CN1401711A - Dye combination colorant and ink composition with high water repellency - Google Patents

Abstract

The present invention discloses a special dye combination colorant for a thermal bubble type ink jet printer, which is a multicolor dye combination colorant with high water-resistance (water-fastness) for color ink jet printing. The dye combination colorant comprises (a) a direct blue 199 dye and an acid blue 9 dye. (b) Reactive red dye 180(reactive red 180), acidic red dye 52(acidic red 52), and direct red dye 75(direct red 75). (c) A direct yellow dye 132(direct yellow 132), and an acid yellow dye 5(acid yellow 5). The dye combination pigment is used in a thermal bubble type ink-jet printer, not only improves the thermal stability and the storability, but also has unique viscosity and surface tension, and has high water-resistance (water-fastness), and the high-quality color image is suitable for various color systems, and can greatly improve the printing quality.

Description

Dye-combined colorant and ink composition with high water repellency

                    

The invention relates to a combination of multi-color dyes with high water resistance, an ink composition containing the color material of the combination, and its application in ink-jet printing.

Background technique

Generally speaking, for the requirements of color inkjet printing, it is necessary to have a wide color range and ideal mixed colors, such as blue or red. The combination of cyan ink, magenta ink, yellow ink and black ink is called primary dye-set. Secondary dye-set refers to other colors that do not contain the first-level dye combination color materials, but are obtained by mixing and matching the first-level dye combination color materials.

In fact, for color inkjet printing, a successful ink combination needs to meet the following requirements: wear resistance (good crusting resistance), stability (good stability), unique viscosity (proper viscosity), unique surface tension (proper surface tension), high color saturation (high color saturation), low ink water resistance (little color-to-color bleed), short drying time (rapid drytime), etc. And when used in an inkjet printer, it will not cause kogation, and when inkjet is used on a carrier, such as on plain paper, it can be as successful as other inkjet special papers ink jet.

The color representation method is divided into two major color expression systems according to the collection of actual color objects. For example, Ostwald color system, Munsell color system, German DIN color system, etc. The other is the color mixing system (color mixing system): it is not a system based on actual color objects, but a system based on the three primary colors of light energy mixed to produce many colors. So far the most important color mixing system is based on the measurement of color by instruments. CIE system. For example, the Munsell color system was created by the American painter Munsell. It is the most famous system that uses three attributes - hue, value, and chroma - to describe colors. The color stimuli (X, Y, Z three stimuli) and the color perception of the CIE system are caused by the combination of the light source, object, and observer. The color gamut is based on the three elements of L ^* , a ^* , and b ^* L ^* represents the lightness of a color, and a ^* and b ^* represent the hue and chroma of the color. a ^* ranges from -a for green to +a for red, and b ^* ranges from -b for blue to +b for yellow. The CIE system also added hue angle and chroma (hue angle, h ⁰ ; chroma, C ^* ) to the 1976 recommendation (equations 1 and 2). In CIELAB's color gamut, color difference (ΔE) refers to the degree of color difference between two color samples (Equation 3). The greater the ΔE difference, the greater the color difference between the two color samples. And OD (Optical density) stands for optical density, which can also be called absorbance (absorbancy), which is defined as the intensity of penetration of a light with an intensity of I _o after irradiating something. The value of log (I _o /I) is called is the optical density (Equation 4).

h ⁰ =tan ^-1 (b ^* /a ^* ) Equation 1

C ^* = (a ^*2 +b ^*2 ) ^1/2 Equation 2

ΔE＝(ΔL ^*2 +Δa ^*2 +Δb ^*2 ) ^1/2 Equation 3

OD=log(I _o /I) Equation 4

Therefore, when an ideal ink combination is used for inkjet printing images, it must be able to provide the best color characteristics, such as appropriate hue and high chroma. In the present invention, the water resistance experiments of each group of combined colorants are mainly based on Equation 3, the size of its ΔE value to determine whether its water resistance is superior or not. A good water resistance ink combination, after water resistance After the performance test, it must be able to provide the smallest ΔE, that is, the less the color fades, the better the water resistance.

For inkjet printing, it is generally known that if only a single color material is used in the ink, it is often easy to cause plugging of the inkjet port, so a variety of humectants are usually added, but it is easy to cause slow drying, and Poor water resistance. For example 1986, U.S.Pat.No.4,631,085, 1987 U.S.Pat.No.4,713,113, 1988, U.S.Pat.No.4,737,190, its ink all is single color material and must add humectant to prevent coagulation. In 1999 U.S.Pat.No.5,925,177, a special ink composition, including acidic yellow dye 23 (acidic yellow 23), urea (urea), water. Adding urea prevents the yellow dye from crystallizing and clogging the inkjet head.

