JP2003238870A - Ink set and ink jet recording method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink set which gives printed images having a good light-resistance and satisfies color reproducibility, clogging resistance, and other properties and to provide a recording method using it. <P>SOLUTION: This ink set is a combination of a magenta ink containing at least one selected from the group consisting of a dye having a structure of formula [I], a dye having a structure of formula [II] and/or C.I. Acid Violet 9, 30, C.I. Acid RED 50, 52, 289, a yellow ink containing C.I. Direct Yellow 86 and C.I. Direct Yellow 132. or C.I. Direct Yellow 86 and C.I. Direct Yellow 173, and a cyan ink containing C.I. Direct Blue 86 or C.I. Direct Blue 199. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink set suitable for an inkjet recording system and an inkjet recording method.

[0002]

2. Description of the Related Art In the ink jet recording method, ink droplets are ejected from fine nozzles provided in a recording head by the action of vibration or heat energy of a piezoelectric element, and the ink droplets are attached to a recording medium such as paper for printing. This method is advantageous in that a high-resolution image can be obtained at high speed and the running cost is low by using a quiet head and a high-density head during recording.

When a color image is formed by using the ink jet recording method, printing is performed using at least three primary colors of magenta ink, yellow ink and cyan ink, but recently, in order to obtain a higher quality image, magenta ink and cyan are used. A general method is to obtain a higher-definition image by using dark and light inks having different densities. It is important that each ink itself has excellent color reproducibility. Further, two or more kinds selected from magenta ink, yellow ink and cyan ink are overprinted to form red, green, blue and black. It is important that good color reproducibility can be realized even in the case of doing so.

Further, as the ink jet ink, a water-based ink is mainly used from the viewpoint of safety such as odor and danger in fire fighting, but the physical properties such as viscosity and surface tension are within proper ranges. Properties such as nozzle clogging, excellent storage stability, high density recording images, and excellent light resistance and water resistance are required.

Many of these properties are satisfied by using a water-based ink containing water or a mixed solution of a water-soluble organic solvent as a main solvent, but color reproducibility, vividness, light resistance, etc. are colorants. It is greatly affected by the above, and various dyes have been studied from the past. However, magenta ink has a problem that fading and color tone change due to light (sunlight, fluorescent light, etc.) are significantly larger than those of other dyes (yellow and cyan dyes). The fact that the magenta ink is inferior in light resistance to other inks means that it is inferior not only in the magenta ink itself but also in the secondary colors (for example, red and blue) that are overlaid with the yellow ink and the cyan ink. And the overall color tone changes,
This will result in degrading quality.

In response to these demands, Japanese Patent Laid-Open No. 5-214
259 and Japanese Patent Laid-Open No. 2001-115072 disclose that an ink set using a specific dye set can provide excellent color reproducibility and light resistance in a secondary color or a tertiary color.

[0007]

However, in the inks using these ink sets proposed hitherto, light resistance, water resistance, moisture resistance, and clear color tone and color reproducibility, clogging reliability, etc. are obtained. Not all were satisfied.

The object of the present invention is therefore to solve these problems. That is, it is an object of the present invention to provide an ink set which is excellent in light resistance and further satisfies water resistance, moisture resistance, color tone, color reproducibility and other characteristics, and a recording method.

[0009]

The above object can be achieved by the present invention described below. That is, the present invention is an ink set comprising an ink containing at least a dye, a water-soluble organic solvent, and water, wherein the ink set contains a first dye and a second dye, and The dye has the following general formula
The second dye is a dye having a structure represented by [I], and the second dye is a dye having a structure represented by the following general formula [II] and / or C.I. I. Acid Violet 9, 30, C.I. I.
Magenta ink, which is one or more dyes selected from Acid Red 50, 52, 289, and contains the first dye and the second dye in a weight ratio of 1: 1 to 1: 5, C. I. Direct Yellow 86
And C. I. Dye containing Direct Yellow 132 in a weight ratio of 1: 3 to 3: 1 and / or C.I.
I. Direct Yellow 86 and C.I. I. D
a yellow ink containing a dye, which contains irradiate yellow 173 in a weight ratio of 1: 4 to 4: 1; I. D
direct Blue 86 and / or C.I. I.
And a cyan ink containing Direct Blue 199.

[0010]

[Chemical 3]

[0011]

[Chemical 4]

Further, the ink set of the present invention is characterized in that the dye is a water-soluble dye.

In the ink set of the present invention, the total amount of the dyes contained in the magenta ink is 1 to 4% by weight of the total weight of the ink, and the total amount of the dyes contained in the yellow ink. The amount is 0.5 to 4% by weight based on the total weight of the ink, and the total amount of the dye contained in the cyan ink is 1 to 4% by weight based on the total weight of the ink.

The ink set of the present invention is characterized by containing a lower alkyl glycol ether and / or an acetylene glycol-based nonionic surfactant.

In the ink set of the present invention, the lower alkyl glycol ether is at least selected from the group consisting of diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether, and dipropylene glycol monobutyl ether. It is characterized in that it contains one compound.

The ink set of the present invention is characterized in that the glycol ethers are contained in an amount of 3 to 30% by weight based on the total weight of the ink.

The ink set of the present invention is characterized in that the acetylene glycol-based nonionic surfactant is contained in an amount of 0.1 to 3% by weight based on the total weight of the ink.

Further, the present invention is an ink jet recording method in which ink droplets are ejected and adhered to a recording medium to perform printing, and the above-mentioned ink set is used as ink.

Further, the present invention is a recorded matter recorded by the above-mentioned recording method.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION By carrying out ink jet recording using the ink set according to the present invention, a multicolor color image having good light fastness, water fastness, moisture fastness, color reproducibility and other characteristics. Can be provided. Hereinafter, the present invention will be described in detail with reference to preferred embodiments of the present invention.

The magenta ink used in the ink set of the present invention comprises a dye having a structure represented by the general formula [I] as a first dye, a dye having a structure represented by the general formula [II] as a second dye, and / Or C.I. I. Acid Viol
et 9, 30, C.I. I. Acid Red 50, 5
It comprises one or more dyes selected from 2,289.

A dye having a structure represented by the general formula [I] used in the present invention, a dye having a structure represented by the general formula [II], and C.I. I. Acid Violet 9, 3
0, C.I. I. Acid Red 50, 52, 289 is preferably a water-soluble dye that is soluble in an aqueous ink from the viewpoint of safety and the like.

Specific examples of the dye represented by the general formula [I] include the followings, but the dyes are not limited to these.

[0024]

[Chemical 5]

[0025]

[Chemical 6]

[0026]

[Chemical 7]

[0027]

[Chemical 8]

[0028]

[Chemical 9]

[0029]

[Chemical 10]

[0030]

[Chemical 11]

[0031]

[Chemical 12]

[0032]

[Chemical 13]

[0033]

[Chemical 14]

[0034]

[Chemical 15]

[0035]

[Chemical 16]

The dye represented by the general formula [II] includes
Specific examples include the following, but the invention is not limited thereto.

[0037]

[Chemical 17]

[0038]

[Chemical 18]

[0039]

[Chemical 19]

[0040]

[Chemical 20]

[0041]

[Chemical 21]

[0042]

[Chemical formula 22]

[0043]

[Chemical formula 23]

[0044]

[Chemical formula 24]

[0045]

[Chemical 25]

[0046]

[Chemical formula 26]

[0047]

[Chemical 27]

[0048]

[Chemical 28]

[0049]

[Chemical 29]

[0050]

[Chemical 30]

[0051]

[Chemical 31]

Further, as the second dye, the above general formula [I
[I]] as a dye that can be used in a mixture with a dye having a structure represented by the formula [I] or alone. I. Acid Vi
olet 9, 30, C.I. I. Acid Red 50,
The xanthene dye selected from 52,289 is mentioned.

When these xanthene dyes are used alone, sufficient light resistance cannot be obtained, but they may be mixed with a dye having the structure represented by the general formula [II] or may be used alone or in the general formula
By mixing with a dye having a structure represented by [I], excellent light resistance can be obtained, and the coloring property as a magenta ink is also improved.

The amount of the dye added is such that the first dye is of the general formula
A dye having a structure represented by [I], a dye having a structure represented by the general formula [II] as a second dye, and / or C.I.
I. Acid Violet 9, 30, C.I. I. Ac
One or more dyes selected from id Red 50, 52, 289, the first dye and the second dye in a weight ratio of 1: 1 to 1: 5, and 1 to 4 of the total weight of the ink. It is preferably in the range of% by weight. That is, by setting the content within this range, it is possible to secure the reliability of the inkjet ink, such as print density, sharpness, ink clogging, and ejection stability. Further, it is possible to provide an ink having excellent solubility in water, sharpness and light resistance.

The yellow ink which can be used in the ink set according to the present invention in combination with the magenta ink is C.I. I. Direct Yellow 8
6 and C.I. I. A dye containing Direct Yellow 132 in a weight ratio of 1: 3 to 3: 1, or C.I. I. D
direct Yellow 86 and C.I. I. Dire
It is preferable that the dye containing ct Yellow 173 in a weight ratio of 1: 4 to 4: 1 is included in an amount of 0.5 to 4% by weight based on the total weight of the ink. Within this range, it is possible to secure the reliability of the inkjet ink, such as print density, sharpness, ink clogging and ejection stability.
Further, it is possible to provide an ink having excellent solubility in water, sharpness and light resistance.

Further, the cyan ink which can be used in the ink set according to the present invention in combination with the above magenta ink is C.I. I. Direct Blue 86 and / or C.I. I. Direct Blue 199
Is preferably contained in the range of 1 to 4% by weight based on the total weight of the ink. Within this range, it is possible to secure the reliability of the inkjet ink, such as print density, sharpness, ink clogging and ejection stability. Further, it is possible to provide an ink having excellent solubility in water, sharpness and light resistance.

The above-mentioned magenta ink, yellow ink,
In the cyan ink, it is preferable to use a mixed liquid of water and a water-soluble organic solvent as a liquid medium in which the above-mentioned specific dye is dissolved. The water is preferably deionized water rather than general water containing various ions, and the water-soluble organic solvent is preferably a low-volatile solvent from the viewpoint of suppressing clogging. For example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, 1,5
-Pentanediol, 1,2-hexanediol, 1,
Polyhydric alcohols such as 2,6-hexanetriol and glycerin, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether,
Glycol ethers such as propylene glycol monomethyl ether, propylene glycol monobutyl ether and dipropylene glycol monomethyl ether, formamide, dimethylformamide, diethanolamine, triethanolamine, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidone, N- Examples thereof include nitrogen-containing solvents such as methyl-2-pyrrolidone and sulfur-containing solvents such as thiodiglycol and dimethyl sulfoxide. But,
The present invention is not limited to these compounds,
You may contain multiple types of water-soluble organic solvents. These solvents may be used alone or in combination of two or more. The content of 3 to 50% by weight based on the total weight of the ink is suitable for an inkjet ink. If the content is less than 3% by weight, clogging at the tip of the nozzle is likely to occur, and if it exceeds 50% by weight, the drying property of the recorded image is deteriorated and the image is bleeding to cause deterioration of print quality. This is because

For the drying property and bleeding of ink, it is effective to contain a lower alkyl glycol ether. Particularly preferred are diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether, and dipropylene glycol monobutyl ether.
The addition amount is preferably selected in the range of 3 to 30% by weight. If it is less than 3 wt%, almost no effect is obtained on dryness and bleeding, and if it is 30 wt% or more, bleeding becomes rather large and the entire image is blurred, and on the contrary, the print quality is deteriorated. It is preferable to use.

Further, with respect to ink drying and bleeding,
An acetylene glycol-based nonionic surfactant is also effective. Specifically, Olfine E1010, Olfine STG, Surfynol 104E (above, Nisshin Chemical Co., Ltd.)
Products) etc. The amount added is preferably in the range of 0.1 to 3% by weight based on the total weight of the ink.

More preferably, by using the above-mentioned acetylene glycol-based nonionic surfactant in combination with glycol ethers, it is possible to obtain a clear image with less bleeding.

The water content at this time is determined in a wide range depending on the kind of the solvent component, its composition or desired characteristics of the recording liquid, but is generally 10 to 70 weight% in the total weight of the ink. It is considered to be within the range that occupies%.

In addition to the above-mentioned components, the ink of the present invention may be used to impart desired performance to the ink, if necessary.
Viscosity adjusting agents such as sodium alginate and polyvinyl alcohol; alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and lithium hydroxide; pH adjusting agents such as pH buffering agents such as ammonium phosphate; preservatives; Rust agent,
You may mix | blend additives, such as an antioxidant, an antifungal agent, and a chelating agent.

According to the ink jet recording method of the present invention, in addition to excellent color reproducibility in magenta, yellow and cyan, a single color or a secondary color,
Good light resistance can be obtained in the tertiary color.

Further, the ink jet recording method of the present invention is a method of recording using the above-mentioned ink, but any conventionally known method can be used as the ejection method of the head, and particularly the vibration of the piezoelectric element is utilized. An excellent inkjet recording method can be performed in the method of ejecting droplets by using the above method and the method of utilizing thermal energy.

[0065]

EXAMPLES Next, the present invention will be described more specifically with reference to examples. Tables 1 and 2 show ink sets of Examples and Comparative Examples.
The ink sets of the present example and the comparative example were prepared by mixing and dissolving in the compounding ratio shown in (1), filtering with a 1 μm pore size membrane filter, and degassing using a vacuum pump.
Each component of the ink shown in the table represents the weight% of each component with respect to the total amount of the ink, and the remaining amount is water.

[0066]

[Table 1]

[0067]

[Table 2]

Tables 1 and 2 will be supplemented as follows. TEGmBE triethylene glycol monobutyl ether DEGmBE diethylene glycol monobutyl ether TEG triethylene glycol DEG diethylene glycol GL glycerin TEA triethanolamine EDTA ethylenediaminetetraacetic acid disodium salt, chelating agent Olphin E1010, Olphin STG is Nisshin Chemical
A commercial product, an acetylene glycol-based surfactant Proxel XL-2 is a commercial product of Avicia Co., a preservative. An ink jet printer using the inks obtained in Examples 1 to 6 and Comparative Examples 1 to 4 above. Printing was performed with EM-930C (manufactured by Seiko Epson). As a recording medium,
Printing is performed using four types of ink jet printer dedicated PM matte paper, photo print paper 2, PM photo paper (above made by Seiko Epson), and plain paper Xerox 4024 (made by Xerox), and using these samples. The tests 1 to 5 shown below were evaluated.

<Test 1: Lightfastness> With respect to each ink set of the example and the comparative example, each ink chamber of the ink cartridge for EM-930C (manufactured by Seiko Epson) was filled with magenta, yellow and cyan inks respectively, and magenta was used. Solid printing of yellow, cyan, red, blue, green and composite black was performed. Red is composed of magenta and yellow inks, blue is composed of magenta and cyan inks, green is composed of yellow and cyan inks, and composite black is composed of magenta, yellow, and cyan inks. . About this printed sample, a xenon weatherometer Ci5000 (manufactured by Atlas Electric Device Co.) was used to irradiate the sample with light for 50 hours, and the hue (L *, a *, b *) before and after the light irradiation was measured with a Gretag densitometer. (Made by Gretag), color difference ΔE
* ab was obtained from the following formula (i) and judged based on the following evaluation criteria.

ΔE * ab = [(ΔL *) ² + (Δa *) ² +
(Δb *) ² ] ^1/2 (Evaluation Criteria) A: When the color difference ΔE * ab is 5 or less B: When the color difference ΔE * ab is more than 5 and 10 or less C: The color difference ΔE * ab is When it exceeds 10 and is 20 or less D: When the color difference ΔE * ab exceeds 20

<Test 2: Bleed> With respect to each ink set of the above-mentioned Examples and Comparative Examples, solid printing of each color was performed on each recording medium, and color bleeding at the boundary with other colors of each color, and imperfect printing. It was evaluated according to the following criteria whether or not they were uniformly mixed.

(Evaluation Criteria) A: There is no bleeding B: There are areas where colors are bleeding or are mixed non-uniformly, but there is no problem in practical use C: Colors are bleeding or areas where they are mixed non-uniformly Conspicuous and practically problematic

<Test 3: Recovery from Nozzle Clogging> The head is filled by repeating cleaning with ink of each ink set, and after confirming that ink is being ejected from each nozzle by printing, without capping 1 in a 40 ° C environment
Left for a month. After leaving, the power of the printer was turned on, and the number of cleaning operations required until the ejection of all nozzles became possible was judged based on the following evaluation criteria.

(Evaluation criteria) A: Cleaning once B: Cleaning 2 to 4 times C: Cleaning 4 times or more D: No discharge

<Test 4: Quick Drying> Using each ink set, solid printing of a single color and solid printing of a combination of two colors were performed for each ink composition. After the elapse of a predetermined time from the printing, the same kind of recording paper as the printed paper was brought into close contact with each other, and it was observed whether ink transfer occurred between the two sheets. The result was judged based on the following evaluation criteria.

(Evaluation Criteria) A: Ink transfer is not recognized even after printing for less than 1 second. B: Ink transfer is not recognized for 2 seconds or more and less than 5 seconds after printing. C: 5 seconds or more after printing. Even if ink is transferred

<Test 5: Ejection stability (continuous recording for a long time)
> Printing was carried out for 48 hours in a temperature environment of 5 ° C., 20 ° C. and 40 ° C. using each ink. The time until the dot omission and ink scattering were observed 10 times in total was measured. The result was judged based on the following evaluation criteria.

(Evaluation Criteria) A: No dot omission at all temperatures and stable printing was possible B: At any temperature, dot omission occurred over time C: At any temperature Table 3 shows the above test results in which missing dots occurred from the beginning.

[0079]

[Table 3]

[0080]

INDUSTRIAL APPLICABILITY As described above, the present invention is excellent in light fastness in the ink jet recording system, and further has color reproducibility,
It is possible to provide an ink set and an inkjet recording method which are excellent in clogging and other characteristics.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J039 BC09 BC13 BC17 BC41 BC52                       BC54 BC73 BC74 BC75 BC77                       BC79 BE02 BE22 CA06 EA15                       EA16 EA17 GA24

Claims (9)

[Claims] 1. An ink set comprising an ink containing at least a dye, a water-soluble organic solvent and water, wherein the ink set contains a first dye and a second dye, and the first dye. Is a dye having a structure represented by the following general formula [I], and the second dye is a dye having a structure represented by the following general formula [II] and / or C.I. I. Acid Violet 9, 30,
C. I. One or more dyes selected from Acid Red 50, 52, 289, comprising a first dye and a second dye in a weight ratio of 1: 1 to 1: 5,
Magenta ink, C.I. I. Direct Yellow 86 and C.I.
I. Direct Yellow 132 and 1: 3 ~
A dye or C.I. I. Direct
Yellow 86 and C.I. I. Direct Ye
yellow ink containing a dye containing LLOW 173 in a weight ratio of 1: 4 to 4: 1; I. Direct Blue 86 and / or C.I. I. An ink set comprising a cyan ink containing Direct Blue 199. [Chemical 1] [Chemical 2] 2. The ink set according to claim 1, wherein each of the dyes of the magenta ink, the yellow ink and the cyan ink is a water-soluble dye. 3. The total amount of the dye contained in the magenta ink is 1 to 4% by weight of the total weight of the ink, and the total amount of the dye contained in the yellow ink is of the total weight of the ink. 3. The ink set according to claim 1, wherein the amount of the dye is 0.5 to 4% by weight, and the total amount of the dye contained in the cyan ink is 1 to 4% by weight of the total weight of the ink. . 4. The ink set according to claim 1, further comprising a lower alkyl glycol ether and / or an acetylene glycol-based nonionic surfactant. 5. The lower alkyl glycol ether contains at least one compound selected from the group consisting of diethylene glycol monobutyl ether, triethylene glycol monobryl ether, propylene glycol monobutyl ether and dipropylene glycol monobutyl ether. The ink set according to claim 4, which is characterized in that. 6. The ink set according to claim 4 or 5, wherein the glycol ether is contained in an amount of 3 to 30% by weight based on the total weight of the ink. 7. The ink set according to claim 4, wherein the acetylene glycol-based nonionic surfactant is contained in an amount of 0.1 to 3% by weight based on the total weight of the ink. 8. An inkjet recording method for forming a color image using at least magenta ink, yellow ink, and cyan ink, wherein the ink set according to any one of claims 1 to 7 is used. . 9. A recorded matter recorded by the recording method according to claim 8.