaline substance, including but not limited to 25.31 g of sodium bicarbonate (NaHCO.sub.3, 0.3014 mol) was added to adjust the pH to 2.0-2.2, maintaining the temperature at 5-8 C., and the second alkaline substance was used within 30 minutes, including but not limited to 15% of sodium carbonate (Na.sub.2CO.sub.3) solution, to adjust the pH to 5.2-5.5. In the late stage of the reaction, the pH would slowly rise to 6-6.5, and the resulting conjugate is a reactive black mixture dye (also known as KN-A vinyl sulfone black dye), which has good stability. The powder dye can be obtained by spray drying.

(13) The KN-A vinyl sulfone black dyes prepared in steps (a) to (f) would be used in the following examples of the present invention, and additive agents were added to evaluate its anti-aging effect.

(14) (g) 10.96 g of the third alkaline substance, including but not limited to caustic soda (NaOH), was dissolved in 100 ml of water.

(15) (h) The KN-A vinyl sulfone black dye obtained in the step (f) is adjusted to pH=7.0 by a small amount of 10% liquid caustic soda. The prepared NaOH solution in the reaction step (g) was added to the above-mentioned conjugate within 1-1.5 hours, the pH was controlled to no more than 11, and the reaction was stirred for 15 minutes. An acidic substance was used, including but not limited to diluted hydrochloric acid, to quickly adjust the pH to 6.0-6.5, and the reaction came to end. A vinyl sulfone black dye mixture with removed sulfate (also known as KN-B vinyl sulfone black dye) is obtained. It has good stability, and its powder dye can also be obtained by spray drying.

(16) The KN-B vinyl sulfone black dye prepared by steps (a) to (h) will be used in the following examples of the present invention, and additive agents were added to evaluate its anti-aging effect.

(17) It should be noted that the above-mentioned acidic solutions, alkaline substances and acidic substances, etc., are only exemplary examples, and the application is not limited to those types.

Example 1

(18) In this embodiment, KN-A and KN-B vinyl sulfone black dyes were subjected to high temperature aging at 60 C. for 7 days. The results are shown in Table 1. The pH value of KN-B dyes decreased less and the pH value was around 6.0. The concentration of dissociated chloride ions and sulfate ions from KN-B was relatively less than from KN-A, which represents that KN-B has higher stability.

(19) TABLE-US-00001 TABLE 1 Changes in pH and stability of vinyl sulfone black dyes KN-A and KN-B during high temperature aging at 60 C. After Aging Before Aging (at 60 C. for 7 days) Dye Solution Cl SO.sub.4 Cl SO.sub.4 Sample No. Concentration Weight pH (ppm) (ppm) pH pH (ppm) (ppm) Black KNA-1 10% 50 g 4.85 / / 3.97 0.88 80 14490 CP-VS KNB-1 6.24 / / 5.78 0.46 16 52 Black KNA-2 5.10 / / 3.35 1.75 90 17910 CP-VS03 KNB-2 6.32 / / 5.83 0.49 10 33 Black KNA-3 5.68 / / 3.54 2.14 185 330 CP-VS04 KNB-3 6.51 / / 6.16 0.35 3 18 CP-VS03 is reddish shade black, and CP-VS04 is bluish shade black.

Example 2

(20) This embodiment was based on three KN-A and KN-B vinyl sulfone black dyes including different additive agents before and after spray drying. The pH change and dye stability were observed. Please see table 2 and table 3. It should be noted that the weight percentage of additive agents is based on the total weight of the dye.