For color inkjet printers, it usually includes magenta ink, cyan ink, yellow ink and black ink, a total of four color inks, most of which use Mainly water-based dyes. In recent years, there are magenta ink, cyan ink, yellow ink, black ink, light magenta ink and light magenta ink. cyan ink), a total of six colors of ink, or add light yellow ink (light yellow ink), to form a total of seven colors of ink. These inks consist of more than one water-soluble dye, water, organic solvents, and other additives. However, such water-soluble dye inks are poor in water resistance and light resistance of printed images.

Therefore, in recent years, a large number of pigment inks with good water resistance and light resistance have been developed, which contain more than one pigment, water, organic solvents, and other additives. Inkjet inks that use pigments as colorants are superior to water-soluble dye inks in terms of water resistance and light resistance of images. Although the pigment has better water resistance and light resistance, it must be combined with an appropriate dispersant and adhesive agent. In addition, the pigment has a larger particle size, so it is more prone to precipitation and aggregation. And clog the inkjet head, reduce the print quality.

Contents of the invention

One of the objects of the present invention is to provide a water-soluble multicolor dye combination colorant (dye set), which has a high degree of water resistance.

The second object of the present invention is to provide an ink composition containing the above multicolor dye combination coloring material.

The third object of the present invention is to provide an inkjet printing method using the above ink composition.

The fourth object of the present invention is to provide a novel water-soluble magenta dye combination color material and an ink composition containing the combination color material.

The fifth object of the present invention is to provide a novel water-soluble yellow dye combination color material and an ink composition containing the combination color material.

In order to achieve the above object, the present invention provides a highly waterproof water-soluble multicolor dye combination coloring material (dye set), comprising:

(a) water-soluble magenta dye combination colorant, including: direct blue dye 199 (directive blue 199), acidic blue dye 9 (acidic blue 9);

(b) Water-soluble magenta dye combination colorant, including: reactive red dye 180 (reactive red 180), acidic red dye 52 (acidic red 52), direct red dye 75 (directive red 75); and

(c) Water-soluble yellow dye combination colorant, including: direct yellow dye 132 (directive yellow 132), acidic yellow dye 5 (acidic yellow 5).

Among the above components, the direct blue dye 199 (directive blue 199) and acidic blue dye 9 (acidic blue 9) used in component (a) are the combined colorants commonly used as blue dyes in the prior art . The combination of magenta and yellow colorants used in component (b) and component (c) is the first invention of the present invention.

In the component (a) magenta dye combination colorant of the present invention, direct blue dye 199 (directive blue 199) and acidic blue dye 9 (acidic blue 9) produced by Clariant Company of Germany are used.

In the component (b) magenta dye combination colorant of the present invention, reactive red dye 180 (reactive red 180) and direct red dye 75 (directive red 75) produced by Bayer Company of Germany are used. Acidic red dye 52 (acidic red 52) was produced by Clariant, Germany. Also within the scope of the present invention are ink compositions containing the magenta dye combination colorant.

In the component (c) yellow dye combination colorant of the present invention, the direct yellow dye 132 (directive yellow 132) used is produced by German Bayer company. Acidic yellow dye 5 (acidicyellow 5) was from BASF, Germany. The scope of the present invention also includes ink compositions containing the yellow dye combination colorant.

The ink composition of the present invention comprises the above-mentioned polychromatic dye combination colorant and an aqueous solution vehicle. The inkjet printing method of the present invention includes providing the ink of the present invention to an inkjet printing device; and ejecting the ink onto a recording medium.

The ink composition provided in this case is used in thermal bubble inkjet printers. It not only improves thermal stability and storage, but also has unique viscosity and surface tension, and is highly waterproof. This high-quality color image, It is suitable for all kinds of color systems and can greatly improve the printing quality.

In the ink composition of the present invention, the addition amount of each of the above-mentioned dyes is about 0.1-10% by weight (based on the total weight of the ink), preferably 2-5% by weight.

An aqueous vehicle is included in the ink composition of the present invention. In addition to water, the water-soluble vehicle may also contain a water-soluble or water-miscible organic solvent, such as cyclohexane (cyclohexane), methanol (methanol), ethanol (ethanol), ethylene glycol (ethylene glycol), Diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, butylene glycol, pentylene glycol or hexylene glycol Alcohol (hexylene glycol) or polyol, etc.

