JP2002317133A - Ink for ink jet recording device, ink jet recording system, ink jet recording device, and ink vessel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink for an ink jet recording device being capable of obtaining a printed matter having a high charge stability and a storage stability, and excellent water resistance, and to provide an ink jet recording system, and the ink jet recording device, and an ink cartridge. SOLUTION: The ink for the ink jet recording device comprises printing ordinary paper with an ink jet printer using an ink A comprising a reactive dye, an organic solvent, and a surfactant, and an ink B comprising adding a polyethylene glycol (#200) of 5 pts.wt. to the ink A, dipping over the whole face of the printing samples into pure water at 25 deg.C, then leading a color difference ΔE, as the color difference ΔEa regarding a printing matter with the ink A, and as the color difference ΔEb regarding the printing matter with the ink B, and satisfying the relationship of the ΔEa and the ΔEb, 0.9>=the ΔEb/the ΔEa. The ink jet recording system, the ink jet recording device, and the ink cartridge using the ink for the ink jet recording device are adopted.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an ink for an ink jet recording apparatus, a printing method using the ink, an ink jet recording apparatus, and an ink cartridge.

[0002]

2. Description of the Related Art Ink-jet printers (IJ printers) have become extremely popular because they have no processes such as development and fixing, and are very easy to colorize, and can print on plain paper. In particular, recently, high-definition color printers and the like corresponding to photographic images are commercially available, and this type of printer is becoming the mainstream of inkjet printers. As described above, a photographic image is required as a printing target of an ink jet printer, and a demand for a printed matter by an IJ printer is that the image quality and storage stability are listed, and an image having the same stability as a silver halide photograph. Is indispensable. Therefore, in order to improve the storage stability of the printed matter, that is, the weather resistance performance, an IJ ink having a high water resistance, which is a recording liquid for an IJ printer, is desired. In general, IJ inks are roughly classified into dye inks using an aqueous dye as a coloring agent and pigment inks dispersing a pigment in water as a coloring agent. At present color printers mainly use dye inks. Dye inks provide clear images, but have the disadvantage that they have poor water resistance.

[0003] Japanese Patent Application Laid-Open No. 56-14763 discloses I
Pigment inks for J recording devices have been proposed. This ink has excellent water resistance of a printed image, but has poor dispersion stability as an IJ ink, and has a problem of causing clogging or the like at the time of ink ejection.

As pigment inks having improved dispersion stability and ejection stability, pigment inks to which a special water-soluble resin is added are disclosed in JP-A-6-100810 and JP-A-6-1810.
No. 22,846, has been proposed. However, these pigment inks also did not satisfy the ejection characteristics required for photographic image printers that eject minute droplets.

[0005]

As described above, it is difficult to use pigment inks as inks for photographic image recording devices, and at present it has to rely on dye inks. Therefore, as a highly water-resistant dye ink, an ink for an ink jet recording apparatus to which a specific resin is added is disclosed in
No. 323,230. However,
This ink still did not satisfy the required water resistance performance.

On the other hand, as an improvement method from the side of a recording medium, a method using a recording sheet formed by a special processing method as disclosed in Japanese Patent Application Laid-Open No. 1-259879 has been proposed. However, this method is not practical because it is more expensive than plain paper. Even if this kind of special paper is used, the required water resistance is not yet satisfied.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an ink for an ink-jet recording apparatus which has high ejection stability and storage stability and is capable of obtaining a printed matter having extremely excellent water resistance, and an ink-jet ink using the same. An object of the present invention is to provide a recording apparatus, an ink jet recording method, and an ink container.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, in an ink for an ink jet recording apparatus comprising a reactive dye, an organic solvent, and a surfactant, the ink was used. A, Ink A used polyethylene glycol # 200 (polyethylene glycol # 200)
Ink B obtained by adding 5 parts by weight of an average molecular weight of 200)
The ink A and the ink B have a droplet amount of 20 droplets.
After printing on plain paper with a piezo-type inkjet printer so as to be arranged on all of the grids with a resolution of 720 dpi in picoliters, the entire printed sample is placed in a glass water tank (capacity 3 L) filled with 25 ° C pure water. immersed in Watari water, the printed sample before and after water immersion CIE (L ^*,
a ^* , b ^* ) Based on the colorimetric results of the display system, the color difference ΔE calculated from the following general formula (1) is calculated based on the color difference ΔEa for the print sample using ink A and the color difference ΔE for the print sample using ink B. Eb, and these △ Ea and △ Eb become △ Eb
According to the ink for an ink jet recording apparatus satisfying the relationship of /△Ea≦0.9, a good printed matter having excellent water resistance and little bleeding can be obtained, and also the ejection stability and the storage stability from the print head can be improved. They have found that they are excellent, and have completed the present invention.

However, the general formula (1) is expressed as follows: △ E = ｛(L1
^{* -L2 *) 2 + (a1} * -a2 *) 2 + (b1 * -b
2 ^* ) ² ｝ ^1/2 , where (L1 ^* , a1 ^* , b
1 ^* ): Colorimetric value of printed matter before immersion in water, (L2 ^* , a
2 ^* , b2 ^* ): Colorimetric values in printed matter after immersion in water.

In the ink of the present invention, by forming a chemical bond between the dye and polyethylene glycol,
Improves the water resistance of the ink. Further, by combining the dye and the polyethylene glycol, it is possible to prevent the ink from spreading extremely in the printed paper and to give a printed image with less bleeding.

The ink of the present invention is preferably constituted by adding 0.1 to 20 parts by weight of polyethylene glycol # 200 (polyethylene glycol average molecular weight 200 to 1000).

The ink of the present invention is preferably constituted by adding 0.1 to 10 parts by weight of an alkali salt.

In the ink of the present invention, the alkali salt may be a carbonate.

In the ink of the present invention, the carbonate is sodium carbonate, potassium carbonate, calcium carbonate,
Lithium carbonate, magnesium carbonate, ammonium carbonate,
It is preferably at least one carbonate selected from sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate and ammonium hydrogen carbonate.

In the ink of the present invention, the alkali salt may be a phosphate.

In the ink of the present invention, the phosphate is trisodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium monophosphate, tripotassium phosphate, dipotassium hydrogen phosphate, Potassium dihydrogen phosphate, potassium monophosphate, tricalcium phosphate, calcium dihydrogen phosphate, calcium monophosphate, magnesium phosphate, trilithium phosphate, lithium dihydrogen phosphate, lithium monophosphate, phosphorus It is preferably at least one phosphate selected from magnesium hydrogen oxyhydrate, magnesium dihydrogen phosphate, triammonium phosphate, ammonium dihydrogen phosphate and ammonium monophosphate.

In the ink of the present invention, the alkali salt may be a borate.