(21) TABLE-US-00002 TABLE 2 Acetic acid/sodium hydroxide effect on the stability change of vinyl sulfone black dyes KN-A and KN-B during high temperature aging at 60 C. After Aging Before Aging (at 60 C. for 7 days) Dye Solution HAc/NaOH Cl SO.sub.4 Cl SO.sub.4 Sample No. Concentration Weight 10% pH (ppm) (ppm) pH pH (ppm) (ppm) Black KNA-1-1 10% 50 g 0.258 g 4.5 / / 3.75 0.75 74 12520 CP-VS HAc KNB-1-1 0.179 g 6.0 / / 5.68 0.32 13 48 HAc Black KNA-2-1 0.105 g 6.0 / / 4.45 1.55 88 16690 CP-VS03 NaOH KNB-2-1 0.093 g 6.5 / / 6.13 0.37 7 24 NaOH Black KNA-3-1 0.011 g 6.0 / / 4.01 1.99 179 292 CP-VS04 NaOH KNB-3-1 / 6.5 / / 6.36 0.14 1 10

(22) TABLE-US-00003 TABLE 3 Sodium acetate effect on the stability change of vinyl sulfone black dyes KN-A and KN-B during high temperature aging at 60 C. After Aging Before Aging (at 60 C. for 7 days) Dye Solution Sodium Cl SO.sub.4 Cl SO.sub.4 Sample No. Concentration Weight Acetate pH (ppm) (ppm) pH pH (ppm) (ppm) Black KNA-1-2 10% 50 g 0.1% 4.5 / / 4.41 0.09 53 12443 CP-VS KNB-1-2 0.4% 6.5 / / 6.21 0.29 5 26 Black KNA-2-2 0.8% 6.0 / / 4.98 1.02 63 16536 CP-VS03 KNB-2-2 0.2% 6.5 / / 6.36 0.14 12 23 Black KNA-3-2 0.1% 6.0 / / 5.15 0.85 166 283 CP-VS04 KNB-3-2 0.2% 7.0 / / 6.88 0.12 7 16

(23) It can be seen from Tables 2 to 3 that acetic acid and sodium hydroxide had a negative effect on the stability of the KN-A vinyl sulfone black dye. With the increase of the amount, the pH drops a lot, and the enhanced concentration of chloride and sulfate ions indicated that the dye has accelerated aging. Although it also has a negative effect on the KN-B vinyl sulfone black dye, the pH difference was less than 0.4, and both concentration of chloride ion and sulfate ion were less than 50 ppm. When the acetic acid/sodium hydroxide buffer solution was added with sodium acetate to enhance the buffering effect, KN-B vinyl sulfone black dyes CP-VS03 and CP-VS04 only need to add 0.2% sodium acetate to achieve stability at high temperature. The pH was maintained between 6.3-7.0, and the KN-A vinyl sulfone black dye CP-VS with 0.1% sodium acetate shows the smallest pH variation, and the concentration of chloride ion and sulfate ion was relatively low, indicating that the dye was relatively stable at pH=4.5.

(24) TABLE-US-00004 TABLE 4 The influence of diluted hydrochloric acid or sodium hydroxide on the stability of 10% vinyl sulfone black dye KN-B during high temperature aging at 60 C. Aging at high temperature 60 C. for 7 days Purity of HPLC Original 1st 2nd 3rd 4th 5th 6th 7th vinyl hydroxyethyl Sample No. pH day day day day day day day sulfone sulfone Black KNB-1-3 4 4.05 4.05 4.02 4.03 4.03 4.02 4.03 94.7% 3.73% CP-VS Black KNB-2-3 4 4.04 4.04 4.04 4.03 4.03 4.03 4.03 94.5% 3.52% CP-VS03 Black KNB-3-3 4 4.05 4.05 4.05 4.04 4.03 4.04 4.04 94.9% 3.28% CP-VS04 Black KNB1-4 5 4.94 4.87 4.85 4.84 4.82 4.80 4.80 94.4% 3.64% CP-VS Black KNB-2-4 5 5.01 5.00 5.00 5.00 4.95 4.93 4.93 94.5% 3.82% CP-VS03 Black KNB-3-4 5 5.00 5.00 5.00 4.97 4.98 4.96 4.96 94.8% 3.20% CP-VS04 Black KNB-1-5 6 6.01 6.00 6.02 6.00 5.97 5.97 5.96 94.6% 3.30% CP-VS Black KNB-2-5 6 6.01 6.00 6.00 5.99 5.97 5.98 5.97 94.9% 3.15% CP-VS03 Black KNB-3-5 6 6.02 6.01 6.01 6.00 6.00 5.98 5.96 94.8% 3.24% CP-VS04 Black KNB-1-6 7 7.00 7.00 6.98 6.99 6.96 6.96 6.95 94.1% 3.80% CP-VS Black KNB-2-6 7 7.01 7.00 7.00 7.00 6.98 6.97 6.97 94.5% 3.63% CP-VS03 Black KNB-3-6 7 7.01 7.00 7.01 7.00 7.00 6.98 6.99 94.7% 3.48% CP-VS04 Black KNB-1-7 8 8.00 8.01 7.97 7.97 7.96 7.95 7.95 94.2% 3.73% CP-VS Black KNB-2-7 8 8.01 8.00 8.00 7.98 7.99 7.96 7.96 94.7% 3.41% CP-VS03 Black KNB-3-7 8 8.01 8.00 7.99 7.97 7.97 7.96 7.96 94.9% 3.16% CP-VS04 Black KNB-1-8 9 8.97 8.95 8.95 8.92 8.91 8.90 8.87 93.9% 4.18% CP-VS Black KNB-2-8 9 8.98 8.95 8.94 8.95 8.93 8.93 8.89 93.5% 4.63% CP-VS03 Black KNB-3-8 9 8.98 8.94 8.93 8.91 8.91 8.88 8.86 93.6% 4.70% CP-VS04