The ink composition of the present invention may further include a surfactant. The main function of the surfactant is to reduce the ink surface tension of the solution, which in turn can improve the ink moisturizing function, make the ink supply and inkjet smooth, and also have the function of a dispersant. In general, disperse dyes themselves are easy to cause The phenomenon of crystallization or agglutination of the colorant will block the nozzle of the ink cartridge, so it is necessary to strengthen the wetting effect of the dispersant to improve the dispersibility of the additive in the ink. Usually, more than one surfactant is added to the general ink formula , including anionic, cationic, nonionic, or amphoteric surfactants. Its total addition range is below 20.0% by weight. The added surfactants are, for example, polyethylene glycol (polyethhandiol), polypropylene glycol (polypropandiol), ethylene oxide/propylene oxide copolymer (EO/PO copolymer), dioctylthiosuccinate Sodium (sodiumdioctyl sulfosuccinate), polybutyl resin (polybutyl resin), cellulose derivative (cellulose derivative), styrene/acrylic copolymer resin (styrene/acrylic copolymer resin), butene/styrene copolymer ( maleic acid/styrene copolymer) or a polymer containing both a hydrophilic segment and a lipophilic segment, etc.

The ink composition of the present invention may further include a humectant. Humectants usually use low-volatility liquids to reduce evaporation, and at the same time, they must have good compatibility with the main solution, which can improve the ink at the nozzle of the ink cartridge due to volatilization to produce sediment or crystals, resulting in nozzle blockage. situation. Typical humectants used in inkjet inks are ethylene glycol, diethylene glycol or glycerin, etc., and the added amount ranges from 10.0 to 30.0% by weight.

The ink composition of the present invention may further include an acid-base buffer. The addition of acid-base buffer solution (buffer) can only show the ideal color system because the color material needs to be within the appropriate pH value range. Appropriate acid-base buffer solutions such as diethanolamine, triethanolamine, hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide (sodium hydroxide) and potassium hydroxide (potassium hydroxide). ammonium hydroxide, carbonates of alkali metals, lithium carbonate, sodium carbonate and potassium carbonate.

The ink composition of the present invention may further include a chelating agent. The addition of chelating agent (Chelation agent) can prevent the generation of crystalline salts, and avoid agglomeration of particles and block the nozzle of the ink cartridge. Suitable chelating agents include sodium ethylenediaminetetraacetate, trisodium nitrilotriacetate, hydroxyethylenediamine trisodium acetate, diethylenetriaminepentasodium acetate and uramil disodium acetate.

In addition, in the ink formula of the present invention, an anti-ultraviolet agent (UV-blocker) can be added to block the absorption of UV light and thereby improve the light resistance of the colorant; Bacteria grow in the ink; add a dispersant (Dispersant) to increase the dispersion ability of the additive in the ink.

In order to make the above and other objects, features, and advantages of the present invention more comprehensible, the preferred embodiments are specifically listed below, together with the accompanying drawings, and are described in detail as follows:

Description of drawings

FIG. 1 is a color gamut diagram of the dye combination coloring material of the three-color ink provided in the embodiment of the present case, which is ink-jetted on general ink-jet printing paper.

FIG. 2 is a color gamut diagram of the dye combination coloring material of the three-color ink of the comparative example provided in this case, which is ink-jetted on general ink-jet printing paper.

Fig. 3 is the color gamut diagram of the three-color ink dye combination coloring material of the embodiment provided in this case, which is ink-jetted on ordinary paper and placed in water for 30 minutes.

FIG. 4 is a color gamut diagram of the three-color ink-dye combination coloring material provided in this case, which is ink-jetted on ordinary paper and placed in water for 30 minutes.

Fig. 5 is the color gamut comparison figure after the water resistance test of the three-color ink dye combination colorant provided by the embodiment and the comparative example (the outer curve represents the ink composition of the embodiment after being placed in water for 30 minutes, and the inner curve represents The ink composition of the comparative example after being placed in water for 30 minutes).

Example

The three-color ink composition of the combined colorant provided in this case includes

(a) 3% by weight direct blue dye 199 (directive blue 199)

2% by weight acidic blue dye 9 (acidic blue 9)

4.0% by weight of PEG 700 (polyethylene glycol 700) (from U.C.C.)