In the ink of the present invention, the borate is sodium borate (sodium metaborate, sodium niborate, sodium tetraborate, sodium pentaborate, sodium hexaborate, sodium octaborate); Potassium borates (potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate), ammonium borates (ammonium metaborate, ammonium tetraborate, ammonium pentaborate, ammonium octaborate), Magnesium borate (magnesium metaborate, trimagnesium tetraborate, pentamagnesium tetraborate, magnesium hexaborate), lithium borates (lithium metaborate, lithium tetraborate, lithium pentaborate), ammonium borate (Ammonium metaborate, ammonium tetraborate Ammonium pentaborate, is preferably 1 or more borate salt selected from eight ammonium borate).

The ink of the present invention may be constituted by adding 0.1 to 10 parts by weight of an organic amine compound.

In the ink of the present invention, the organic amine compound is ethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine,
It is preferably at least one organic amine compound selected from triethanolamine.

The ink of the present invention may be constituted by adding 0.1 to 10 parts by weight of a pyridine compound.

In the ink of the present invention, the pyridine compound is pyridine, 1-methylpyridine, 2-methylpyridine, 4-methylpyridine, 1-ethylpyridine,
It is preferably at least one pyridine compound selected from 2-ethylpyridine, 3-ethylpyridine, and 2-methoxypyridine.

The ink of the present invention may be constituted by adding 0.1 to 10 parts by weight of a hydroxide compound.

In the ink of the present invention, the hydroxide compound is at least one hydroxide compound selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, and ammonium hydroxide. Is preferred.

In the ink of the present invention, a carboxylic acid compound may be added in an amount of 0.1 to 10 parts by weight.

In the ink of the present invention, the carboxylic acid compound is sodium acetate, sodium hydrogen acetate, sodium oxalate, sodium hydrogen oxalate, potassium acetate, potassium hydrogen acetate, potassium oxalate, potassium hydrogen oxalate, calcium acetate , Calcium oxalate,
Lithium acetate, lithium hydrogen acetate, lithium oxalate,
It is preferably at least one carboxylic acid compound selected from lithium hydrogen oxalate, magnesium acetate, magnesium oxalate, ammonium acetate, ammonium hydrogen acetate, ammonium oxalate, and ammonium hydrogen oxalate.

In the ink of the present invention, the reactive dye is preferably a water-soluble reactive dye.

In the ink of the present invention, the water-soluble reactive dye preferably has a reactive group containing a chlorine group in the molecule.

In the ink of the present invention, the reactive group containing a chlorine group is preferably chlorotriazine or dichlorotriazine.

In the ink of the present invention, the dye is preferably contained in an amount of 1 to 10 parts by weight based on the total amount of the ink.

In the ink of the present invention, at least one of the organic solvents is preferably ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerin, triethylene glycol monobutyl ether, or diethylene glycol monobutyl ether.

In the ink of the present invention, the organic solvent preferably has 1 to 50 parts by weight based on the total amount of the ink.

In the ink of the present invention, the surfactant is preferably a nonionic surfactant.

In the ink of the present invention, the surfactant is preferably contained in an amount of 0.01 to 10 parts by weight based on the total amount of the ink.

In the ink of the present invention, the static surface tension at 25 ° C. is preferably 20 to 50 dyne / cm.

In the ink of the present invention, the pH at 25 ° C. is preferably 6.5 to 11.

Next, the ink jet recording system of the present invention is characterized in that printing is performed using the ink for an ink jet recording apparatus described above.

Next, an ink jet recording apparatus according to the present invention is characterized by using any one of the inks for an ink jet recording apparatus described above.

Next, an ink container according to the present invention is provided with the ink for an ink jet recording apparatus described above.

[0040]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments.

The ink for an ink jet recording apparatus according to the present invention is an ink for an ink jet recording apparatus comprising a reactive dye, an organic solvent and a surfactant, wherein the ink is ink A, and the ink A is polyethylene glycol # 200 (polyethylene glycol average molecular weight 200 ) From 0.1 to 5
A part by weight of the ink B was used as the ink B, and the ink A and the ink B each had a droplet volume of 20 picoliter and a resolution of 720.
After printing on plain paper with a piezo-type inkjet printer so as to be arranged on all the grids of dpi, the printed sample is immersed in water over the entire surface in a glass water tank (capacity 3 L) filled with 25 ° C pure water. The color difference ΔE calculated from the following general formula (1) is printed with ink A based on the result of colorimetry of a print sample before and after water immersion using a CIE (L *, a *, b *) display system. Color difference ΔEa for the printed matter and color difference ΔEb for the printed matter with ink B, ΔEa, ΔEb
Satisfy the relationship of △ Eb / △ Ea ≦ 0.9.

The general formula (1) is defined as follows: △ E = ｛(L1 ^{*
-L2 *) 2 + (a1 *} -a2 *) 2 + (b1 * -b2 *) 2}
^The equation shown by ^1/2 is shown. However, (L1 ^* , a1
^* , B1 *): colorimetric values in the print sample before immersion in water, and (L2 ^* , a2 ^* , b2 ^* ): colorimetric values in the print sample after immersion in water.

Hereinafter, a method for preparing the print sample, a method for measuring the optical density (OD value), and a method for immersion in water will be described.

(Preparation Method of Print Sample) The print samples are arranged on all the grids with a resolution of 720 dpi by a piezo-type inkjet printer adjusted so that the amount of one ink droplet becomes 20 picoliters. It is produced by printing ink for an ink jet recording apparatus on plain paper. The plain paper is not particularly limited as long as it is a commercially available plain paper, but preferably L paper manufactured by Xerox is used.

(Water immersion method)
This is performed by filling a glass water tank (capacity: 3 L) with pure water at 25 ° C., immersing the printed sample in the water over the entire surface, or by leaving it at 25 ° C. for 5 minutes.

(Colorimetry) The colorimetry of the print sample is 93
8 Spectro-Densitometer (X-
Using the L ^* a ^* b ^* color system (CIEL)
(AB color system). In the present invention, the ink A is an ink for an ink jet recording apparatus comprising a reactive dye, an organic solvent, and a surfactant, and the ink B is an ink A in which 5 parts by weight of polyethylene glycol #
200 (polyethylene glycol average molecular weight 200) was added, and the print samples printed with ink A and ink B were immersed in water, and both print samples before and after immersion in water were subjected to L ^* a ^* b ^* table. Color system (CIE
LAB color system), and the color difference ΔE is calculated by introducing the color measurement result into the following general formula (1). In addition.
The color difference of the printed matter by the ink A is ΔEa, and the color difference of the printed matter by the ink B is ΔEb.

The general formula (1) △ E = {( L1 * -L2 *) 2 + (a1 * -a2 *) 2 + (b1 * - b2 *) 2} 1/2 However, (L1 ^*, a1 ^* , B1 ^* ): Colorimetric values in the print sample before immersion in water, (L2 ^* , a2 ^* , b2 ^* ): Colorimetric values in the print sample after immersion in water.

The ink of the present invention is characterized in that the ink is made water-resistant by chemically bonding the reactive dye and polyethylene glycol. The reaction in the present ink will be described below.

