TWI342887B - A yellow dye compound and an ink composition comprising the same - Google Patents

Description

1342887 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a yellow dye compound, especially a yellow dye compound suitable for ink jet printing inks; the invention also relates to a yellow ink composition containing the aforementioned 5 yellow dye compounds Things. [Prior Art] Inkjet printing technology is a non-impact printing technology, which is characterized by the need to provide a clear, burr-free image, while the 10 inks used for inkjet printing need to have good light fastness. Optical density, solubility, storage stability, print fluency, etc. 'to achieve excellent print quality. At present, there are several kinds of yellow dyes used in inkjet printing inks, for example: Reactive Yellow No. 95, Direct Yellow No. 86, Direct Yellow No. 132, and Acid Yellow No. 23 ' in Taiwan Patent TWI 265, 181 and US Patent US 6,867,286 15 There are yellow dyes that expose inkjet printing inks. However, the yellow dyes formulated by the prior art are caused by poor light fastness and low solubility, which cause problems such as sinking and blocking. Further affecting the printing quality, resulting in uneven color, broken lines and other phenomena. The development of new yellow dyes with good light fastness and solubility has made the choice of yellow inkjet printing inks more choices and is a continuous effort. SUMMARY OF THE INVENTION 5 1342887 The present invention provides a novel yellow dye compound suitable for use as a yellow dye compound for ink jet inks. The more chromonic dye compound of the present invention has the structure of the following formula G) ··

(I)

Wherein, HCH3 or _COOH; r2, R3, and R4 are each independently H, -a, -so3h, -so2nha-so2CH2CH2〇h. 10 Specific examples of the yellow dye compound of the formula (1) of the present invention are as follows:

15

rO so3h 6 1342887 (1-3) η

So2nh2

π

So2ch2ch2oh (1-8) 7 15 1342887 In the present invention, the 'dye molecule' is represented by the form of a free acid, but the actual form may be a metal salt or an ammonium salt, more preferably an alkali metal salt or an ammonium salt. The yellow dye compound of the present invention can be further prepared into a composition of yellow ink 5. The yellow ink composition of the present invention comprises: (A) a yellow dye compound of the following formula (I):

Wherein 'R^-CH3 or -COOH; R2, r3, and 4 are each independently Η, -Cl, -so3h, -so2nh2 or -so2ch2ch2oh; wherein the content of the component (A) yellow dye compound is 〇 1 to 35.0% by weight; (B) an organic solvent selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol (propylene glycol), butylene glycol (butylene glycol), ethylene glycol monoethyl ether, ethylene glycol glycol monobutyl ether, diethylene glycol monobutyl & I (diethylene Glycol monobutyl ether), diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethyl Triethylene glycol monobutyl ether, glycerine, 2- 8 1342887 0-pyrrolidone, N-methyl-2-pyrrolidone ' 1,3-Dimethyl_2_ imidazoline _ (1,3- a group consisting of dime thyl-2-imidazolidinone) and triethanolamine; wherein the component (B) is in an organic solvent content of 5.0 to 35.0% by weight; and (c) water; wherein the composition Part (c) water content is from 3 94 to 94 9 weight percent. The yellow ink composition of the present invention may further comprise: 10 15 20 (D) a nonionic surfactant having a content of from 0.1 to 5.0% by weight of the nonionic surfactant. Suitable nonionic surfactants are, for example, acetylene glycol-based surfactants or alkoxylate surfactants. Specific examples of the acetylene glycol-based surfactant include:

Surfynol 485, Surfynol 465, Surfynol 440, Surfynol 420 '

Surfynol 104 (sold by Air Products & Chemicals, Inc.). Specific examples of the oxyalkylate surfactant include: Tergit〇l 15_s_5,