(25) 300 g of KN-B vinyl sulfone black dye powder was diluted to 3000 ml solution, which was filtered through a Buchner funnel, equipped with ultrafiltration membrane for desalination, and nanofiltration membrane for concentration to a solid content of 10% to obtain the final refined product. The diluted hydrochloric acid or liquid caustic soda was used to adjust the pH of the refined product to 4, 5, 6, 7, 8, 9, and perform a high temperature aging test at 60 C. for 7 days. The pH value was tested every day. At the end, the HPLC purity was tested.

(26) It can be seen from Table 4 that after high-temperature aging of KN-B vinyl sulfone black dyes at different pH values, the changes in pH value after aging were all the same, the HPLC purity did not change significantly, and the difference was very small. At pH=9, the hydroxyethyl sulfone increased slightly, indicating that the dye itself was stable under various pH conditions.

(27) 300 grams of KN-A and KN-B vinyl sulfone black dye powders were diluted to 3000 ml solutions, and were filtered with a Buchner funnel, equipped with ultrafiltration membrane for desalination, and nanofiltration membrane for concentration to 10% solid content to obtain the final refined product. 0.2 wt. % of HEPES (4-(2-Hydroxyethyl)-1-piperazine ethanesulfonic acid) and TES (N-[Tris(hydroxymethyl)methyl]-2-aminoethanesulfonic acid) were respectively added according to Table 5 (shown in the drawing), then diluted liquid caustic was used to adjust the pH to 7.5, and a high temperature aging experiment was conducted at 60 C. for 7 days to detect the pH value. After finishing the aging experiment, HPLC purity was tested.

(28) It can be seen from Table 5 that after high-temperature aging with different additive agents, the pH stability of the KN-A vinyl sulfone black dye was quite different, and the HPLC purity was also very different compared to the original dye. On the contrary, for KN-B vinyl sulfone black dye, as long as HEPES and TES were added, the pH value can be relatively stable at 7.4-7.5, and it would not rise. The HPLC purity of TES was lower, but the range is not large.

(29) TABLE-US-00005 TABLE 6 The changes of pH and HPLC purity of 10% vinyl sulfone black dyes KN-A and KN-B with 0.2% HEPES additive agent after simulated spray drying. pH before pH after HPLC purity after simulated spray drying Sample No. spray drying spray drying pH vinyl sulfone hydroxyethyl sulfone Black KNA-1-9 7.51 4.52 2.99 47.4% 44.7% CP-VS KNB-1-9 7.50 7.43 0.07 93.2% 4.8% Black KNA-2-10 7.52 4.66 2.86 55.1% 40.8% CP-VS03 KNB-2-10 7.51 7.45 0.06 93.8% 4.7% Black KNA-3-11 7.50 4.19 3.31 64.0% 31.9% CP-VS04 KNB-3-11 7.51 7.44 0.07 93.5% 4.6%

(30) Please refer to Table 6, an appropriate HEPES additive agent was selected and a simulated spray drying experiment was conducted. After the simulated spray drying was completed, the pH and HPLC purity were also tested. After the simulated spray drying, the pH drop of the three KN-B vinyl sulfone black dyes was relatively close, and the HPLC purity was about 1% lower than the original. Therefore, compared to the aging at 60 C. for 7 days, the simulated spray drying had a smaller influence on the HPLC purity.