In the ink of the present invention,
Reactive dye and polyethylene glycol do not react. That is, the reaction between the reactive dye and polyethylene glycol is
The dye and polyethylene glycol coexist stably in the ink which is easily inhibited by water and in which a large amount of water exists. For this reason, the ink of the present invention has an advantage that storage stability is excellent.

On the other hand, the reaction between the dye and polyethylene glycol proceeds after printing the ink. That is, after printing the ink on the printing paper, the moisture in the ink is reduced by evaporation and permeation into the paper, so that the reaction between the dye and the polyethylene glycol easily proceeds. The reaction between the dye and the polyethylene glycol is also characterized in that the reaction is accelerated by exposure to visible light. After printing, the reaction is accelerated by light absorption.

Further, if the ink of the present invention is used,
The water resistance of not only plain paper but also special paper can be improved. Usually, in dyeing fibers with a reactive dye, a chemical reaction proceeds between the reactive group of the reactive dye and the hydroxyl group of cellulose fibers (including plain paper), and the water resistance is improved by stabilizing fixing of the dye. However, the reaction of the reactive dye for the purpose of increasing the water resistance requires a cellulose fiber to be reacted with the dye. For this reason, plain paper whose printing surface is formed of cellulose fiber is effective,
In the case of glossy paper or the like in which the printing surface is formed of a receiving layer, the effect of improving water resistance is not exhibited. On the other hand, in the ink of the present invention, a dye is combined with polyethylene glycol to increase the water resistance of the ink, and high water resistance can be realized, and the range of selection of a printing medium is wide.

The ink of the present invention is preferably constituted by adding polyethylene glycol (average molecular weight: 200 to 1,000). By adding polyethylene glycol to the ink of the present invention, it is possible to improve the water resistance of printed matter produced using this ink. The amount of polyethylene glycol added was 1
-20 parts by weight are preferred. When the amount exceeds 20 parts by weight, the viscosity of the ink is greatly increased, and when the amount is less than 1 part by weight, the effect of improving the water resistance is not seen. The polyethylene glycol is not particularly limited as long as it is a commercially available compound, but it is preferable to use polyethylene glycol having an average molecular weight of 200 to 1,000.

The ink of the present invention can be constituted by adding an alkali salt. By adding an alkali salt, formation of a chemical bond between polyethylene glycol and a dye is promoted, and the water resistance of the ink can be improved. Further, the addition amount of the alkali salt is preferably 0.1 to 10 parts by weight, and when added in an amount exceeding 10 parts by weight, the viscosity of the ink is significantly increased. Also,
If the amount is less than 0.1 part by weight, the effect of improving water resistance cannot be obtained.

The ink of the present invention is preferably constituted by adding a carbonate. The carbonate is selected from sodium carbonate, potassium carbonate, calcium carbonate, lithium carbonate, magnesium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, calcium bicarbonate, lithium bicarbonate, magnesium bicarbonate, and ammonium bicarbonate. It is preferable to use one or more types. These carbonates are used as an active catalyst for a chemical reaction between the dye and the cellulose fiber.

The ink of the present invention is preferably constituted by adding a phosphate. Examples of the phosphate include trisodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium monophosphate, tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, and phosphorous monophosphate. Potassium phosphate, tricalcium phosphate, calcium dihydrogen phosphate, calcium monophosphate, magnesium phosphate, trilithium phosphate, lithium dihydrogen phosphate, lithium monophosphate, magnesium hydrogen phosphate, magnesium dihydrogen phosphate , One selected from triammonium phosphate, ammonium dihydrogen phosphate and ammonium monophosphate
It is preferred to use more than one species. These phosphates are used as an active catalyst for a chemical reaction between the dye and the cellulose fiber.

The ink of the present invention is preferably constituted by adding a borate. Examples of the borate include sodium borates (sodium metaborate, sodium niborate, sodium tetraborate, sodium pentaborate, sodium hexaborate, sodium octaborate), potassium borates (potassium metaborate, Potassium tetraborate, potassium pentaborate, potassium hexaborate), ammonium borates (ammonium metaborate, ammonium tetraborate, ammonium pentaborate, ammonium octaborate),
Magnesium borate (magnesium metaborate, trimagnesium tetraborate, pentamagnesium tetraborate, magnesium hexaborate), lithium borates (lithium metaborate, lithium tetraborate, lithium pentaborate), ammonium borate It is preferable to use at least one member selected from the group consisting of aminomonium metaborate, ammonium tetraborate, ammonium pentaborate and ammonium octaborate.
These borates are used as an active catalyst for a chemical reaction between the dye and the cellulose fiber.

The ink of the present invention is preferably constituted by adding an organic amine compound. As the organic amine compound, it is preferable to use one or more selected from ethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, and triethanolamine. These organic amine compounds are used as an active catalyst for a chemical reaction between the dye and the cellulose fiber.

The ink of the present invention is preferably constituted by adding a pyridine compound. Examples of the pyridine compound include pyridine, 1-methylpyridine, 2-methylpyridine, 4-methylpyridine, 1-ethylpyridine,
It is preferable to use one or more selected from -ethylpyridine, 3-ethylpyridine, and 2-methoxypyridine. These pyridine compounds are used as an active catalyst for a chemical reaction between the dye and the cellulose fiber.

The ink of the present invention is preferably constituted by adding a hydroxide compound. As the hydroxide compound, it is preferable to use one or more selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, and ammonium hydroxide. These hydroxide compounds are used as an active catalyst for a chemical reaction between the dye and the cellulose fiber.

The ink of the present invention is preferably constituted by adding a carboxylic acid compound. Examples of the carboxylic acid compound include sodium acetate, sodium hydrogen acetate, sodium oxalate, sodium hydrogen oxalate, potassium acetate, potassium hydrogen acetate, potassium oxalate, potassium hydrogen oxalate, calcium acetate, calcium oxalate,
Lithium acetate, lithium hydrogen acetate, lithium oxalate,
It is preferable to use at least one selected from lithium hydrogen oxalate, magnesium acetate, magnesium oxalate, ammonium acetate, ammonium hydrogen acetate, ammonium oxalate, and ammonium hydrogen oxalate. In addition,
These carboxylic acid compounds are used as an active catalyst for a chemical reaction between the dye and the cellulose fiber.

In the ink of the present invention, the reactive dye is not particularly limited as long as it is a dye specified in the category of the reactive dye, but it is preferable to use an aqueous dye. Examples of the aqueous reactive dye include Reactive Black 3, Reactive Black 4, Reactive Black 7, Reactive Black 11, Reactive Black 12, Reactive Black 17, Reactive Yellow 1, Reactive Yellow 5, and Reactive Black 5. Active Yellow 11, Reactive Yellow 13, Reactive Yellow 14, Reactive Yellow 20, Reactive Yellow 21, Reactive Yellow 22, Reactive Yellow 25, Reactive Yellow 40, Reactive Yellow 47, Reactive Yellow 51, Reactive Yellow Active Yellow 55, Reactive Yellow 65, Reactive Yellow 67, Reactive Red 1, Reactive Red 14, Reactive Red 17, Reactive Red 25, Reactive Red Active Red 26, Reactive Red 32, Reactive Red 37, Reactive Red 44, Reactive Red 46, Reactive Red 55, Reactive Red 60, Reactive Red 6
6, Reactive Red 74, Reactive Red 7
9, Reactive Red 96, Reactive Red 9
7, Reactive Blue 1, Reactive Blue 2, Reactive Blue 7, Reactive Blue 14, Reactive Blue 15, Reactive Blue 23, Reactive Blue 32, Reactive Blue 35, Reactive Blue 38, Reactive Blue 41, Reactive Blue 63, Reactive Blue 80, Reactive Blue 95, and the like, but are not particularly limited thereto.
Any water-soluble reactive dye can be used.