Tergitol 15-S-7, Tergitol 15-S-9 (sold by Union Carbide). The yellow ink composition of the present invention may be added with (E) a buffering agent and/or a microbicide as needed. Suitable buffering agents are, for example, acetic acid, acetate, phosphoric acid, phosphate, borax, borate or citrate. Microbicides, such as .NUOSEPT (sold by Nudex Inc., a division of Huls Americal), UCARCIDE (sold by Union Carbide), VANCIDE (sold by RT Vanderbilt Co.) and PROXEL (by ICI Americas) Sold by). The above-mentioned additional components are disclosed in Taiwan Patent No. TW589,352 or U.S. Patent No. 1,1,342,887, US Pat. No. 5,725,641. The microbicide is calculated based on the total weight of the ink, and is usually used in an amount of 0.01 to 1% by weight. [Embodiment] 5 The yellow dye compound of the present invention can be synthesized in the following manner. First, 2-naphthylamine-3,6,8-trisulphonic acid is dissolved and dispersed in glacial acid water, followed by sodium nitrite solution. The diazotization reaction is carried out. Further, l-phenyl-3-methyl-5-pyazolone was dispersed in water, and the dispersion was added to the above diazotization reaction solution to carry out a coupling reaction, thereby obtaining the following Formula (1_2)