Example 3

(31) This embodiment focuses on the formula of additive agents (pH buffer agent) in KN-A and KN-B vinyl sulfone black dye inks. Please refer to the following data.

(32) TABLE-US-00006 TABLE 7 KN-A and KN-B vinyl sulfone black dye, CP- VS, in ink formula I (KN-A-VSI & KN-B-VSI) Material wt. % Proxel GXL (antibacterial agent) 0.08% Surfynol 465 (surfactant) 0.59% Ethylene glycol 19.50% 1,2-propanediol 9.80% Glycerin 2.50% CP-VS (KN-A/KN-B powder dye) 17.74% Deionized water Balance Total 100.00% pH value 5.0-5.5 Conductivity (ms) 8.0-10.0 Viscosity (at 25 C.) 7.0-8.0 Surface tension (at 25 C.) 36.0-37.0

(33) TABLE-US-00007 TABLE 8 The pH comparison of the ink (KN-A-VSI) containing buffer solution of 20% HEPES before and after the aging test CP-VS black ink KN-A KN-B KN-A KN-B KN-A KN-B Addition of 20% HEPES 0.73 0.10 1.42 0.2 aqueous solution (g) Adjusted pH value 5.06 7.67 5.50 7.70 5.90 7.84 Aging at 60 C. for 7 days 4.33 7.36 4.39 7.40 4.41 7.53 Aging at 60 C. for 14 days 4.21 7.28 4.10 7.31 4.09 7.36 Aging at 60 C. for 21 days 4.16 7.24 3.96 7.26 3.93 7.28

(34) From the comparison in Table 8, it can be seen that the pH value of formula I ink, KN-A vinyl sulfone black ink (KN-A-VSI) after high temperature aging for one week, all pH values dropped to about 4.4 and maintained at about 4.0 after aging for 2 to 3 weeks. The KN-B vinyl sulfone black dye ink (KN-B-VSI) with removed sulfate had pH value of 7.67 before adjusting with buffer solution. As the pH increased to 7.84 after three weeks of high temperature aging, pH was maintained between 7.20 and 7.30. As a result, it was estimated that the stable pH value of KN-A-VSI was about 4.0 and there was a risk of corrosion of the nozzles on print-heads. However, the stable pH value of KN-B-VSI was about 7.25 to protect the general nozzles. In addition, 20% HEPES in Table 8 is the weight percentage concentration of additive agent itself.

(35) TABLE-US-00008 TABLE 9 KN-A and KN-B vinyl sulfone black dye, CP-VS03, in ink formula A (KN-A-VS03A & KN-B-VS03A) Material wt. % Proxel GXL (antibacterial agent) 0.08% Surfynol 465 (surfactant) 0.59% Ethylene glycol 19.50% 1,2-propanediol 9.80% Glycerin 2.50% CP-VS03 (powder dye) 17.74% Deionized water Balance Total 100.00% pH value 5.0-5.5 Conductivity (ms) 8.0-10.0 Viscosity (at 25 C.) 7.0-8.0 Surface tension (at 25 C.) 36.0-37.0

(36) The embodiment in Table 9 uses sodium acetate (CH.sub.3COONa), ammonium acetate (CH.sub.3COONH.sub.4), sodium hydroxide (NaOH), disodium hydrogen phosphate (Na.sub.2HPO.sub.4), sodium dihydrogen phosphate (NaH.sub.2PO.sub.4) and other aqueous solutions as an additive agent. The amount is shown in Table 10 below. The stability of KN-A-VS03A ink and KN-B-VS03A ink is evaluated after adjusting pH value to 5.5 and 7.5, respectively.