The amount of the dye to be added is preferably 1 to 10 parts by weight based on the total amount of the ink, and when 10 or more parts of the dye are added, the stability of the ink is poor. Easily occurs, and the viscosity is greatly increased. On the other hand, when the amount of the dye added is less than 1 part by weight, there is a problem that a good printed image cannot be obtained because the dye concentration is low.

In the ink for an ink jet recording apparatus of the present invention, water is used as a liquid for dissolving the dye. As the water, ion-exchanged water is preferable from the viewpoint of dye stability, but commercially available distilled water may be used.

In the ink of the present invention, it is preferable to use a dye having a reactive group containing a chlorine group in the molecule. With such a configuration, a chemical reaction is promoted between the chlorine group in the dye molecule and the hydroxyl group of the cellulose fiber constituting the paper, the bond stability between the dye and polyethylene glycol is improved, and the ink is used. The water resistance of the printed matter produced by the above is improved. Further, in the ink of the present invention, it is preferable to use a dye containing a chlorotriazine group or a dichlorotriazine group. By using a chlorotriazine or dichlorotriazine group as a reactive group that reacts with the cellulose fiber, the binding stability between the dye and the polyethylene glycol is improved.

Examples of the organic solvent used in the ink for an ink jet recording apparatus of the present invention include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol MW200, polyethylene glycol MW300, and polyethylene glycol MW6.
00, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, methyl carbitol, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, diethyl carbitol, triethylene glycol monomethyl ether, triethylene glycol monoethyl Ether, triethylene glycol monobutyl ether, glycerin, triethanolamine, formamide, dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidine, and the like, but not particularly limited thereto. Not done. Further, among these organic solvents, at least one organic solvent selected from the group consisting of diethylene glycol, propylene glycol, polyethylene glycol, glycerin, triethylene glycol monobutyl ether and diethylene glycol monobutyl ether has ink storage stability, It is preferably used in terms of permeability.

These organic solvents are used as a penetrant and a dye dissolution aid, and the amount of the organic solvent is preferably 50 parts by weight or less based on the total amount of the ink. If the amount of the organic solvent exceeds 50 parts by weight, the drying property on paper may be poor, and a good printed image may not be obtained.

In the ink of the present invention, it is preferable to use a nonionic surfactant. Examples of the surfactant include an acetylene glycol-based compound and a propylene oxide-ethylene oxide copolymer.
It is not particularly limited to this. The addition amount of the surfactant is preferably from 0.01 to 10 parts by weight. If the amount is less than 0.01 part by weight, the effect is insufficient as a surface tension adjuster because the amount is small. On the other hand, when the amount is 10 parts by weight or more, the viscosity of the ink is greatly increased due to the high amount of addition, and thus there is a possibility that inconvenience such as clogging of the print head may occur.

Further, conventionally known additives such as a pH adjuster, a fungicide and a chelating agent can be mixed with the ink for an ink jet recording apparatus of the present invention. Examples of the pH adjuster include potassium carbonate, sodium carbonate, triethanolamine and the like. Examples of the antifungal agent include sodium benzoate.
Examples of the chelating agent include sodium diethylenetriaminepentaacetate.

The surface tension of the ink for an ink jet recording apparatus of the present invention is preferably 20 to 50 dyne / cm at 25 ° C. The surface tension in the present invention is a static surface tension when the liquid surface is at rest, and can be measured by a Wilhelmy plate hanging method or the like. This static surface tension is more than 50 dyne / cm, or 20 d
With an ink for an ink jet recording apparatus having a particle diameter of less than yne / cm, the permeability and the drying property are deteriorated at the time of image formation, and a good printed image may not be obtained.

The viscosity of the ink for an ink jet recording apparatus of the present invention is preferably adjusted to a range of 1 to 5 cps at 25 ° C. Viscosity greater than 5 cps or 1
With an ink for an ink jet recording apparatus having a cps of less than cps, the ink ejection stability of the head is deteriorated, and a good printed image may not be obtained.

The pH of the ink for an ink jet recording apparatus of the present invention is preferably adjusted to 6.5 to 11.5 at 25 ° C. PH of ink for inkjet recording device
Is adjusted to 6.5 to 11.5, the long-term storability of the ink is improved, changes in various physical properties such as surface tension and viscosity are reduced, and stable ink ejection is possible over a long period of time.

Since the ink for an ink jet recording apparatus of the present invention uses an aqueous dye, it has high ejection stability and can obtain a printed matter excellent in sharpness.

The ink for an ink-jet recording apparatus of the present invention is suitably used for an ink-jet recording apparatus and an ink-jet recording system for performing print recording by discharging ink droplets. It is not limited to this.

The ink container of the present invention has a storage chamber for storing the ink of the present invention, and at least a joint portion of the storage chamber with the present invention is made of a material inert to the ink of the present invention. The material inert to the ink for an ink jet recording apparatus of the present invention is a material that does not dissolve at least in the ink of the present invention, and does not adversely affect the ink of the present invention when stored, such as a resin, Materials such as metals and ceramics.

The ink jet recording apparatus of the present invention has an ink discharge port for discharging the ink of the present invention, and can perform recording on paper or the like using the ink of the present invention. As described above, the ink of the present invention is used in an ink jet recording apparatus that performs print recording by discharging ink droplets, but its use is not particularly limited.

Since such an ink jet recording apparatus and the ink jet recording method use the ink for an ink jet recording apparatus of the present invention, the printed matter having excellent ejection stability and storage stability and very excellent sharpness is provided. Can be obtained.

[0077]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. First, with respect to each evaluation item of the ink and the printed matter produced in the present example, a measuring device, a measuring condition, an evaluation method and an evaluation standard will be described below.

(Static surface tension) Measurement was performed using a Wilhelmy surface tensiometer (automatic surface tensiometer CBVP-A3, manufactured by Kyowa Interface Chemical Co., Ltd.). The measurement temperature was 25 ° C. (Viscosity) It was measured by an automatic viscosity meter DVM-EII (manufactured by Tokimec). The measurement temperature was 25 ° C. (PH) Measured with a personal pH meter PH81 (manufactured by Yokogawa Electric Corporation). The measurement temperature was 25 ° C.

