HK1091506B - Black dyes composition for ink-jet inks - Google Patents

Description

Black ink dye composition

Technical Field

The present invention relates to a black ink dye composition, particularly to a black ink dye composition suitable for paper inkjet printing.

Background

The inkjet printing technology is a non-impact printing technology (non-impact printing), and the technical characteristic requirements of the technology comprise: it is desirable to provide clear (sharp), non-feathered (non-feathering) images, good water-fastness, light-fastness, optical density, fast drying and storage stability, good printing smoothness, non-clogging jets, and the like.

Reactive dyes are used, for example: when the reactive Red 180(c.i. reactive Red 180) or the reactive Black 31(c.i. reactive Black 31) in the Color Index is used as a dye component of the ink-jet ink, the pH of the ink becomes unstable due to the hydrolysis of the reactive group with time, and the salts in the ink increase with the hydrolysis reaction, causing problems such as nozzle clogging and Color change of the ink.

In US4,694,302 and US5,062,892, it is disclosed that the Black ink dye composition used in the past, such as edible Black 2(c.i. food Black 2), has not good properties such as light fastness, and fails to meet the printing requirements of the former writing; for example, direct Black 168(c.i. direct Black 168) has good light fastness but has low solubility and is limited to be used as an ink-jet dye component.

Therefore, how to provide a black dye composition in a dye composition for ink-jet printing ink, which has the characteristics of good light fastness, wide color gamut (color space), good solubility, good printing fluency and the like, is the direction of continuous effort.

Disclosure of Invention

The invention aims to provide a black ink dye composition, in particular to a black ink dye composition suitable for paper inkjet printing, which can obtain an ink dye composition with good light fastness and good solubility.

In order to achieve the above object, the present invention provides a composition, which mainly comprises:

(A) a compound of the formula (I)

Wherein R is₁is-SO₂CH₂CH₂OSO₃H or-SO₂CH＝CH₂or-SO₂CH₂CH₂OH; m is H, Na or Li;

(B) a compound of the formula (II)

Wherein R is₁is-SO₂CH₂CH₂OSO₃H or-SO₂CH＝CH₂or-SO₂CH₂CH₂OH; m is H, Na or Li; and

(C) a compound of the following formula (III)

Wherein R is₁Can be-SO₂CH₂CH₂OSO₃H or-SO₂CH＝CH₂Or SO₂CH₂CH₂OH; m may be H, Na or Li.

Wherein R in the compound of formula (I)₁is-SO₂CH＝CH₂Or SO₂CH₂CH₂OH。

Wherein R in the compound of formula (II)₁is-SO₂CH＝CH₂Or SO₂CH₂CH₂OH。

Wherein R in the compound of formula (III)₁is-SO₂CH＝CH₂Or SO₂CH₂CH₂OH。

Wherein the compound of the formula (I) is a compound of the formula (I-1),

wherein M is H, Na or Li.

Wherein the compound of formula (II) is a compound of formula (II-1)

Wherein M is H, Na or Li.

Wherein the compound of the formula (III) is a compound of the formula (III-1),

wherein M is H, Na or Li.

Wherein the weight percentage of the compound of formula (I) in the component (A) is 50-94%; the weight percentage of the compound of formula (II) of the component (B) is 3-47%; and the weight percentage of the compound of formula (III) in the component (C) is 3-30%.

Also comprises a group of component (D) organic solvents which are selected from the group consisting of: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, 2-pyrrolidone, N-methyl-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, triethanolamine.

Also comprises a group of components (E) of a surfactant, wherein the surfactant is a compound shown as the following formula:

wherein the sum of n and m is an integer between 0 and 50.

Wherein the compound of the formula (I) is a compound of the formula (I-1),

wherein M is H, Na or Li; the compound of formula (II) is a compound of formula (II-1)

Wherein M is H, Na or Li; and the compound of formula (III) is a compound of formula (III-1),

wherein M is H, Na or Li.

Also comprises a group of component (D) organic solvents which are selected from the group consisting of: ethylene glycol (ethylene glycol), diethylene glycol (diethylene glycol), triethylene glycol (triethylene glycol), propylene glycol (propylene glycol), butylene glycol (butylene glycol), ethylene glycol monoethyl ether (ethylene glycol monoethyl ether), ethylene glycol monobutyl ether (ethylene glycol monobutyl ether), diethylene glycol monoethyl ether (ethylene glycol monomethyl ether), 2-pyrrolidone (2-pyrrolidone), N-methyl-pyrrolidone (N-methyl-2-pyrrolidone), 1, 3-dimethyl-2-imidazolidinone (1, 3-dimethyl-2-imidazolidone), triethanolamine (triethanolamine).