(37) TABLE-US-00009 TABLE 10 The dosage of various pH adjusters contained in vinyl sulfone black dye (CP-VS03) in ink formula A No. Additive agent wt. % 1 N/A 0.0% 2 CH.sub.3COONa(20%)aq 0.5% 3 CH.sub.3COONH.sub.4(20%)aq 0.4% 4 NaOH(20%)aq 0.3% 5 NaH.sub.2PO.sub.4(7.5%)aq 0.3% 6 Na.sub.2HPO.sub.4(7.5%)aq + NaH.sub.2PO.sub.4(7.5%)aq 1.0%

(38) TABLE-US-00010 TABLE 11 The pH changes of inks (KN-A-VS03A & KN-B-VS03A) containing various pH adjusters after high temperature aging at 60 C. pH before No. CP-VS03 ink aging 1.sup.st day 2.sup.nd day 3.sup.rd day 5.sup.th day 7.sup.th day PH 1 KN-A 5.16 5.12 5.09 5.06 5.01 4.93 0.17 KN-B 7.37 7.33 7.31 7.30 7.27 7.26 0.11 2 KN-A 5.50 5.48 5.47 5.47 5.46 5.45 0.05 KN-B 7.50 7.47 7.45 7.41 7.38 7.34 0.16 3 KN-A 5.50 5.46 5.43 5.39 5.38 5.36 0.14 KN-B 7.50 7.43 7.36 7.32 7.29 7.27 0.23 4 KN-A 5.50 4.80 4.52 4.34 4.20 4.06 1.44 KN-B 7.50 7.45 7.41 7.34 7.31 7.28 0.22 5 KN-A 5.50 4.71 4.50 4.31 4.17 4.03 1.47 KN-B 7.50 7.44 7.40 7.37 7.34 7.26 0.24 6 KN-A 5.50 4.86 4.55 4.36 4.20 4.18 1.32 KN-B 7.50 7.46 7.43 7.40 7.35 7.29 0.21

(39) The embodiment of Table 10 added some pH adjuster aqueous solutions in different groups, and adjusted the ink to pH 5.50. Since the number 1 was not adjusted, the KN-A vinyl sulfone black ink (KN-A-VS03A) had pH value of 5.16, and the pH value of KN-B vinyl sulfone black ink (KN-B-VS03A) was 7.37; the % in the left column is the weight percentage concentration of the additive agent itself, and the % in the right column is the weight percentage concentration of the additive agent based on the total weight of the ink. In No. 2-6 of Table 11, each pH value slowly decreased with aging time. Among them, the combination of KN-A-VS03I ink and the additive agents with less change in pH value is No. 2 with sodium acetate (CH.sub.3COONa(20%)aq). Its pH value was still above 5 (pH=5.45) on the 7th day, and the pH value of No. 3 (CH.sub.3COONH.sub.4(20%)aq) was also above 5 (pH=5.36), which meant that there was still a risk of corrosion of the print-head nozzles. The pH value of ink KN-B-VS03A changed less without adding various additives, but the addition of sodium acetate can maintain the pH value between 7.30 and 7.40 after aging. Other additive agents made pH value of the ink drop to about 7.27 without obvious stabilizing effect. The characteristics of KN-B vinyl sulfone black ink formula A of this embodiment can be applied to general industrial nozzles, such as Konica Minolta, Ricoh, DigiFilm, etc.