(Evaluation 1 of Water Resistance) Ink A of this example was used
Used, the amount of one ink droplet is 20 pl (pico liter)
Piezo-type inkjet pudding adjusted to
Grid of a printhead with a resolution of 720 dpi
Inkjet recording of the embodiment so that
Ink for recording device printed on glossy paper in 2cm x 2cm square
Printing was performed to obtain a print sample. Solid of this print sample
Color value (L1^*, A1^*, B1^*), L^*a^*b^*Color
The color was measured with a system (CIELAB color system). Water immersion described later
The print sample is immersed in water under the conditions
Color value (L2^*, A2^*, B2 ^*), L^*a^*b^*Color
The color was measured with the system. In addition, water-resistant
The deterioration change rate ΔEc was calculated by the following equation (1). Printing
As the paper, two photo prints made by Epson were used. Equation (1) ΔEc = ｛(L1^*-L2^*)^Two+ (A1^*-A2^*)^Two+ (B1^*−b 2^*)^Two｝^1/2 The color value is 938 Spectro-Densi.
measurement using a X-Rite (manufactured by X-Rite)
Was.

(Water immersion conditions) Glass water tank (capacity 10
L) was filled with pure water at 25 ° C., and the printed sample was immersed in water over the entire surface and left at 25 ° C. for 5 minutes. The printed sample lifted from the water tank was dried at room temperature for 3 hours.

(Evaluation of bleeding) The amount of one ink droplet was 20
pl (picoliter) using a piezo-type inkjet printer adjusted to a resolution of 720 dp.
The ink for an ink jet recording device was printed in a square of 2 cm × 2 cm on plain paper so as to be arranged on all the grids of i, thereby obtaining a print sample. As printing paper, L paper (A4 size) manufactured by Xerox was used. The bleeding degree of the image of this print sample was confirmed, and the ejection stability was evaluated according to the following evaluation criteria.

：: All are good printed images. Δ: Most of the images were good, but some abnormal images were observed. ×: Many abnormal printed images were observed.

(Evaluation of Ejection Stability) A printing test was performed on 100 sheets using a piezo-type inkjet printer with a resolution of 720 dpi adjusted so that the amount of one ink droplet was 10 pl (picoliter). Commercially available recycled paper (A4 size) was used as the printing paper. The sharpness of the image was confirmed for the 100 print samples, and the ejection stability was evaluated according to the following evaluation criteria.

：: All are good print images. Δ: Most of the images were good, but some abnormal images were observed. ×: Many abnormal printed images were observed.

(Evaluation of Storage Stability) The ink for an ink jet recording apparatus was stored in a polyethylene container at 60 ° C. for one month, and examined for changes in surface tension, viscosity and pH, and the presence or absence of precipitates. The storage stability was evaluated according to the following.

：: There is almost no change in physical properties, and no precipitate is observed. Δ: Physical properties slightly changed, but no precipitate was observed. C: Physical properties were significantly changed, and precipitates were confirmed.

[Example 1] (Ink A) Reactive Yellow 67 3 parts Diethylene glycol 15 parts Glycerin 10 parts Nonionic surfactant 1 part Ion-exchanged water balance

In the ink A of Example 1, the surface tension γ = 3
0.2 dyne / cm, viscosity η = 3.0 cps, pH =
8.6.

(Ink B) Ink B was prepared by adding 5 parts by weight of polyethylene glycol # 200 to ink A of Example 1 above.

95.2 parts of ink A (100/105 parts) Polyethylene glycol # 200 balance (5/105 parts)

In the ink B of Example 1, the surface tension γ = 3
0.3 dyne / cm, viscosity η = 3.4 cps, pH =
8.7.

[Example 2] (Ink A) Reactive Yellow 67 3 parts Diethylene glycol 15 parts Polyethylene glycol # 200 5 parts Glycerin 10 parts Nonionic surfactant 1 part Ion-exchanged water balance

In the ink A of Example 2, the surface tension γ = 3
0.5 dyne / cm, viscosity η = 3.5 cps, pH =
8.5.

(Ink B) Ink B was prepared by adding 5 parts by weight of polyethylene glycol # 200 to ink A of Example 2 above.

95.2 parts of ink A (100/105 parts) Polyethylene glycol # 200 balance (5/105 parts)

In the ink B of Example 2, the surface tension γ = 3
0.6 dyne / cm, viscosity η = 3.8 cps, pH =
8.6.

Example 3 (Ink A) Reactive Yellow 67 3 parts Diethylene glycol 15 parts Polyethylene glycol # 200 5 parts Glycerin 10 parts Nonionic surfactant 1 part Sodium carbonate 1 part Ion-exchanged water balance

In the ink A of Example 3, the surface tension γ = 3
0.3 dyne / cm, viscosity η = 3.6 cps, pH =
9.1.

(Ink B) Ink B was prepared by adding 5 parts by weight of polyethylene glycol # 200 to ink A of Example 3 above.

95.2 parts of ink A (100/105 parts) Polyethylene glycol # 200 balance (5/105 parts)

In the ink B of Example 3, the surface tension γ = 3
0.4 dyne / cm, viscosity η = 3.9 cps, pH =
9.2.

Example 4 (Ink A) Reactive Yellow 67 3 parts Diethylene glycol 15 parts Polyethylene glycol # 200 5 parts Glycerin 10 parts Nonionic surfactant 1 part Trisodium phosphate 1 part Ion-exchanged water balance

In the ink A of Example 4, the surface tension γ = 3
0.3 dyne / cm, viscosity η = 3.6 cps, pH =
9.5.

(Ink B) Ink B was prepared by adding 5 parts by weight of polyethylene glycol # 200 to ink A of Example 4 above.

95.2 parts of ink A (100/105 parts) Polyethylene glycol # 200 balance (5/105 parts)

In the ink B of Example 4, the surface tension γ = 3
0.5 dyne / cm, viscosity η = 3.9 cps, pH =
9.6.

Example 5 (Ink A) Reactive Yellow 67 3 parts Diethylene glycol 15 parts Polyethylene glycol # 200 5 parts Glycerin 10 parts Nonionic surfactant 1 part Potassium borate 1 part Ion-exchanged water balance

In the ink A of Example 5, the surface tension γ = 3
0.4 dyne / cm, viscosity η = 3.6 cps, pH =
9.4.

(Ink B) Ink A was prepared by adding 5 parts by weight of polyethylene glycol # 200 to ink A of Example 5.

95.2 parts of ink A (100/105 parts) Polyethylene glycol # 200 balance (5/105 parts)

In the ink B of Example 5, the surface tension γ = 3
0.5 dyne / cm, viscosity η = 3.9 cps, pH =
9.5.

[Example 6] (Ink A) Reactive Yellow 67 3 parts Diethylene glycol 15 parts Polyethylene glycol # 200 5 parts Glycerin 10 parts Nonionic surfactant 1 part Triethylamine 1 part Ion-exchanged water Remaining part

In the ink A of Example 6, the surface tension γ = 3
0.6 dyne / cm, viscosity η = 3.6 cps, pH =
9.3.