Also included is a component (E) which is an acetylene glycol (acetylene glycol) derivative selected from the group consisting of the compounds of the formula:

wherein the sum of n and m is an integer between 0 and 50.

Wherein M of the compounds of formula (I-1), formula (II-1) and formula (III-1) is Li.

Detailed Description

70 parts of dye in formula (I), 15 parts of dye in formula (II) and 15 parts of dye in formula (III) in the composition are uniformly mixed to obtain the dye composition of the embodiment; specific structures and sources of the formula (I), the formula (II) and the formula (III) in the composition of the present invention are exemplified as follows, but not limited to the following illustrative examples:

the specific structure of the compound of formula (I) in the composition of the present invention is exemplified by: reactive Black 5. I.reactive

The source is obtained from commercially available reactive black dyes, available under trade names such as: everzol black b.

The specific structure of the compound of formula (II) in the composition of the present invention is exemplified by:

the preparation method is disclosed in German patent publication No. DEl 911427.

The specific structure of the compound of formula (III) in the composition of the present invention is exemplified by:

a process for producing the same is disclosed in Japanese patent publication No. JP-B-45-40182.

The proportion of the components of the compounds of formula (I), (II) and (III) in the composition of the present invention is not particularly limited; in general, the minimum relative weight percentage of each component proportion is 3%, and the maximum relative weight percentage is 95%.

The proportion of each component in the composition of the present invention is preferably 50 to 94% by weight of the compound of formula (I) in component (A); 3 to 47% by weight of a compound of the formula (II) as the component (B); 3 to 30% by weight of the compound of formula (III) as the component (C).

Buffers which can be used are, for example: acetic acid, acetate, phosphoric acid, phosphate, borax, borate or citrate. Antibacterial agents that can be used are, for example: NUOSEPT (sold by Nudex inc., a division of shells america), UCARCIDE (sold by Union Carbide), VANCIDE (sold by RTVanderbilt co., and PROXEL (sold by ICI Americas); the above components are disclosed in Taiwan patent TW589352 or US5,725,641.

The following are specific processes for the preparation of the compounds (I), (II) and (III) of the present invention, examples of which are not intended to be limiting:

dye preparation example 1

30kg of dye of formula I-3, adjusting the pH value to 9-10 by 500ml of 45% sodium hydroxide aqueous solution, controlling the temperature to 25-30 ℃, carrying out hydrolysis reaction for 60 minutes, adjusting the pH value to 7-7.5 by 30ml of 32% hydrochloric acid solution, carrying out reverse osmosis desalination, replacing lithium salt by about 30%, and carrying out spray drying to obtain the powder (lithium salt) of formula I-2.

Dye preparation example 2

The following II-2 powder (lithium salt) of the present invention was obtained by repeating the procedure of the dye preparation example 1 above, with the II-3 dye substituted for the dye of formula I-3.

Dye preparation example 3

The step of the dye preparation example 1 is repeated by using the III-3 dye to replace the dye of the formula I-3, so as to obtain the following III-2 powder (lithium salt) of the invention.

Dye preparation example 4

Dissolving 2kg of dye compound powder of formula I-2 in 18kg of water, adjusting the pH value to 7-7.5 by 30ml of 32% hydrochloric acid solution, carrying out reverse osmosis desalination, replacing lithium salt by about 30%, and carrying out spray drying to obtain the powder (lithium salt) of formula I-1.

Dye preparation example 5

The II-2 dye is used for replacing the dye with the formula I-2, and the step of the dye preparation example 4 is repeated to obtain the formula II-1 powder (lithium salt) of the invention.

Dye preparation example 6

The dye of formula I-2 is replaced by the dye of formula III-2, and the procedure of the dye preparation example 4 is repeated to obtain the powder (lithium salt) of formula III-1 of the invention.