The yellow dye compound of the present invention. 15

The water-soluble dye in the yellow ink composition of the present invention may be used singly or in combination with the above dye or an alkali metal salt of the above dye. Preferably, it is preferred to have a low salt content, i.e., the dye should have a total salt content of less than 0.5 weight percent based on the weight of the dye. The dye produced by the ten preparations and/or having a relatively high salt content due to the subsequent addition of the diluent may be desalted, for example, by a membrane separation method such as ultrafiltration, nebulization, reverse osmosis or analysis. The salt is removed. The preparation of the yellow ink composition of the invention is not particularly limited, and the components can be prepared by mixing the components in a desired amount by a conventional method. 20 1342 887 - The following examples are merely illustrative of the invention, but the scope of the application of the invention is not limited thereby. Although the compound is represented by free acid II, its actual form may be metal ruthenium or salt, and it may be a metal salt or a salt. Unless otherwise specified, the temperature is in degrees Celsius, and the relationship between the number of shots and the percentage of the weight and the percentage of the volume is the relationship between kilograms and liters. Example 1 1 〇 0·0400 mol (丨5,32 g) of 2-naphthylamine-3,6,8-trisuiphomc acid (2-naphthylamme-3,6,8-trisuiphomc acid) as 5〇 Disperse in deionized water, add O.UOO Mo (13.7 g) of hydrochloric acid, and keep the reaction temperature at Ot: in an ice bath. In addition, 0.0412 mol (2 84 g) of nitrite was dissolved in 1 ml of deionized water. After the dissolution was completed, the nitrous 15 salt solution was added dropwise to 2-naphthylamine-3,6. In the dispersion of 8-trisulphonic acid, at this time, the temperature is controlled to be 0 to 5C. After 60 minutes of reaction, the excess nitrite was removed as an amine sulfonic acid solution. In a separate beaker, first 0.0412 moles (8.59 grams) of 1-(2,5,-dioxa-4-sulfophenyl)-3-indolyl.5. The thiazolone (1_(2,,5,_dichi〇r〇_ 20 4-sulfophenyl)-3-methyl-5-pyazol〇ne) was dispersed in 100 ml of deionized water. Pour this dispersion into the diazonium salt solution of 2_naphthylamine_3,6,8-trisulphonic acid prepared in the previous stage, and control the temperature to 5~1〇乞^ followed by sodium carbonate. The value (pH value) is slowly adjusted to 8. 〇 or more, the reaction solution is stirred for 6 〇 minutes, and finally 8% volume of sodium hydride is added for salting out, then the product precipitate is obtained and filtered and dried. A compound of the formula 1) of the invention. 25 1342887 Example 2 0.0400 mol (15.32 g) of 2-naphthylamine-3,6,8-trisulphonic acid was dispersed in 50 ml of deionized water, followed by 〇·丨200 mol (13.7 g). Hydrochloric acid, and the reaction temperature was maintained at 〇 ° C with 5 ic. In addition, 0.0412 mol (2.84 g) of nitrosyl salt was found in 10 ml of deionized water. After the dissolution was completed, the nitrite solution was added dropwise to 2-naphthylamine _3,6. In the dispersion of 8_trisulphonic acid, the temperature is controlled to 51:. After 60 minutes of reaction, excess nitrite was removed as an amine sulfonic acid solution. 10 In a separate beaker, first 0.0412 mol (7.18 g) of 1-phenyl-3-indolyl-5-pyrene (1 - phenyl-3-methyl-5-pyazolone) with 100 ml deionized Water is dispersed. This dispersion was poured into a diazonium salt solution of 2_naphthylamine-3,6,8-trisulphonic acid prepared in the previous stage, and the temperature was controlled at 5 to 1 (). Then slowly adjust the pH value to 8.0 or more with sodium carbonate, and stir the reaction solution for 6 〇 15 minutes. Finally, add 8% volume of sodium hydride for salting out, then the product can be obtained and filtered and dried. A compound of the formula (?_2) of the present invention is obtained. > Example 3 0.0400 mol (15.32 g) of 2-naphthylamine-3,6,8-trisulphonic acid was dispersed in 50 ml of deionized water, and 0.1200 mol (13.7 g) of hydrochloric acid was further added. The reaction temperature was maintained at 〇 ° C in an ice bath. In addition, 0 〇4丨2 mol (2.84 g) of nitrite was dissolved in 10 ml of deionized water. After the dissolution was completed, the nitrite solution was added dropwise to 2-naphthylamine·3,6. In the dispersion of 8-trisulphonic acid, the temperature is controlled at 0 to 5 ° C at this time. After the reaction for 60 minutes, the excess nitrite was removed with an aminosulfonic acid solution 25. 12 1342887 In another beaker, first 0 0412 mol (10.63 g) of 1-(p-sulfophenyl)-3-methyl-5-. I-(4,-sulfophenyl-3-methyl-5-pyazolone) was dispersed in 1 mL of deionized water. This dispersion was poured into a diazonium salt solution of 2-naphthylamine-3,6,8-trisulphonic acid prepared in the previous stage, and the temperature was controlled at 5 to 1 °C. Then slowly adjust the pH value to 8.0 or more with sodium carbonate', stir the reaction solution for 60 minutes, and finally add 8% volume of sodium carbonate for salting out, then the product precipitate can be obtained and filtered and dried. A compound of the formula (1-3) of the invention. 10 Example 4 0.0400 mol (15.32 g) of 2-naphthylamine-3,6,8-trisulphonic acid was dispersed in 50 ml of deionized water and then 0,1200 mol (13.7 g) of hydrochloric acid was added, and The reaction temperature was maintained in an ice bath. Hey. In addition, 〇〇412 摩尔 (2 84 g) of nitrite was dissolved in 10 ml of deionized water. After the dissolution was completed, the nitrite solution was added to 2-naphthylamine-3 by the dropwise addition method. In the dispersion of 6,8-trisulphonic acid, the temperature is controlled at 0 to 5 at this time. (: After 60 minutes of reaction, the excess nitrite was removed with an amine sulfonic acid solution. > In another beaker, 0.0412 mol (1 〇 4 g) of 丨_(p-sulfonamide was first stupid) Base)·3-methyl_5-» ratio. Sesone (l_(4_sulphamid〇phenyl)-20 3_1TiethyM-pyazolone) was dispersed in 100 ml of deionized water. This dispersion was poured into the 2-naphthalene prepared in the previous stage. Azine-3,6,8-trisulphonic acid in a diazonium salt solution, and the temperature is controlled to 5 to 10. (:. Then slowly adjust the pH value to 8.0 or more with sodium carbonate) After 〇 minutes, finally adding 8% by volume of sodium hydride for salting out, the product precipitate can be obtained and filtered and dried to obtain the compound of the formula (1-4) of the present invention. 13 1342887 Example 5 0.0400 mol (15.32 g) of 2-naphthylamine-3,6,8-trisulphonic acid was dispersed in 50 ml of deionized water, then 〇.12〇〇 mol (13 7 g) of hydrochloric acid was added, and 5 The ice bath was kept at a reaction temperature of 〇 ° C. In addition, cerium salt of 〇 〇 412 摩尔 (2.84 g) was dissolved in 10 ml of deionized yttrium, and after completion of dissolution, nitrite was added dropwise. The solution is added to a dispersion of 2-naphthylamine-3,6,8-trisulphonic acid, at which time the temperature is controlled to 0 to 5. (: After 60 minutes of reaction, the amine-based acid-soluble solution will be Excess nitrite is removed. 10 In another beaker, '0.0412 mol (8.59 g) of 1-(2-phenylphenyl)-3-methyl-5- ° 嗤_ (1-( 2,-chlorophenyl)-3-methyl- 5-pyazolone) Disperse in 1 ml of deionized water. Pour this dispersion into the prepared 2-naphthylamine-3,6,8-trisulphonic acid. In the diazonium salt solution, and control the temperature at 5~10. (:. Then slowly adjust the pH value to 8 with sodium carbonate, 〇 to 15, stir the reaction solution for 6 〇 minutes, and finally add 8%. A volume of sodium hydride is subjected to salting out to obtain a product precipitate which is filtered and dried to obtain a compound of the formula (1-5) of the present invention. Example 6 20 will be 0.0400 mol (15.32 g) of 2 -Naphthylamine-3,6,8-trisulphonic acid was dispersed in 50 ml of deionized water, then hydrazine 12 Torr (137 g) of hydrochloric acid was added, and the reaction temperature was maintained at 〇〇C with ice. Place 〇〇412 莫 (2 84 g) of nitrosylurethane salt in 1 〇 ml In deionized water, after the solution is completely dissolved, the nitrite solution is added dropwise to the dispersion of 2_naphthylamine_3,6,8-trisulphonic acid, and the temperature is controlled at 0 to 5 at 14 1342887. °C. After 60 minutes of reaction, the excess nitrite was removed with an amine sulfonic acid solution. In another beaker, 0.0412 mol (8.59 g) of 1-(3-phenylphenyl)-3 was first introduced. - 1 -(3'-chlorophenyl)-3-methyl-5 5-pyazolone was dispersed in 100 ml of deionized water. This dispersion was poured into a diazonium salt solution of 2-naphthylamine-3,6,8-trisulphonic acid prepared in the previous stage, and the temperature was controlled at 5 to 10 °C. Subsequently, the pH value is slowly adjusted to 8.0 or more with sodium carbonate. The reaction solution is stirred for 60 minutes, and finally 8% by volume of sodium carbonate is added to the salting solution to obtain a product precipitate, which is filtered and dried. The compound of the formula (1-6) of the present invention 10 is obtained. Example 7 0.0400 mol (15.32 g) of 2-naphthylamine-3,6,8-trisulphonic acid was dispersed in 50 ml of deionized water, and then 0.1200 mol (13.7 g) of hydrochloric acid was added, and 15 ice was added. The bath is kept at the reaction temperature. (:. Further, 0.0412 mol (2.84 g) of nitrite was dissolved in 10 ml of deionized water. After the dissolution was completed, the nitrite solution was added dropwise to 2-naphthylamine _3,6. In the dispersion of 8-trisulphonic acid, the temperature was controlled at this time. After 6 minutes, the excess nitrite was removed with an aminosulfonic acid solution. 20 In another beaker 0.0412 mol (11.7 g) of 1-(4-sulfophenyl)-3-carboxy-5-pyrazolone (l-(4-sulfophenyl)-3-carboxy-5-pyaZ〇l〇ne)a Disperse in 100 ml of deionized water. Pour this dispersion into the diazonium salt solution of 2-naphthylamine_3,6,8-trisulphonic acid prepared in the previous stage, and control the temperature at 5~l〇t. Slowly adjust the pH value to more than 8〇 with sodium carbonate, 25 to mix the reaction solution for 60 minutes, and finally add 8% volume of sodium hydride to salt 15 1342887 • Analysis to obtain product precipitate and filter Drying gives the compound of the formula (1-7) of the present invention. Example 8 5 Dispersing 0.0400 mol (15.32 g) of 2-naphthylamine-3,6,8-trisulphonic acid in 50 ml of deionized water , then add 0.1200 m (13.7 g) Hydrochloric acid, and keep the reaction temperature in 冰.〇. In addition, 0.0412 mol (2.84 g) of nitrite is dissolved in 10 ml of deionized water, and after being dissolved completely, it is added dropwise. The nitrate solution is added to the dispersion of 2-naphthylamine-3,6,8-trisulphonic acid. At 10 o'clock, the temperature is controlled to 5 ° C. After 60 minutes of reaction, the acid-based acid solution will be excessive. The nitrite was removed. In another beaker '0.0412 m (10.63 g) of 1-(4-β-hydroxyethylsulfonylphenyl)-3-indolyl-5-. 1-(4-p-hydroxyethylsulfonylphenyl)-3-methyl- 5-pyazolone 15 Disperse in 100 ml of deionized water. This dispersion was poured into a diazonium salt solution of 2-naphthylamine-3,6,8-trisulphonic acid prepared in the previous stage, and the temperature was controlled at 5 to 1 °C. Then slowly adjust the pH value to above 8·〇 with sodium carbonate, mix the reaction solution for 6 minutes, and finally add 8% volume of sodium carbonate for salting out, then the product precipitate can be obtained and filtered. Drying is carried out to obtain the octa 20 of the formula (1-8) of the present invention. Example 9 Preparation of yellow ink composition: (Α) (1-1) compound 3 parts, (Β) solvent diethylene glycol 5 parts, diethyl 25-butanol monobutyl ether 5 parts, glycerin 5 parts, and (c The yellow ink composition of the present invention can be obtained by adding water to 100 parts by mechanically stirring 2 16 1342887 • stirring for half an hour, and then performing absolute-filtration with 0.45 # m filter paper. Example 1 0 5 Preparation of Yellow Ink Composition (A) 3 parts of the compound of the formula (1-2), 5 parts of the solvent diethylene glycol, 5 parts of diethylene glycol monobutyl ether, 5 parts of glycerin, (D) ) Surfyn 〇 M65 surfactant ι parts, and (C) add water to 1 〇〇 part, stir with a mechanical mixer for half an hour, and then absolute filtration with φ 0.45 # 111 filter paper, the yellow ink composition of the invention can be obtained 10 0 Example 11 Preparation of yellow ink composition (A) 3 parts of the compound of the formula (1-3), (8) 5 parts of the solvent diethylene glycol, 1 part of diethyl hexadecanol _ 5 parts, 5 parts of glycerin, (D Surfynol 465 surfactant ι, (E) Pr〇xei χ [2 microbicide 〇. 3 parts, and (〇 add water to 1 〇〇, stir with a mechanical mixer for half an hour, then 0.45 // The yellow ink composition of the present invention can be obtained by performing the absolute filtration of the paper. 20 Example 1 2 Substituting the compound of the formula (1-4) for the compound of the formula (1-1), the same example A yellow ink composition was prepared in the same manner. Example 13 17 1342887. Substituting the compound of formula (1) 5) for the compound of formula (1-1), the same procedure as in Example 11 Prepare a yellow ink composition. Example 14 5 Substituting the compound of the formula (1-6) for the compound of the formula (M) The same procedure as in Example 11 was carried out to prepare a yellow ink composition. Example 15 Φ A yellow ink composition was prepared by the same procedure as in Example 10 11 except that the compound of the formula (1-1) was used instead of the compound of the formula (1-1). Example 16 Substituting the compound of the formula (1-8) A compound of the formula (μ) was prepared in the same manner as in Example 11 to prepare a yellow ink composition. 15 Comparative Example 1 Preparation of yellow ink • 3 parts of acid yellow No. 23 (commercially available from Yongguang Co., Ltd.), diethylene glycol 5 Injury, 5 parts of diethylene glycol monobutyl ether, 5 parts of glycerin, 1 part of Surfynol 465 interface 20, pr〇xel XL2 microbicide 〇. 3 parts, and added water to 100 parts, mixed with a mechanical mixer The hourly 'again filter with 0.45 #m filter paper' can produce yellow ink. Comparative Example 2 25 Yellow ink preparation 18 1342887 One wide take direct yellow No. 132 No. 3 (commercially available from Yongguang Company), two 5 parts of ethylene glycol monobutyl ether, 5 parts of glycerol, Surfynol 465 boundary, Μ 1 know, Pr〇xel XL2 microbicide 〇 · 3 parts, and add water to 1 〇〇 wound with a mechanical stirrer for half an hour, then Make a yellow ink with 0.45 # m filter paper for absolute 5 Comparative Example 3 Yellow ink was prepared by taking No. 86 No. 86 (commercially available from Yongguang Co., Ltd.), diethylenediamine 10 仏 'diethylene glycol monobutyl ether 5 parts, glycerin 5 parts, Surfynol 465 interface 1 part of active agent, 3 parts of Proxel XL2 microbicide, and 1 part of water, stirred by a mechanical stirrer for half an hour, and then dried over 0.45 μm filter paper to obtain a yellow ink. 15 Photofastness Test Methods and Results Print Test Conditions: Ink: The inks prepared in Examples 9 to 16 and Comparative Examples 1 to 3. * Printed paper: Plain paper. Printer: EPSONSTYLUS C45 PRINTER. 20 Print Strength ( Depth): FORMULA : CIE L*a*b*. Light fastness test conditions: Irradiate the printed paper with a xenon arc lamp, irradiate the total energy of 85KJ, and then measure the ray arc lamp with ICS The change of color difference, if the larger the DE, the greater the color change before and after the irradiation, the worse the light fastness. The rating is 25: AATCC and ISO A05.

The ink test results are organized as follows: Table 1, ink test results, yellow ink, and more

17% 100 ε/L

Example 13 Example 14

As can be seen from Table 1, the yellow ink composition of the embodiment of the present invention has a j-day brilliance and a preferable solubility, which should be in the comparative example on the ink-jet ink. >, _ 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚 迚However, the above-mentioned embodiments are merely illustrative for the convenience of the description of 20 10 1342887, and the scope of the claims of the present invention is subject to the scope of the patent application, and not only Limited to the above embodiment. [Simple description of the diagram] 5 None. [Main component symbol description] None. 10

twenty one

Claims (1)

1342887 X. Patent application scope: The structure is as follows (I): 1. A yellow dye compound Standing as ^ ; R2, R3, κ4 are "Η, -Cl, -SO3H, -S〇, NH bucket, U2NH2tS〇2CH2CH2OH. 2. The yellow dye compound as described in the patent application No. 丨, wherein Ri is -CH3. The yellow dye compound according to item 1 is a yellow dye compound of the formula (1-1). 3. The patent range is as follows: wherein Ri is -COOH. 4 · As claimed in the patent scope, wherein the compound of the formula (I) is as follows So3h 20 its yellow face 22 1342887 S〇3H wherein 6. The yellow compound of the formula (I) is as follows (1_7), Compound, dye compound, S03H 15 7· A more color ink composition comprising: (Α) — a yellow dye compound as described in the scope of the patent application, wherein the composition of the bismuth (Α) is 0, 1~35.0% by weight; (8) Once the organic solvent is formed, the content of the organic solvent is from 5 〇 to 35:0, and the organic solvent is selected from the group consisting of: ethylene glycol, glycol-ethyl alcohol , propylene glycol, butanediol, ethylene glycol monoethyl ether, ethylene glycol, monobutyl ether, diethylene glycol monotop, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether 'three a group of ketones, glycerol, 2-D pirone, Ν-methyl, rosin, W dimethyl-2-keto ketone, and triethanolamine; and (C Κ It is set to 3 〇. 〇 to 94 9 weight percent. 8. The scarf. Yellow ink composition as described in item 7 of the patent scope, 23 20 1342887 Medium Ri is -CH3. 9. The yellow ink composition according to item 7 of the patent application, wherein R is -COOH. The yellow ink composition according to claim 7, wherein the compound of the formula (I) is as follows (1-1) Compound. 11. The yellow ink composition according to claim 7, wherein the compound of the formula (I) is as follows (1-3) Compound. 12. The yellow ink composition according to claim 7, wherein the compound of the formula (I) is as follows (1-7) 24 compounds. -7-7) 13. As claimed in the seventh item of claim 4, which is a vapor-colored ink composition 'iQ κ ; 楂 non-ionic surfactant, the content of the wound (9) non-ionic surfactant is (U to 5.0) The yellow ink composition of claim 13, wherein the nonionic surfactant is an alkyne-based surfactant or a ceramide surfactant.