(Ink B) Ink B was prepared by adding 5 parts by weight of polyethylene glycol # 200 to ink A of Example 6.

Ink A 95.2 parts (100/105 parts) Polyethylene glycol # 200 balance (5/105 parts)

In the ink B of Example 6, the surface tension γ = 3
0.5 dyne / cm, viscosity η = 3.9 cps, pH =
9.4.

Example 7 (Ink A) Reactive Yellow 67 3 parts Diethylene glycol 15 parts Polyethylene glycol # 200 5 parts Glycerin 10 parts Nonionic surfactant 1 part Pyridine 1 part Deionized water remaining part

In the ink A of Example 7, the surface tension γ = 3
0.5 dyne / cm, viscosity η = 3.6 cps, pH =
9.2.

(Ink B) Ink B was prepared by adding 5 parts by weight of polyethylene glycol # 200 to ink A of Example 7.

95.2 parts of ink A (100/105 parts) Polyethylene glycol # 200 balance (5/105 parts)

In the ink B of Example 7, the surface tension γ = 3
0.7 dyne / cm, viscosity η = 3.9 cps, pH =
9.4.

[Example 8] (Ink A) Reactive Yellow 67 3 parts Diethylene glycol 15 parts Polyethylene glycol # 200 5 parts Glycerin 10 parts Nonionic surfactant 1 part Sodium hydroxide 1 part Ion-exchanged water balance

In the ink A of Example 8, the surface tension γ = 3
0.5 dyne / cm, viscosity η = 3.6 cps, pH =
10.1.

(Ink B) Ink A was prepared by adding 5 parts by weight of polyethylene glycol # 200 to ink A of Example 8.

95.2 parts of ink A (100/105 parts) Polyethylene glycol # 200 balance (5/105 parts)

In the ink B of Example 8, the surface tension γ = 3
0.7 dyne / cm, viscosity η = 3.9 cps, pH =
10.2.

Example 9 (Ink A) Reactive Blue 7 3 parts Diethylene glycol 15 parts Polyethylene glycol # 200 5 parts Glycerin 10 parts Nonionic surfactant 1 part Sodium carbonate 1 part Ion-exchanged water balance

In the ink A of the ninth embodiment, the surface tension γ = 3
0.8 dyne / cm, viscosity η = 3.6 cps, pH =
8.9.

(Ink B) Ink B was prepared by adding 5 parts by weight of polyethylene glycol # 200 to ink A of Example 9.

95.2 parts of ink A (100/105 parts) Polyethylene glycol # 200 balance (5/105 parts)

In the ink B of the ninth embodiment, the surface tension γ = 3
0.9 dyne / cm, viscosity η = 3.9 cps, pH =
8.8.

Example 10 (Ink A) Reactive Red 14 3 parts Diethylene glycol 15 parts Polyethylene glycol # 200 5 parts Glycerin 10 parts Nonionic surfactant 1 part Sodium carbonate 1 part Ion-exchanged water balance

In the ink A of Example 10, the surface tension γ =
30.1 dyne / cm, viscosity η = 3.6 cps, pH
= 8.9.

(Ink B) Ink B was prepared by adding 5 parts by weight of polyethylene glycol # 200 to ink A of Example 10.

95.2 parts of ink A (100/105 parts) Polyethylene glycol # 200 balance (5/105 parts)

For the ink B of Example 10, the surface tension γ =
30.3 dyne / cm, viscosity η = 3.9 cps, pH
= 9.0.

Example 11 (Ink A) Reactive Black 176 parts Diethylene glycol 15 parts Polyethylene glycol # 200 5 parts Glycerin 10 parts Nonionic surfactant 1 part Sodium carbonate 1 part Ion-exchanged water balance

In the ink A of Example 11, the surface tension γ =
30.5 dyne / cm, viscosity η = 3.9 cps, pH
= 9.2.

(Ink B) Ink B was prepared by adding 5 parts by weight of polyethylene glycol # 200 to ink A of Example 11.

Ink A 95.2 parts (100/105 parts) Polyethylene glycol # 200 balance (5/105 parts)

In the ink B of Example 11, the surface tension γ =
30.6 dyne / cm, viscosity η = 4.4 cps, pH
= 9.3.

Example 12 (Ink A) Chlorotriazine dye 3 parts Diethylene glycol 15 parts Polyethylene glycol # 200 5 parts Glycerin 10 parts Nonionic surfactant 1 part Sodium carbonate 1 part Deionized water balance

In the ink A of Example 12, the surface tension γ =
30.1 dyne / cm, viscosity η = 3.6 cps, pH
= 9.4.

(Ink B) Ink B was prepared by adding 5 parts by weight of polyethylene glycol # 200 to ink A of Example 12.

Ink A 95.2 parts (100/105 parts) Polyethylene glycol # 200 balance (5/105 parts)

In the ink B of Example 12, the surface tension γ =
30.3 dyne / cm, viscosity η = 3.9 cps, pH
= 9.5.

Example 13 (Ink A) 3 parts of dichlorotriazine dye 15 parts of diethylene glycol 5 parts of polyethylene glycol # 200 5 parts of glycerin 1 part of nonionic surfactant 1 part of sodium carbonate 1 part of ion-exchanged water

In the ink A of Example 13, the surface tension γ =
30.6 dyne / cm, viscosity η = 3.6 cps, pH
= 9.1.

(Ink B) Ink B was prepared by adding 5 parts by weight of polyethylene glycol # 200 to ink A of Example 13.

Ink A 95.2 parts (100/105 parts) Polyethylene glycol # 200 balance (5/105 parts)

In the ink B of Example 13, the surface tension γ =
30.7 dyne / cm, viscosity η = 3.9 cps, pH
= 9.2.

Comparative Example 1 (Ink A) Direct Yellow 120 3 parts Diethylene glycol 15 parts Glycerin 10 parts Nonionic surfactant 1 part Ion-exchanged water balance

In the ink A of Comparative Example 1, the surface tension γ = 3
0.5 dyne / cm, viscosity η = 3.0 cps, pH =
8.5.

(Ink B) Ink B was prepared by adding 5 parts by weight of polyethylene glycol # 200 to ink A of Comparative Example 1.

Ink A 95.2 parts (100/105 parts) Polyethylene glycol # 200 balance (5/105 parts)

In the ink B of Comparative Example 1, the surface tension γ = 3
0.4 dyne / cm, viscosity η = 3.3 cps, pH =
8.4.

Comparative Example 2 (Ink A) Direct Yellow 120 3 parts Diethylene glycol 15 parts Polyethylene glycol # 200 5 parts Glycerin 10 parts Nonionic surfactant 1 part Deionized water remaining

In the ink A of Comparative Example 2, the surface tension γ = 3
0.5 dyne / cm, viscosity η = 3.4 cps, pH =
8.6.

(Ink B) Ink B was prepared by adding 5 parts by weight of polyethylene glycol # 200 to ink A of Comparative Example 2.