The dye compounds obtained in the above preparation examples were combined with an ink vehicle to prepare an ink composition, and compared with Bayscript Black SP product from Bayer corporation and Duasyn Direct Black HEF-SF product from Clafiant corporation, which are currently common Black ink compositions in the market, the printing characteristics and the light fastness test methods and data thereof are shown in the following ink examples.

Example 1: the composition of the present invention

70 parts of dye of formula (I-1), 15 parts of dye of formula (II-1) and 15 parts of dye of formula (III-1) are respectively put into a beaker, mixed with each other and stirred for 30 minutes by a stirrer to obtain a uniform dye composition, the pH value is adjusted to 7-7.5 by 32% hydrochloric acid solution, reverse osmosis desalination is carried out, about 30% of lithium salt is replaced, and the dye composition is obtained after spray drying.

Example 2: the composition of the present invention

70 parts of dye of formula (I-3), 15 parts of dye of formula (II-3) and 15 parts of dye of formula (III-3) are respectively put into a beaker, mixed with each other and stirred for 30 minutes by a stirrer to obtain a uniform dye composition, then the pH value is adjusted to 9-10 by 45% sodium hydroxide aqueous solution, the temperature is controlled to be 25-30 ℃, hydrolysis reaction is carried out for 60 minutes, then the pH value is adjusted to 7-7.5 by 32% hydrochloric acid solution, reverse osmosis desalination is carried out, lithium salt is replaced by about 30%, and the dye composition can be obtained after spray drying.

Example 3: the composition of the present invention

70 parts of dye of formula (I-2), 15 parts of dye of formula (II-2) and 15 parts of dye of formula (III-2) are respectively put into a beaker, mixed with each other and stirred for 30 minutes by a stirrer to obtain a uniform dye composition, then the pH value is adjusted to 7-7.5 by 32% hydrochloric acid solution, reverse osmosis desalination is carried out, about 30% of lithium salt is replaced, and the dye composition is obtained after spray drying.

Application example 1: ink composition formula

Taking the following ink formula components in percentage by weight: the ink composition of application example 1 was obtained by adding 4.8% of the dye composition of example 1, 10% of DEG, 10% of DEGMBE, 7% of glycerin, 4651% of S-PROXEL-XL, and 52.9% of distilled water to respective portions of the formulation in a beaker, stirring the mixture for about half an hour with a stirrer, and then filtering the mixture absolutely with a 0.45 μm filter paper (absolute-filtration).

Application example 2: ink composition formula

Taking the following ink formula components in percentage by weight: the ink composition of application example 2 was prepared by adding 5.0% of the dye composition of example 3, 10% of DEG, 10% of DEGMBE, 7% of glycerin, S-4651%, 20.3% of PROXEL-XL, and 52.7% of distilled water to respective portions of the formulation in a beaker, stirring the mixture for about half an hour with a stirrer, and then filtering the mixture absolutely with a 0.45 μm filter paper (absolute-filtration).

Test methods and results

Comparison of light fastness

Printing test and solubility test are carried out on the ink samples of application examples 1 to 2, and the test results are shown in table 2;

TABLE 1 ink formulation

Glycerol	7％	7％	7％	7％
					S-465	1％	1％	1％	1％
PROXEL-XL2	0.3％	0.3％	0.3％	0.3％
					DI-water	52.9％	52.7％	54％	53.95％
Abs./λmax(100ppm)	0.149/592nm	0.149/598nm	0.148/618nm	0.146/573nm

The abs./λ max (100ppm) indicated that the ink composition was prepared at a concentration of 100ppm (100mg/l) and measured with a UV tester at full wavelength, where the UV maximum absorption wavelength was λ max and the UV absorption was abs.

DYE I represents a vinylsulfone (-SO2CH ═ CH2) containing compound of the present invention (the specific chemical structure is as shown in formulas I-2, II-2, III-2);

DYE II represents the vinylsulfone hydrolysis (-SO2CH2CH2OH) containing compound of the invention (the specific chemical structure is shown as formula I-1, II-1, III-1);

DYE III is the Duasyn Direct Black HEF-SF DYE composition of CLARIANT;

DYE IV is the Bayscript Black SP DYE composition of BAYER.

Print test conditions-as shown below;

PRINTER-EPSONSTYLUS PHOTO 830U PRINTER, print paper-PLAINPAPER, light fastness test-total energy 85 KJ;

table 2 printing and solubility test results

From the results in Table 2, it can be seen that the subject matter of the present invention has a light fastness comparable to commercially available mainstream products, and the jetness performance can also reach the average level in the industry.

Ink example 2: constant temperature solubility

2-1 weighing Xg quantitative dye (X table dye needs to be dissolved concentration (g/l), if testing 100g/l solubility, weighing 15g dye, adding 150cc distilled water into 250ml beaker, and stirring with glass rod.

2-2, stirring uniformly in a magnet stirrer, heating to a constant temperature of 80 ℃ and keeping the temperature within the range of +/-2 ℃ for 5 min.

2-3, pre-wetting TOYO No.1 filter paper and a magnetic funnel, pumping, draining, rapidly pouring dye test solution, pumping, draining.

And 2-4, taking out the filter paper, and naturally drying to judge the result.

The test results are shown in table 3 below;

table 3 results of the constant temperature solubility test:

as can be seen from the results in Table 3, the ink composition A, B of the present example has a solubility of at least about 300g/L, which is superior to commercially available mainstream products.

Small knot

As can be seen from the above table, the ink compositions A, B of the ink examples of the present invention have both good light fastness and good solubility.

In summary, the present invention shows features different from those of the prior art in terms of the purpose, technique and effect, or in terms of the technical level and research and development design. It should be noted that the above-mentioned embodiments are merely illustrative for convenience of description, and the claimed invention should not be limited to the above-mentioned embodiments, but only by the claims.

Claims (14)

1. A black ink dye composition, comprising:

(A) a compound of the formula (I)

Wherein R is₁is-SO₂CH₂CH₂OSO₃H or-SO₂CH＝CH₂or-SO₂CH₂CH₂OH; m is H, Na or Li;

(B) a compound of the formula (II)

Wherein R is₁is-SO₂CH₂CH₂OSO₃H or-SO₂CH＝CH₂or-SO₂CH₂CH₂OH; m is H, Na or Li; and

(C) a compound of the following formula (III)

Wherein R is₁is-SO₂CH₂CH₂OSO₃H or-SO₂CH＝CH₂Or SO₂CH₂CH₂OH; m is H, Na or Li.

2. The composition of claim 1, wherein in the compound of formula (I), R is₁is-SO₂CH＝CH₂Or SO₂CH₂CH₂OH。

3. The composition of claim 1, wherein R in the compound of formula (II)₁is-SO₂CH＝CH₂Or SO₂CH₂CH₂OH。

4. The composition of claim 1, wherein R in the compound of formula (III)₁is-SO₂CH＝CH₂Or SO₂CH₂CH₂OH。

5. The composition of claim 1, wherein the compound of formula (I) is a compound of formula (I-1),

wherein M is H, Na or Li.

6. The composition of claim 1, wherein the compound of formula (II) is a compound of formula (II-1) as follows

Wherein M is H, Na or Li.

7. The composition of claim 1, wherein the compound of formula (III) is a compound of formula (III-1),

wherein M is H, Na or Li.

8. The composition of claim 1, wherein the compound of formula (I) of component (a) is present in an amount of 50 to 94% by weight; the weight percentage of the compound of formula (II) of the component (B) is 3-47%; and the weight percentage of the compound of formula (III) in the component (C) is 3-30%.

9. The composition of claim 1, further comprising a component (D) of an organic solvent selected from the group consisting of: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, 2-pyrrolidone, N-methyl-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, triethanolamine.

10. The composition of claim 9, further comprising a surfactant component (E), wherein the surfactant component is a compound of the formula:

wherein the sum of n and m is an integer between 0 and 50.

11. The composition of claim 1, wherein the compound of formula (I) is a compound of formula (I-1),

wherein M is H, Na or Li; the compound of formula (II) is a compound of formula (II-1)

Wherein M is H, Na or Li; and the compound of formula (III) is a compound of formula (III-1),

wherein M is H, Na or Li.

12. The composition of claim 11, further comprising a component (D) of an organic solvent selected from the group consisting of: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, 2-pyrrolidone, N-methyl-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, triethanolamine.

13. The composition of claim 12, further comprising a surfactant component (E), wherein the surfactant component is a compound of the formula:

wherein the sum of n and m is an integer between 0 and 50.

14. The composition of claim 11, wherein M of the compounds of formula (I-1), formula (II-1) and formula (III-1) is Li.