4.0% by weight of 2-pyrrolidone (2-pyrrolidone) (from DOW)

4.0% by weight of 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (EHMPD; from Lancaster)

2.0% by weight of surfactant 13-S-5 (from Sino-Japanese Synthesis)

2.0% by weight of surfactant 13-S-7 (from Zhongri Synthesis) 3.0% by weight of surfactant OT-75 (from KYOWA) 0.5% by weight of surfactant 465 (from air producet) 2.5% by weight of 1 , 4-butanediol (from Lancaster) 0.5% by weight of bactericide SL-700 (from KYOWA) deionized water (b) 2% by weight of reactive red dye 180 (reactive red 180) (from Bayer), 1.5% by weight Acid red dye 52 (acidic red 52) (from Clariant), 1 wt% direct red dye 75 (directive red 75) (from Bayer), 4.0 wt% of PEG 700 (polyethylene glycol 700) (from U.C.C.) 4.0 wt % of 2-pyrrolidone (from DOW) 4.0% by weight of 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (EHMPD; from Lancaster) 2.0% by weight of surfactant 13 -S-5 (from Sino-Nichisei) 2.0% by weight of Surfactant 13-S-7 (from Sino-Nichisei) 3.0% by weight of Surfactant OT-75 (from KYOWA) 0.5% by weight of Surfactant 465 (from air producet) 2.5% by weight of 1,4-butanediol (from Lancaster) 0.5% by weight of bactericide SL-700 (from KYOWA) deionized water (c) 2.5% by weight of direct yellow dye 132 (directive yellow 132) (from Bayer), 1% by weight of acidic yellow dye 5 (acidic yellow 5) (from BASF) 4.0% of PEG 700 (polyethylene glycol 700) (from U.C.C.) 4.0% of 2-pyrrolidone (2-pyrrolidone) (from DOW) 4.0% 2-Ethyl-2-(hydroxymethyl)-1,3-propanediol (EHMPD; from Lancaster) 2.0% Surfactant 13-S-5 (from Sino-Japanese Synthesis) 2.0% interface ACTIVE AGENT 13-S-7 (from Sino-Japanese synthesis) 3.0% surfactant OT-75 (from KYOWA) 0.5% surfactant 465 (from air producet) 2.5% 1,4-butanediol (from Lancaster) 0.5% fungicide SL-700 (from KYOWA) deionized water The paper used in this case is commercially available plain paper. The inkjet printer used in this case is a commercially available special inkjet printer.

For the three-color ink composition provided in this case, the color gamut of this dye combination inkjet printing on general paper is shown in Figure 1. The method of testing water resistance is to measure the color optical properties of each color of the full-color pattern printed by inkjet, put it in deionized water for 30 minutes, take it out, let it dry naturally at room temperature, and then measure the color of each color. Optical properties, the color gamut of this dye combination colorant is shown in Figure 2.

Comparative example

The three-color ink composition of the combined coloring materials provided in this case comes from the ink of the commercially available Epson (Epson) 193 color ink cartridge.

The paper used in the control experiment of this case is commercially available plain paper.

The inkjet printer used in Benning's control experiment is a general commercially available inkjet printer.

For the three-color ink composition provided in this case, the color gamut of this dye combination inkjet printing on common paper is shown in Figure 3. The method of testing water resistance is to measure the color optical properties of each color of the full-color pattern printed by inkjet, put it in deionized water for 30 minutes, take it out, let it dry naturally at room temperature, and then measure the color of each color Optical properties, the color gamut of this dye combination colorant is shown in Figure 4.

The comparison chart of the color gamut after the waterproof test of the examples and comparative examples provided in this case is shown in FIG. 5 .

Table 1 shows the comparison of the ΔE values of magenta and yellow after the water resistance test of the examples and comparative examples provided in this case. magenta ink yellow ink Example comparative example Example comparative example ΔE ◎ △ ○ △

Note 1: ◎ indicates that the ΔE value is below 30

  ○ means that the ΔE value is between 30-50

   Δ means that the ΔE value is between 50-70

× means that the ΔE value is above 70

Note 2: The value of ΔE can be used to determine whether its water resistance is superior or not. An ink combination with good water resistance must be able to provide the smallest ΔE, that is, the less the color fades, the better its water resistance.

Effect of Invention

The three-color ink combination color material provided according to the present invention includes (1) direct blue dye 199 (directive blue 199), acidic blue dye 9 (acidic blue 9). (2) Reactive red dye 180 (reactive red 180), acidic red dye 52 (acidic red 52), direct red dye 75 (directive red 75); (3) direct yellow dye 132 (directive yellow 132), acidic red dye Yellow dye 5 (acidic yellow 5). The application of this dye combination colorant in thermal bubble inkjet printers not only improves thermal stability and storage, but also has unique viscosity and surface tension, and is highly waterproof (water-fastness), especially in foreign countries. In terms of water resistance of red and yellow, the effect is more obvious. This high-quality color image is suitable for various color systems, which can greatly improve the printing quality.

Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Anyone skilled in the art can make some changes and modifications without departing from the spirit and scope of the present invention. Therefore, this The scope of protection of the invention shall prevail as defined by the appended claims.

Claims (25)

1. A water-soluble dye combination colorant, which comprises: (a) direct blue dye 199, acid blue dye 9; (b) reactive red dye 180, acid red dye 52, direct red dye 75; and (c) Direct yellow dye 132, acid yellow dye 5. 2. A water-soluble magenta colorant combination comprising: Reactive red dye 180, acid red dye 52, and direct red dye 75. 3. A water-soluble yellow dye combination colorant, which comprises: Direct yellow dye 132, and acid yellow dye 5. 4. An ink composition comprising: A dye combination colorant comprising: (a) direct blue dye 199, acid blue dye 9; (b) reactive red dye 180, acid red dye 52, direct red dye 75; and (c) direct Yellow Dye 132, Acid Yellow Dye 5; and The medium is an aqueous solution. 5. The ink composition according to claim 4, wherein the component (a) comprises 0.1-10% by weight of the direct blue dye 199, and 0.1-10% by weight of the acid blue dye 9. 6. The ink composition according to claim 4, wherein component (b) comprises 0.1 to 10% by weight of reactive red dye 180, 0.1 to 10% by weight of acid red dye 52, and 0.1 to 10% by weight of direct red dye 75. 7. The ink composition according to claim 4, wherein the component (c) comprises 0.1-10% by weight of the direct yellow dye 132, and 0.1-10% by weight of the acid yellow dye 5. 8. The ink composition according to claim 4, wherein the vehicle further comprises an organic solvent. 9. The ink composition as claimed in claim 4, wherein the vehicle further comprises a surfactant. 10. The ink composition according to claim 4, wherein the vehicle further comprises an acid-base buffer. 11. The ink composition of claim 4, wherein the vehicle further comprises a chelating agent. 12. The ink composition of claim 4, wherein the vehicle further comprises a bactericide. 13. A magenta ink composition comprising: A dye combination colorant comprising: Reactive Red Dye 180, Acid Red Dye 52, and Direct Red Dye 75; and vehicle, which is an aqueous solution. 14. The magenta ink composition as claimed in claim 13, wherein the dye combination colorant comprises: 0.1 to 10% by weight of reactive red dye 180, 0.1 to 10% by weight of acid red dye 52, and 0.1 to 10% by weight Direct red dye 75. 15. A yellow ink composition comprising: A dye combination colorant comprising: direct yellow dye 132, and acid yellow dye 5; and The medium is an aqueous solution. 16. The yellow ink composition as claimed in claim 15, wherein the dye combination coloring material comprises: 0.1-10 wt% direct yellow dye 132, and 0.1-10 wt% acid yellow dye 5. 17. An inkjet printing method comprising the steps of: Provide ink for an inkjet printing device, the ink includes: (1) dye combination colorant, which comprises: (a) direct blue dye 199, acid blue dye 9; (b) reactive red dye 180, acid red dye 52, direct red dye 75; and (c ) direct yellow dye 132, acid yellow dye 5; and (2) a vehicle, which is an aqueous solution; and The ink is ejected onto the record carrier. 18. The inkjet printing method according to claim 17, wherein the component (a) comprises 0.1-10 wt% of the direct blue dye 199, and 0.1-10 wt% of the acid blue dye 9. 19. The inkjet printing method according to claim 17, wherein component (b) comprises 0.1 to 10% by weight of reactive red dye 180, 0.1 to 10% by weight of acid red dye 52, and 0.1 to 10% by weight of direct red dye Dye 75. 20. The inkjet printing method as claimed in claim 17, wherein the component (c) comprises 0.1-10% by weight of the direct yellow dye 132, and 0.1-10% by weight of the acid yellow dye 5. 21. The inkjet printing method as claimed in claim 17, wherein the ink further comprises an organic solvent. 22. The inkjet printing method as claimed in claim 17, wherein the ink further comprises a surfactant. 23. The inkjet printing method as claimed in claim 17, wherein the ink further comprises an acid-base buffer. 24. The inkjet printing method of claim 17, wherein the ink further comprises a chelating agent. 25. The inkjet printing method as claimed in claim 17, wherein the ink further comprises a biocide.

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