95.2 parts of ink A (100/105 parts) Polyethylene glycol # 200 balance (5/105 parts)

In the ink B of Comparative Example 2, the surface tension γ = 3
0.6 dyne / cm, viscosity η = 3.8 cps, pH =
8.7.

Comparative Example 3 (Ink A) Direct Yellow 120 3 parts Diethylene glycol 15 parts Polyethylene glycol # 200 5 parts Glycerin 10 parts Sodium carbonate 1 part Nonionic surfactant 1 part Deionized water remaining

In the ink A of Comparative Example 3, the surface tension γ = 3
0.4 dyne / cm, viscosity η = 3.4 cps, pH =
9.3.

(Ink B) Ink B was prepared by adding 5 parts by weight of polyethylene glycol # 200 to ink A of Comparative Example 3.

95.2 parts of ink A (100/105 parts) Polyethylene glycol # 200 balance (5/105 parts)

In the ink B of Comparative Example 3, the surface tension γ = 3
0.5 dyne / cm, viscosity η = 3.8 cps, pH =
9.3.

Comparative Example 4 (Ink A) Direct Red 80 3 parts Diethylene glycol 15 parts Polyethylene glycol # 200 5 parts Glycerin 10 parts Sodium carbonate 1 part Nonionic surfactant 1 part Deionized water remaining

In the ink A of Comparative Example 4, the surface tension γ = 3
0.8 dyne / cm, viscosity η = 3.4 cps, pH =
9.1.

(Ink B) Ink B was prepared by adding 5 parts by weight of polyethylene glycol # 200 to ink A of Comparative Example 4.

95.2 parts of ink A (100/105 parts) Polyethylene glycol # 200 balance (5/105 parts)

In the ink B of Comparative Example 4, the surface tension γ = 3
0.8 dyne / cm, viscosity η = 3.8 cps, pH =
9.2.

Comparative Example 5 (Ink A) Acid Blue 249 3 parts Diethylene glycol 15 parts Polyethylene glycol # 200 5 parts Glycerin 10 parts Sodium carbonate 1 part Nonionic surfactant 1 part Deionized water remaining

In the ink A of Comparative Example 5, the surface tension γ = 3
0.5 dyne / cm, viscosity η = 3.4 cps, pH =
9.0.

(Ink B) Ink B was prepared by adding 5 parts by weight of polyethylene glycol # 200 to ink A of Comparative Example 5.

Ink A 95.2 parts (100/105 parts) Polyethylene glycol # 200 balance (5/105 parts)

In the ink B of Comparative Example 5, the surface tension γ = 3
0.6 dyne / cm, viscosity η = 3.8 cps, pH =
9.1.

Comparative Example 6 (Ink A) Acid Black 24 6 parts Diethylene glycol 15 parts Polyethylene glycol # 200 5 parts Glycerin 10 parts Sodium carbonate 1 part Nonionic surfactant 1 part Deionized water remaining

In the ink A of Comparative Example 6, the surface tension γ = 3
0.5 dyne / cm, viscosity η = 3.7 cps, pH =
9.1.

(Ink B) Ink B was prepared by adding 5 parts by weight of polyethylene glycol # 200 to ink A of Comparative Example 6.

95.2 parts of ink A (100/105 parts) Polyethylene glycol # 200 balance (5/105 parts)

In the ink B of Comparative Example 6, the surface tension γ = 3
0.5 dyne / cm, viscosity η = 4.1 cps, pH =
9.0.

Next, the evaluation results of the respective inks prepared above will be described with reference to Tables 1 and 2. As shown in Tables 1 and 2, the inks of Examples 1 to 13 in which ΔEb / ΔEa was set to 0.9 or less had little bleeding of printed matter and were excellent in water resistance and storage stability. confirmed.

[0183]

[Table 1]

[0184]

[Table 2]

[0185]

As described above in detail, the ink for an ink jet recording apparatus according to the present invention is obtained by converting the ink A and the ink B described in the text into a grid having a droplet volume of 20 picoliters and a resolution of 720 dpi. As placed in
After printing on plain paper with a piezo-type inkjet printer, a glass water tank filled with 25 ° C pure water (capacity 3
L), the printed sample was immersed in water over the entire surface, and the printed sample before and after immersion in water was measured with a CIE (L ^* , a ^* , b ^* ) display system. The calculated color difference ΔE is calculated using the color difference Δ
In the printed matter using Ea and ink B, the color difference is ΔEb, and ΔEb
Since a and △ Eb satisfy the relationship of ｂEb / △ Ea ≦ 0.9, a printed material having high ejection stability and storage stability, less bleeding, and excellent water resistance is obtained. be able to.

[0186] Formula (1) △ E = {( L1 * -L2 *) 2 + (a1 * -a2 *) 2 + (b1 * - b2 *) 2} 1/2 However, (L1 ^*, a1 ^* , B1 ^* ): Colorimetric values in printed matter before immersion in water, (L2 ^* , a2 ^* , b1 ^* ): Colorimetric values in printed matter after immersion in water.

In addition, the ink of the present invention can improve the water resistance not only on plain paper but also on special paper, so that a wide range of printing media can be selected. In addition, printed matter using the ink for an ink jet recording apparatus can improve the weather resistance, which has conventionally been a problem.

The ink jet recording apparatus of the present invention is an ink jet recording apparatus which performs recording by discharging a recording liquid from a fine hole in accordance with a recording signal, since the recording liquid is the ink for an ink jet recording apparatus of the present invention. A printed material having excellent ejection stability and storage stability and having extremely excellent water resistance can be obtained.

Further, the ink jet recording system of the present invention is an ink jet recording system in which recording is performed by discharging a recording liquid from a fine hole in accordance with a recording signal, wherein the ink for an ink jet recording apparatus of the present invention is used as the recording liquid. Therefore, it is possible to obtain a printed matter having excellent ejection stability and storage stability, and having extremely excellent water resistance.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Hiroyuki Ueki 5-7-1 Shiba, Minato-ku, Tokyo F-term in NEC Corporation (reference) 2C056 EA13 FC01 FC02 2H086 BA01 BA53 BA56 BA59 BA60 BA61 BA62 4J039 AE07 BA14 BA16 BA19 BA24 BC10 BC11 BC13 BC14 BC15 BC19 BC27 BC34 BC35 BC50 BC52 BC72 BE06 BE22 EA34 EA38 EA41 EA44 EA46 EA47 GA24

Claims (31)