(40) TABLE-US-00011 TABLE 12 KN-A and KN-B vinyl sulfone black dye, CP-VS04, in ink formula B (KN-A-VS04B & KN-B-VS04B) Material wt. % Proxel GXL (antibacterial agent) 0.08% Surfynol 465 (surfactant) 0.59% Ethylene glycol 11.25% 1,2-propanediol 6.50% Glycerin 2.75% CP-VS04 (powder dye) 9.00% Deionized water Balance Total 100.00% pH value 5.0-5.5

(41) TABLE-US-00012 TABLE 13 KN-A and KN-B vinyl sulfone black dye, CP-VS04, in ink formula C (KN-A-VS04C & KN-B-VS04C) Material wt. % Proxel GXLBIT-20 (antibacterial agent) 0.08% Surfynol 465 (surfactant) 0.14% Caprolactam 3.00% Ethylene glycol 13.50% Glycerin 5.00% Diethylene glycol 5.00% CP-VS04 (liquid dye) 64.10% Deionized water Balance Total 100.00% pH value 5.0-5.5 Conductivity (ms) 8.0-10.0 Viscosity (take 25 C. as standard) 6.0-7.0 Surface tension (take 25 C. as standard) 35.0-36.0

(42) TABLE-US-00013 TABLE 14 The pH changes of ink KN-A-VS04B, KN-B-VS04B, KN-B-VS04C and KN-B-VS04C containing additive agents after high temperature aging at 60 C. Aging at 60 C. for 7 days CP-VS04 Additive pH before pH after aging Cl SO.sub.4 No. ink agents Dosage (g) aging for 7 days pH (ppm) (ppm) B KN-A 10% Sodium 0.13 6.00 5.36 1.14 6 27 Acetate 20% HEPES 1.50 6.00 4.48 1.52 8 32 20% BES 1.54 6.00 4.23 1.77 11 35 KN-B 10% Sodium 0.27 7.50 7.46 0.04 8 18 Acetate 20% HEPES 0.16 7.50 7.43 .0.07 7 20 20% BES 0.20 7.50 7.42 0.08 7 21 C KN-A 10% Sodium 0.15 6.00 5.38 1.12 6 26 Acetate 20% HEPES 1.54 6.00 4.49 1.51 7 33 20% BES 1.61 6.00 4.25 1.75 11 34 KN-B 10% Sodium 0.30 7.50 7.45 0.05 5 12 Acetate 20% HEPES 0.16 7.50 7.44 .0.06 7 14 20% BES 0.21 7.50 7.42 0.08 6 15

(43) The embodiments in Tables 12 and 13 used 10% sodium acetate, 20% HEPES, and 20% BES (N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid) aqueous solutions to perform the stability evaluation for inks formula B and C containing KN-A and KN-B vinyl sulfone black dye, CP-VS04, in forms of powder and liquid respectively. After adjusting the pH value of KN-A-VS04 ink to 6.0 and KN-B-VS04 ink to 7.5, the changes in pH, free chloride ion and free sulfate ion were detected.

(44) It can be seen from Table 14 that the pH value of the dye KN-A-VS04 in the ink formula B and C was adjusted by additive agents. After the aging test, the pH value dropped below 5.5, and the chloride ion and sulfate ion were obviously released. However, the dye KN-B-VS04 maintained the pH value between 7.4 and 7.5 in each ink formula. The decline of powder and liquid dyes was almost close, and the concentration of chloride ion and sulfate ion was respectively maintained below 50 ppm, which shows that the dye including these three types of additive agents has obvious stabilizing effect. The characteristics of ink KN-B-VS03B can be applied to mainstream inkjet printheads, such as Epson printhead, while the characteristics of ink KN-B-VS04C can be applied to major high-speed inkjet printhead, such as Kyocera printhead. In addition, the additive agent % in Table 14 is the weight percentage concentration of the additive agent itself.

(45) All the features disclosed in the specification of the present invention can be combined in any way. The features disclosed in this specification can be replaced by features with the same, equivalent or similar purpose. Therefore, except for the emphasis placed on special statements, the technical feature disclosed in this specification is merely an embodiment of a series of equivalent or similar features.

(46) It will be understood that the above description of embodiments is given by way of example only and that various modifications may be made by those with ordinary skill in the art. The above specification, examples, and data provide a complete description of the present invention and use of exemplary embodiments of the invention. Although various embodiments of the invention have been described above with a certain degree of particularity, or with reference to one or more individual embodiments, those with ordinary skill in the art could make numerous alterations or modifications to the disclosed embodiments without departing from the spirit or scope of this invention.