[Claims] 1. An ink for an ink jet recording apparatus comprising a reactive dye, an organic solvent and a surfactant, wherein the ink is ink A, and the ink A is polyethylene glycol # 20.
0 (polyethylene glycol average molecular weight 200) to 5
The ink A and the ink B are printed on plain paper by a piezo-type inkjet printer so that the amount of one drop of the ink A and the ink B is arranged on all of the grids having a resolution of 720 dpi with the amount of one drop being 20 picoliters. To prepare a print sample, and the print sample is heated at 25 ° C.
Immersed in water in a glass water tank (capacity 3 L) filled with pure water.
The color difference ΔE calculated from the following general formula (1) is calculated based on the result of color measurement using the IE (L ^* , a ^* , b ^* ) display system. In the print sample, the color difference ΔEb is used, and the ΔEa, ΔEb
Satisfies the following relationship: ΔEb / ΔEa ≦ 0.9. However, the general formula (1) is expressed as follows: △ E = ｛(L1
^{* -L2 *) 2 + (a1} * -a2 *) 2 + (b1 * -b
2 ^* ) ² ｝ ^1/2 , where (L1 ^* , a1 ^* , b
1 ^* ): colorimetric value of the print sample before immersion in water,
(L2 ^* , a2 ^* , b2 ^* ): Colorimetric values of the print sample after immersion in water. 2. Polyethylene glycol (polyethylene glycol having an average molecular weight of 200 to 1,000) of 0.1 to
2. The ink for an ink jet recording apparatus according to claim 1, wherein 20 parts by weight are added. 3. The ink for an ink jet recording apparatus according to claim 1, wherein 0.1 to 10 parts by weight of an alkali salt is added. 4. The ink for an ink jet recording apparatus according to claim 3, wherein the alkali salt is a carbonate. 5. The at least one carbonate selected from sodium carbonate, potassium carbonate, calcium carbonate, lithium carbonate, magnesium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, lithium hydrogencarbonate and ammonium hydrogencarbonate. 15. The ink for an ink jet recording apparatus according to claim 14, wherein the ink is a carbonate. 6. The ink for an ink jet recording apparatus according to claim 3, wherein the alkali salt is a phosphate. 7. The method according to claim 1, wherein the phosphate is trisodium phosphate,
Disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium monophosphate, tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium monophosphate, tricalcium phosphate, dihydrogen phosphate Calcium, monobasic calcium phosphate, magnesium phosphate, trilithium phosphate, lithium dihydrogen phosphate, lithium primary phosphate, magnesium hydrogen phosphate, magnesium dihydrogen phosphate, triammonium phosphate, ammonium dihydrogen phosphate, The ink for an ink jet recording apparatus according to claim 6, wherein the ink is at least one phosphate selected from ammonium monophosphate. 8. The ink according to claim 4, wherein the alkali salt is a borate. 9. The sodium borate (sodium metaborate, sodium niborate, sodium tetraborate, sodium pentaborate, sodium hexaborate, sodium octaborate) and potassium borate (9). Potassium metaborate, potassium tetraborate, potassium pentaborate,
Potassium hexaborate), ammonium borates (ammonium metaborate, ammonium tetraborate, ammonium pentaborate, ammonium octaborate), magnesium borates (magnesium metaborate, trimagnesium tetraborate, pentaborate tetraborate) Magnesium, magnesium hexaborate), lithium borates (lithium metaborate, lithium tetraborate, lithium pentaborate), ammonium borates (anomonium metaborate, ammonium tetraborate)
9. The ink for an ink jet recording apparatus according to claim 8, wherein the ink is one or more borates selected from ammonium pentaborate and ammonium octaborate. 10. The ink for an ink jet recording apparatus according to claim 1, wherein 0.1 to 10 parts by weight of an organic amine compound is added. 11. The inkjet according to claim 10, wherein the organic amine compound is at least one organic amine compound selected from ethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, and triethanolamine. Ink for recording devices. 12. The ink according to claim 1, wherein a pyridine compound is added in an amount of 0.1 to 10 parts by weight. 13. The method according to claim 13, wherein the pyridine compound is pyridine,
-Methylpyridine, 2-methylpyridine, 4-methylpyridine, 1-ethylpyridine, 2-ethylpyridine, 3
The ink for an inkjet recording apparatus according to claim 12, wherein the ink is at least one pyridine compound selected from -ethylpyridine and 2-methoxypyridine. 14. The ink for an ink jet recording apparatus according to claim 1, wherein 0.1 to 10 parts by weight of a hydroxide compound is added. 15. The method according to claim 1, wherein the hydroxide compound is one or more hydroxide compounds selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, and ammonium hydroxide. Item 15. Ink for an inkjet recording apparatus according to item 14. 16. The ink for an ink jet recording apparatus according to claim 1, wherein a carboxylic acid compound is added in an amount of 0.1 to 10 parts by weight. 17. The method according to claim 17, wherein the carboxylic acid compound is sodium acetate, sodium hydrogen acetate, sodium oxalate, sodium hydrogen oxalate, potassium acetate, potassium hydrogen acetate, potassium oxalate, potassium hydrogen oxalate, calcium acetate, calcium oxalate; At least one carboxylic acid compound selected from lithium acetate, lithium hydrogen acetate, lithium oxalate, lithium hydrogen oxalate, magnesium acetate, magnesium oxalate, ammonium acetate, ammonium hydrogen acetate, ammonium oxalate, and ammonium hydrogen oxalate 17. The method according to claim 16, wherein
5. The ink for an ink jet recording apparatus according to item 1. 18. The ink for an ink jet recording apparatus according to claim 1, wherein the reactive dye is a water-soluble reactive dye. 19. The method according to claim 18, wherein the water-soluble reactive dye has a reactive group containing a chlorine group in the molecule.
5. The ink for an ink jet recording apparatus according to item 1. 20. The ink for an ink jet recording apparatus according to claim 19, wherein the reactive group containing a chlorine group is chlorotriazine or dichlorotriazine. 21. The dye is added to the ink in an amount of 1 to
The ink for an inkjet recording apparatus according to any one of claims 1 to 20, wherein the ink has 10 parts by weight. 22. The method according to claim 1, wherein at least one of the organic solvents is ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerin, triethylene glycol monobutyl ether, or diethylene glycol monobutyl ether. Item 2. An ink for an ink jet recording apparatus according to item 1. 23. The method according to claim 20, wherein the organic solvent is
23. The composition according to claim 1, which has 1 to 50 parts by weight.
The ink for an inkjet recording device according to any one of the above. 24. The ink for an ink-jet recording apparatus according to claim 1, wherein the surfactant is a nonionic surfactant. 25. The ink for an ink jet recording apparatus according to claim 1, wherein the surfactant is contained in an amount of 0.01 to 10 parts by weight based on the total amount of the ink. 26. A static surface tension at 25 ° C. of 20
2. The method according to claim 1, wherein the pressure is from about 50 dyne / cm.
26. The ink for an inkjet recording apparatus according to any one of items 25 to 25. 27. The ink for an ink jet recording apparatus according to claim 1, wherein the pH at 25 ° C. is 6.5 to 11. 28. The ink for an inkjet recording apparatus according to claim 1, wherein the viscosity at 25 ° C. is 1 to 5 cps. 29. An ink jet recording method for printing using the ink for an ink jet recording apparatus according to claim 1. Description: 30. An ink jet recording apparatus using the ink for an ink jet recording apparatus according to claim 1. Description: 31. An ink container comprising the ink for an ink jet recording apparatus according to claim 1. Description: