JPH11315238A - Ink, ink set, ink cartridge, recording unit, image recording process, and image recording apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink which, even when used in long-time ink jet recording with a system in which the ink is delivered by means of a heater, exerts little influence such as a change in an ink delivery performance on the heater. SOLUTION: This ink comprises at least one substance selected from among a dicarboxylic acid, a dicarboxylate, a tricarboxylic acid, and a tricarboxylate; bishydroxyethyl sulfone; a water-soluble colorant; and an aqueous medium. It is desirable that the total amount of the dicarboxylic acid, the dicarboxylate, the tricarboxylic acid, and the tricarboxylate is 0.7 wt.% based on the total weight of the ink.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink, particularly an ink which can be suitably used for ink jet recording, in which an ink is ejected from an orifice according to a recording signal to perform recording on a recording medium, an ink set and an ink cartridge using the same. And a recording unit, an image recording apparatus, and an image recording method.

[0002]

2. Description of the Related Art Various types of ink jet recording techniques have been proposed so far. For example, a method in which charged ink droplets are continuously generated and a part of the ink droplets are used for recording, a piezoelectric element is used. A method in which a signal is applied to a recording head having a recording head and ink is ejected in accordance with the signal to perform recording, or thermal energy corresponding to the recording signal is applied to ink in a room of the recording head using, for example, a heating heater.
And recording by ejecting ink with the energy. For example, as described in Japanese Patent Application Laid-Open No. 54-59936, an ink jet recording method in which ink is ejected by utilizing a bubbling phenomenon of ink due to thermal energy is used for an opening (hereinafter referred to as an "orifice") where ink is ejected. This method is one of the mainstays of the current ink jet recording method because it is easy to achieve high integration and high density.

On the other hand, inks for use in these ink jet recording techniques have been reported and proposed with various compositions for the purpose of, for example, obtaining better quality images. Especially in recent years, copy paper, repo-
Detailed research and development from various aspects such as ink composition and ink physical properties, in order to perform good recording on plain paper commonly used in offices such as paper, notes, stationery, etc., and even on cloth. Has been made.

By the way, for example, ink used in an ink jet recording technique of a system in which thermal energy corresponding to a recording signal is applied to ink using a heating heater and the ink is ejected from an orifice to perform recording. One of the preferable characteristics is that, for example, a foreign substance (hereinafter referred to as "koge") is generated on the heating heater during printing.
Of no or little precipitation.
In other words, in the ink jet recording technology of a method of discharging ink using thermal energy, foreign substances gradually deposit on the surface of the heating head, resulting in a decrease in thermal conductivity to the ink, and sufficient generation of bubbles required for discharge. A phenomenon may occur in which the ink is not formed and the amount of ink required for normal printing is not discharged, or the ink is not discharged at all. That is, the ejection stability of the ink is reduced.

To cope with such technical problems, conventionally, for example, JP-A-3-160070 discloses an attempt to improve the generation of kogation by including an oxo anion in the ink. Japanese Patent Application Laid-Open No. Hei 7-334361 discloses a technique for suppressing the generation of kogation by including phytic acid and / or a salt thereof in an ink.
JP-A-8-80664 discloses a liquid composition containing a cationic substance and bishydroxyethyl sulfone (BHE).
A technique has been disclosed in which the use of S) prevents kogation on the heating head and improves the ejection durability.

[0006]

The inventors of the present invention have studied in detail the problem of kogation especially for an aqueous ink containing a water-soluble coloring material as a coloring material. As a result, the addition of BHES shows a significant improvement in kogation. However, it has been found that if the recording time is long, a kogation different from the conventional one may occur on the heating heater. When the kogation was examined, it was found that it contained sulfur, carbon, and inorganic metals such as calcium and iron. Although sulfur atoms may be present as sulfonic acid groups in water-soluble coloring materials, the generation of kogation containing sulfur atoms was hardly observed on the exothermic heater when BHES was not used. From this, it was assumed that the cause of this kogation was derived from BHES. This kogation is slightly smaller than the kogation generated on the heating heater by the ink to which BHES is not added, but for example, in order to satisfy the demand for higher definition for an ink jet recorded image, the configuration of the recording head of the ink jet recording apparatus is When the configuration is such that the amount of ink ejected from the orifice by one ejection operation is smaller than in the past, the amount of energy given to the ink by the heating heater is small, so that a fine kogation Even if ink adheres, it may cause a change in the ink ejection amount that affects the recording of high-definition images. To develop high-quality images stably, technological development to solve this is necessary. We came to the conclusion that it was necessary.

The present inventors have conducted further studies on such new technical problems, and as a result, have found that water-soluble coloring materials and BH
By adding at least one substance selected from dicarboxylic acid, dicarboxylic acid salt, tricarboxylic acid and tricarboxylic acid salt to the aqueous ink containing ES, the generation of kogation can be extremely effectively suppressed even over a long recording time. This led to the present invention.

SUMMARY OF THE INVENTION An object of the present invention is to provide an ink which is less likely to change the ink ejection performance of the heater when used for long-time ink jet recording by a method of ejecting ink using the heater. The point is to provide.

Another object of the present invention is to provide an image recording method capable of stably recording an image of excellent quality even after long-time recording.

Another object of the present invention is to provide an image recording apparatus capable of stably recording an image of excellent quality even when recording for a long time, an ink cartridge, an ink set, and a recording unit that can be used therein. Is to provide.

Another object of the present invention is to reduce the influence of changing the ink ejection performance on the heat generating heater when the method is used for long-time ink jet recording by a method of discharging ink using the heat generating heater. In addition, an object of the present invention is to provide an ink in which non-discharge from the orifice hardly occurs after printing is temporarily stopped even in various use environments or when the orifice is further miniaturized.

It is another object of the present invention to stably record an image of excellent quality even when recording for a long time, and to stably form or record a high-quality image even in various use environments. An object of the present invention is to provide an image recording method capable of stably exhibiting the effect even when the orifice is miniaturized for further improving the quality of an image.

It is another object of the present invention to stably form an image of excellent quality even after long-time recording, and to stably form a high-quality image even in various use environments. Further, an image recording apparatus capable of stably exerting its effect even when the orifice is miniaturized for further improving the quality of a recorded image, an ink cartridge, an ink set, and a recording unit that can be used for the image recording apparatus. To provide.

[0014]

According to one embodiment of the present invention, which can achieve the above object, there is provided an ink comprising at least one selected from dicarboxylic acids, salts of dicarboxylic acids, tricarboxylic acids and salts of tricarboxylic acids. A substance, bishydroxyethyl sulfone, and a water-soluble coloring material are contained in an aqueous medium.

Further, the ink as another embodiment of the present invention which can achieve the above-mentioned object is a dicarboxylic acid,
A salt of a dicarboxylic acid, at least one substance selected from tricarboxylic acids and salts of tricarboxylic acids, bishydroxyethyl sulfone, and a coloring material, wherein the dicarboxylic acid;
The total amount of dicarboxylic acid salt, tricarboxylic acid and tricarboxylic acid salt is 0.7% by weight or less based on the total weight of the ink.

The ink cartridge according to an embodiment of the present invention, which can achieve the above object, comprises at least one substance selected from the group consisting of dicarboxylic acids, salts of dicarboxylic acids, tricarboxylic acids and salts of tricarboxylic acids. It is characterized by comprising an ink storage section for storing ink containing ethyl sulfone and a water-soluble coloring material in an aqueous medium.

According to another embodiment of the present invention, there is provided an ink cartridge according to another embodiment of the present invention, comprising at least one substance selected from dicarboxylic acids, salts of dicarboxylic acids, tricarboxylic acids, and salts of tricarboxylic acids.
An ink containing section containing bishydroxyethyl sulfone and a colorant, wherein the total amount of dicarboxylic acid, dicarboxylic acid salt, tricarboxylic acid and tricarboxylic acid salt is 0.7% or less based on the total weight of the ink; It is characterized by having.

The recording unit according to an embodiment of the present invention, which can achieve the above object, comprises at least one substance selected from dicarboxylic acids, salts of dicarboxylic acids, tricarboxylic acids, and salts of tricarboxylic acids. An ink storage unit that stores an ink containing ethyl sulfone and a water-soluble coloring material in an aqueous medium, a unit that applies the recording ink to a recording medium, and a unit that supplies the ink to the unit. It is characterized by having.

According to another embodiment of the present invention, which can achieve the above object, the recording unit comprises at least one substance selected from dicarboxylic acids, salts of dicarboxylic acids, tricarboxylic acids, and salts of tricarboxylic acids; Hydroxyethyl sulfone, and a coloring material, wherein the total amount of the dicarboxylic acid, dicarboxylic acid salt, tricarboxylic acid and tricarboxylic acid salt is 0.7% based on the total weight of the ink.
An ink storage section containing the following ink, means for applying the recording ink to a recording medium, and means for supplying the ink to the means are provided.

The ink set according to an embodiment of the present invention, which can achieve the above object, comprises at least one substance selected from dicarboxylic acids, salts of dicarboxylic acids, tricarboxylic acids, and salts of tricarboxylic acids. An ink set in which ethyl sulfone, an ink containing a water-soluble first coloring material in an aqueous medium, and an ink containing a second coloring material, wherein the first and second coloring materials are 1 each selected from yellow, magenta, cyan, black, red, blue and green
It is characterized by two color materials.

The image recording method according to one embodiment of the present invention which can achieve the above object includes a dicarboxylic acid,
A step of applying an ink containing at least one substance selected from a dicarboxylic acid salt, a tricarboxylic acid and a tricarboxylic acid salt, bishydroxyethyl sulfone, and a water-soluble coloring material in an aqueous medium to an image forming area of a recording medium. It is characterized by having.

The image recording method according to another embodiment of the present invention capable of achieving the above object includes a method of recording at least one substance selected from dicarboxylic acids, salts of dicarboxylic acids, tricarboxylic acids, and salts of tricarboxylic acids. Bishydroxyethyl sulfone, and a coloring material, wherein the total amount of the dicarboxylic acid, the salt of the dicarboxylic acid, the tricarboxylic acid and the salt of the tricarboxylic acid is 0.7% based on the total weight of the ink.
% Of the ink to be applied to the image forming area of the recording medium.

An image recording apparatus according to an embodiment of the present invention which can achieve the above object includes a dicarboxylic acid,
A dicarboxylic acid salt, at least one substance selected from tricarboxylic acids and tricarboxylic acid salts, bishydroxyethyl sulfone, and an ink containing section containing an ink containing a water-soluble coloring material in an aqueous medium; A recording unit having means for applying the recording ink to the recording medium, and a means for supplying the ink to the recording medium; and a means for applying the recording ink to the recording medium in response to a recording signal. Means is provided.

An image recording apparatus according to another embodiment of the present invention, which can achieve the above-mentioned object, comprises at least one substance selected from dicarboxylic acids, salts of dicarboxylic acids, tricarboxylic acids, and salts of tricarboxylic acids. Wherein the total amount of the dicarboxylic acid, the salt of the dicarboxylic acid, the tricarboxylic acid and the salt of the tricarboxylic acid is 0.7% based on the total weight of the ink.
An ink storage unit that stores the following ink, a unit that applies the ink to a recording medium, and a recording unit that includes a unit that supplies the ink to the unit, and a recording unit that responds to a recording signal. It is characterized by comprising means for operating means for applying recording ink to a recording medium.

According to each of the above embodiments, the change in the ink ejection performance is small even when the ink is ejected for a long time.
An image of excellent quality can be stably recorded for a long time.

The image recording method according to one embodiment of the present invention which can achieve the above object includes a dicarboxylic acid,
A dicarboxylic acid, at least one substance selected from tricarboxylic acids and salts of tricarboxylic acids, bishydroxyethyl sulfone, urea and a water-soluble coloring material contained in an aqueous medium, the dicarboxylic acid, a salt of dicarboxylic acid, tricarboxylic acid and An ink storage unit for storing an ink in which the total amount of the salt of tricarboxylic acid is 0.7% or less based on the total weight of the ink; and a means for discharging the recording ink from an orifice to a recording medium. A recording unit comprising: a recording head; a unit for supplying the ink to the recording head, wherein the recording head is configured to be able to eject 0.1 to 40 picoliters of ink from the orifice in one ejection operation; Means for operating the recording unit in response to a recording signal. It characterized by having a step of adhering the region.

An image recording apparatus according to an embodiment of the present invention which can achieve the above object includes a dicarboxylic acid,
A dicarboxylic acid salt, at least one substance selected from tricarboxylic acids and tricarboxylic acid salts, bishydroxyethyl sulfone, urea and a water-soluble coloring material in an aqueous medium, wherein the dicarboxylic acid, dicarboxylic acid salt, tricarboxylic acid And an ink storage unit for storing an ink in which the total amount of salts of tricarboxylic acid is 0.7% or less based on the total weight of the ink, and means for discharging the recording ink from an orifice to a recording medium. A recording unit, comprising: a recording head for supplying the ink to the recording head, wherein the recording head is capable of discharging 0.1 to 40 picoliters of ink from an orifice in a single discharging operation; And means for operating the recording unit in response to a recording signal.

The recording unit according to an embodiment of the present invention that can achieve the above object includes a dicarboxylic acid,
A dicarboxylic acid salt, at least one substance selected from tricarboxylic acids and tricarboxylic acid salts, bishydroxyethyl sulfone, urea and a water-soluble coloring material in an aqueous medium, wherein the dicarboxylic acid, dicarboxylic acid salt, tricarboxylic acid And an ink storage unit for storing an ink in which the total amount of salts of tricarboxylic acid is 0.7% or less based on the total weight of the ink, and means for discharging the recording ink from an orifice to a recording medium. And a means for supplying the ink to the recording head, wherein the recording head is configured to be able to eject 0.1 to 40 picoliters of ink from the orifice in one ejection operation. And

According to each of the above-described embodiments, and according to each of the above-described embodiments, there is little change in ink discharge performance even after long-time ink discharge, and further, in various use environments or when the orifice is smaller. Even in the case of further miniaturization, clogging of the orifice after the temporary suspension of recording is unlikely to occur, and a higher quality image can be recorded extremely stably.

(Function) Regarding each embodiment of the present invention described above, a water-soluble coloring material and B
When at least one substance selected from dicarboxylic acid, salt of dicarboxylic acid, tricarboxylic acid and salt of tricarboxylic acid is contained in the aqueous ink containing HES, it is not clear why ink ejection stability is increased. The nature of the kogation generated on the heater is changed by the addition of the substance, and even if it is deposited on the heating heater, the adhesion to the heating heater is weak. It is thought that it is done.

[0031]

Next, the present invention will be described in more detail with reference to preferred embodiments.

(First Embodiment) The ink according to the first embodiment of the present invention comprises at least one substance selected from dicarboxylic acids, salts of dicarboxylic acids, tricarboxylic acids and salts of tricarboxylic acids, BHES, and aqueous solution. Coloring material is contained in the aqueous medium.

(BHES / Amount) BHES has a structure represented by the following structural formula (I), and a commercially available product synthesized by a conventionally known method can be used.

[0034]

[Outside 1]

The content of BHES in the ink is, for example, 0.1 to 30% by weight, particularly 1 to 30% by weight based on the total weight of the ink.
Preferably, it is about 20% by weight. With such a range, it is possible to more effectively suppress kogation on the heating heater, for example, kogation derived from the coloring material in the ink.

(Dicarboxylic acid, salt of dicarboxylic acid, salt of tricarboxylic acid and salt of tricarboxylic acid) Specific examples of dicarboxylic acid, salt of dicarboxylic acid, tricarboxylic acid and salt of tricarboxylic acid are described below. Specific examples of dicarboxylic acids include, for example, succinic acid, maleic acid and phthalic acid. Specific examples of tricarboxylic acids include, for example, citric acid. Further, examples of the salts of these dicarboxylic acids and tricarboxylic acids include salts of metals such as sodium. In particular, when at least one of citric acid and sodium citrate is contained in an ink containing BHES and a water-soluble coloring material, generation of kogation on the heating heater is strongly suppressed, and under normal recording conditions. In this case, the heating heater is not broken, and can be used very favorably for further improving the ejection stability.

The content of such a substance in the ink is preferably 0.0001 to 0.7% by weight, more preferably 0.002 to 0.5% by weight, based on the total weight of the ink. By setting it within this range, more excellent ejection stability can be obtained.

(Coloring material / content thereof) The coloring material is not particularly limited as long as it is water-soluble. For example, conventionally known water-soluble dyes such as water-soluble anionic dyes and direct dyes , An acid dye, a reactive dye, and the like. The content of the dye in the ink is preferably, for example, 0.5 to 15% by weight, particularly preferably 1 to 12% by weight based on the total weight of the ink, in consideration of the density of the recorded image and the ejection characteristics of the ink. .

(Aqueous Medium) The aqueous medium holds the above-mentioned substance selected from dicarboxylic acids, salts of dicarboxylic acids, tricarboxylic acids and salts of tricarboxylic acids, BHES, and a water-soluble coloring material in a dissolved state. It is intended to be configured as. The aqueous medium preferably contains at least water as a component, and a water-soluble organic solvent may be mixed to increase the solubility of various components of the ink or to adjust various characteristics of the ink.
The ratio of water to the total weight of the ink is, for example, 20 to
It is preferably 95% by weight, preferably 40 to 95% by weight, more preferably 60 to 95% by weight.

(Specific Examples of Water-Soluble Dyes) Examples of the water-soluble dyes containing an anionic group which can be used for the coloring material of the ink according to the present embodiment include the following.

(Black Ink) Examples of dyes used for black ink include C.I. I. Direct Black 17, C.I. I. Direct Black 19, C.I. I.
Direct Black 22, C.I. I. Direct Black 31, C.I. I. Direct Black 32, C.I. I. Direct Black 51, C.I. I. Direct Black 6
2, C.I. I. Direct Black 71, C.I. I. Direct Black 74, C.I. I. Direct black 11
2, C.I. I. Direct Black 113, C.I. I. Direct Black 154, C.I. I. Direct Black 1
68, C.I. I. Acid Black 2, C.I. I. Acid Black 48, C.I. I. Acid black 110, C.I.
I. Reactive Black 1, C.I. I. Reactive Black 8, C.I. I. Reactive black 12, C.I.
I. Reactive Black 13, C.I. I. Food black 1, C.I. I. Food Black 2 and the like.

(Yellow Ink) Examples of the dye used in the yellow ink include C.I. I. Acid Yellow 11, C.I. I. Acid Yellow 17, C.I. I. Acid Yellow 23, C.I. I. Acid Yellow 25,
C. I. Acid Yellow 29, C.I. I. Acid Yellow 42, C.I. I. Acid Yellow 49, C.I. I. Acid Yellow 61, C.I. I. Acid Yellow 71,
C. I. Direct Yellow 12, C.I. I. Direct Yellow 24, C.I. I. Direct Yellow 26, C.I.
I. Direct Yellow 44, C.I. I. Direct Yellow 86, C.I. I. Direct Yellow 87, C.I. I.
Direct Yellow 98, C.I. I. Direct Yellow 100, C.I. I. Direct Yellow 130, C.I. I.
Direct Yellow 142 and the like.

(Magenta Ink) As the dye used in the magenta ink, C.I. I. Acid Red 1, C.I.
I. Acid Red 6, C.I. I. Acid Red 8,
C. I. Acid Red 32, C.I. I. Acid Red 35, C.I. I. Acid Red 37, C.I. I. Acid Red 51, C.I. I. Acid Red 52, C.I. I. Acid Red 80, C.I. I. Acid Red 85, C.I.
I. Acid Red 87, C.I. I. Acid Red 9
2, C.I. I. Acid Red 94, C.I. I. Acid red 115, C.I. I. Acid Red 254, C.I. I.
Acid Red 289, C.I. I. Direct Red 1,
C. I. Direct Red 4, C.I. I. Direct Red 13, C.I. I. Direct Red 17, C.I. I. Direct Red 23, C.I. I. Direct Red 28,
C. I. Direct Red 31, C.I. I. Direct Red 62, C.I. I. Direct Red 79, C.I. I. Direct Red 81, C.I. I. Direct Red 83,
C. I. Direct Red 89, C.I. I. Direct Red 227, C.I. I. Direct Red 240, C.I.
I. Direct Red 242, C.I. I. Direct Red 243 and the like.

(Cyan Ink) As the dye used for the cyan ink, C.I. I. Acid Blue 9, C.I. I.
Acid Blue 22, C.I. I. Acid Blue 40,
C. I. Acid blue 59, C.I. I. Acid Blue 93, C.I. I. Acid blue 102, C.I. I. Acid blue 104, C.I. I. Acid blue 113, C.I.
I. Acid blue 117, C.I. I. Acid Blue 1
20, C.I. I. Direct Blue 6, C.I. I. Direct Blue 22, C.I. I. Direct Blue 25, C.I.
I. Direct Blue 71, C.I. I. Direct Blue 78, C.I. I. Direct Blue 86, C.I. I. Direct Blue 106, C.I. I. Direct Blue 199 and the like.

As the dye contained in the ink of the present invention, a dye having at least one --COOM group (M represents an alkali metal, ammonium or organic ammonium) in a molecule is preferably used. Specifically, for example, dyes represented by the following general formulas [II] to [V] are effectively used in the present invention.

[0046]

[Outside 2] [Wherein A and B represent a hydroxyl group or a hydrogen atom, C represents a hydrogen atom or SO ₃ M, and D represents SO ₃ M, respectively. ]

[0047]

[Outside 3] [In the formula, CuPc represents a copper phthalocyanine skeleton. G represents any of the following structural formulas (1) to (4);

[0048]

[Outside 4] Z represents NHCH ₂ CH ₂ OH, N (CH ₂ CH ₂ OH) ₂ or the like, and in the above formula (3), R and R ′ represent H or a lower alkyl group or the like. ]

[0049]

[Outside 5] [In the formula, J represents any of the following structural formulas (5) to (7);

[0050]

[Outside 6] L represents the following structural formula (8) or (9);

[0051]

[Outside 7] X represents any of the following structural formulas (10) to (12);

[0052]

[Outside 8] R ^{1 to} R ⁴ represent —H, a lower alkyl group or the like, and in the above structural formulas (5) to (12), B represents —H or —COOH; W represents —H, —CN, an amide group, a pyridinium group. Or -COO
H, m is a number from 2 to 8, Z is an alkoxy group, -OH,
Alkylamino group or -NH ₂ other, Y is -H, -Cl
Or -CN, E is a -Cl or -CN, R ⁵ is -H,
Represents a lower alkyl group or the like. ]

[0053]

[Outside 9] [Wherein J represents the following structural formula (13);

[0054]

[Outside 10] L represents the following structural formula (14) or (15);

[0055]

[Outside 11] X represents any of the following structural formulas (16) to (18);

[0056]

[Outside 12] R ₁ and R ₂ represent —H or a lower alkyl group, and in the above structural formulas (16) to (18), Z represents an alkoxy group, —O
H, an alkyl amino group or -NH ₂ and the like, Y is -H, -
E represents Cl or -CN, and E represents -Cl or -CN. ]

(Relationship between Coloring Material and Ink pH) When the above coloring material, particularly a water-soluble coloring material containing -COOM in a molecule, is contained in the ink, the pH of the ink is adjusted to 8 to 12,
In particular, it is preferable to adjust to about 9 to 11. That is, by setting the pH of the ink within this range, the solubility of the coloring material in the aqueous medium is further improved, and a change in characteristics of the ink during storage can be suppressed. By setting the pH of the ink within the above range, the occurrence of kogation on the heating heater is extremely strongly suppressed. The present inventors have found that when the pH of an ink containing a water-soluble coloring material and BHES is within the above range, generation of kogation on the heating heater is extremely effectively suppressed. The synergistic effect of adding at least one compound of an acid, a salt of a dicarboxylic acid, a salt of a tricarboxylic acid and a salt of a tricarboxylic acid to the ink and adjusting the pH of the ink has a strong effect of suppressing kogation on the heating heater. Is achieved. Furthermore, when the pH is adjusted to be within the above range, the dissociation of the carboxylic acid proceeds in the ink, so that the content of the carboxylic acid, the salt of the dicarboxylic acid, the salt of the tricarboxylic acid and the salt of the tricarboxylic acid in the ink. In the above range, a sufficient effect can be obtained even with a small amount.

(Gold-Containing Dyes) In recent years, proposals have been made to apply ink jet recording technology to dyeing fabrics. As a result of the present inventors' research so far, as a water-soluble coloring material to be contained in the ink used for dyeing the fabric, considering the adhesion to the fabric and the strong light resistance required for the fabric, chromium It has been found that gold-containing dyes containing chromium or cobalt in the molecule can be suitably used. Further, the present inventors have further studied these coloring materials. As a result, the metal ions in the molecule are liberated in the ink to easily form kogation on the heat generating heater. It has been found that it is necessary to prepare an extremely delicate ink in order to secure the ink ejection performance. However, according to the invention of the present embodiment, even with an ink employing such a coloring material, generation of kogation on the heating heater can be effectively suppressed, and ejection stability can be improved. Further, as a coloring material used in inks for ink jet recording in the related art, it is possible to greatly expand the application range of coloring materials whose use is limited.

Here, specific examples of the gold-containing dye which can be used as the coloring material of the ink according to this embodiment include the following coloring materials.

CI Acid Yellow 59, 121, 1
51, 158, 194, 204, 207, 232, 23
5, 241

CI Acid Orange 142, 144,
166, 168

CI Acid Red 215, 296, 3
15, 357, 359, 362, 399

CI Acid Violet 90 (see the following structural formula (VI)), 92 (see the following structural formula (VII)), 121,

[0064]

[Outside 13]

[0065]

[Outside 14]

CI Acid Blue 167, 193 (see the following structural formula), 229, 284, 296, 300, 3
35, 338, 342

[0067]

[Outside 15]

CI Acid Brown 19, 282, 2
83, 289, 298, 355, 357, 365, 41
3,415

CI Acid Black 52, 52: 1
(See structural formula IX below), 60, 99, 107, 155,
188, 194, 222

[0070]

[Outside 16]

CI Acid Green 73, 104, 1
08

(Regarding Gold-Containing Dye and pH of Ink) When the above-described gold-containing dye is used as a coloring material in the ink according to the present embodiment, the pH of the ink is adjusted to 3.5 to 7.5, particularly to 3 It is preferable to adjust the value to 0.5 to 6.5. That is, by setting the pH of the ink within this range, the ion dissociation of the dye in the ink can be suppressed, and the occurrence of kogation on the heating heater can be further suppressed. Further, as another example of a coloring material that can be used for the ink according to the present embodiment, for example, the dye structure itself is inferior in heat resistance, and the ink structure is used for ink jet recording using thermal energy in order to easily generate kogation and the like. Dyes of the type described above may also be used. A specific example of such a color material is CI Acid Yellow 79, for example.

(Specific Examples of Water-Soluble Organic Solvent) Examples of the water-soluble organic solvent which may be contained in the aqueous medium of the ink according to the present embodiment include, for example, methanol, ethanol, and the like.
Monohydric alcohols such as isopropyl alcohol, ketones or keto alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; diethylene glycol, triethylene glycol;
Tetraethylene glycol, dipropylene glycol,
Tripropylene glycol, polyethylene glycol,
An oxyethylene or oxypropylene addition polymer such as polypropylene glycol; an alkylene group such as ethylene glycol, propylene glycol, trimethylene glycol, butylene glycol, or hexylene glycol having 2
Alkylene glycols containing up to 6 carbon atoms; 1,
Triols such as 2,6-hexanetriol; thiodiglycol; glycerin; lower polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, and triethylene glycol monomethyl (or ethyl) ether Alkyl ethers; lower dialkyl ethers of polyhydric alcohols such as triethylene glycol dimethyl (or ethyl) ether and tetraethylene glycol dimethyl (or ethyl) ether; The content of the water-soluble organic solvent is generally in the range of 0 to 40%, preferably 2 to 30% by weight based on the total weight of the ink. When the above medium is used in combination, it can be used alone or as a mixture. Preferred water-soluble organic solvents are monohydric alcohols, ketones, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, thiodiglycol, and the like. Glycol, propylene glycol, dipropylene glycol, tripropylene glycol and derivatives thereof (among others, alkyl ethers thereof).

(Other Components) In the ink according to the present embodiment, various other defoaming agents, viscosity adjusters, surface tension adjusters, pH adjusters, and the like may be used as long as the effects of the ink are not impaired.
A regulator and the like may be added as needed.

(Second Embodiment / Addition of Urea) As an ink according to the second embodiment of the present invention, there is an ink containing urea further contained in the ink according to the above embodiment. According to the ink according to the second embodiment,
In addition to the effects achieved by the ink according to the first embodiment, it is possible to provide the ink with improved re-discharge properties as compared with the related art. Here, the re-discharge property refers to an operation of discharging ink from the orifice again after recording is temporarily stopped. The present inventors have found that some of the water-soluble inks containing a water-soluble coloring material, based on previous studies, have ink that faces the orifice during the suspension of recording and solidifies the orifice completely or partially. In some cases, it may be impossible to re-discharge the ink, or it may not be possible to discharge a predetermined amount of ink in the correct direction. It has been found that the use of ink-jet printing apparatuses is diversified in terms of use conditions in accordance with the miniaturization of orifices and the spread of ink-jet printing apparatuses, especially when the ink-jet printing apparatus is used in a low-temperature environment. However, by further containing urea in the ink according to the present embodiment, it is possible to stabilize the re-discharge property even under the above-described conditions, in addition to the effect exhibited by the ink according to the first embodiment. The effect is also obtained.

By the way, it is not clear why the above-mentioned effect is achieved by adopting such a configuration. However, BHES in the ink is solid at normal temperature, and when the proportion of the BHES in the aqueous medium exceeds 20 (wt?)%, Since the ink tends to precipitate in the form of a wax, it is considered that this phenomenon starts with the evaporation of water from the orifice from a microscopic point of view even in the ink facing the orifice. On the other hand, urea greatly enhances the affinity between water and the water-soluble dye.
By coexisting HES and urea, in the ink facing the orifice, the synergistic effect of the effect of suppressing the evaporation of water in the ink from the orifice due to the precipitation of BHES and the effect of suppressing the rapid rise in the dye concentration of the ink near the orifice It is thought that it depends on. In this embodiment, the amount of urea is preferably 0.1 to 20% by weight, particularly preferably 0.1 to 15% by weight, based on the total weight of the ink, and the total amount of urea and BHES based on the total weight of the ink. The amount is 0.2-
It is preferably 30% by weight, particularly preferably 0.6 to 25% by weight.

(Apparatus) Next, an ink jet recording apparatus which can use the above-described ink and an image recording method using the same will be described.

(Head Configuration) FIG. 1 shows an orifice portion from which ink is ejected in one embodiment of a head which constitutes one of the main parts of an ink jet recording apparatus of the type which uses thermal energy to eject ink. It is a schematic sectional drawing of the direction which crosses vertically. FIG. 2 is a sectional view taken along line AA of FIG. 1 and 2, a head 13 is made of a glass, ceramic or plastic plate having a groove 14 through which ink passes, and a heating head 15 used for thermal recording (the head is shown in the drawings, but is not limited to this). Is not obtained). The heating head 15 includes a protective film 16 made of silicon oxide or the like, and the aluminum electrode 1.
7-1, 17-2, heating resistor layer 18 formed of nichrome or the like, heat storage layer 19, substrate 2 having good heat dissipation such as alumina
It is 0. The ink 21 reaches a discharge orifice (fine hole) 22 and forms a meniscus 23 at a predetermined pressure P. When an electric signal is applied to the electrodes 17-1 and 17-2, the area indicated by “n” of the heating head 15 rapidly generates heat, and bubbles are generated in the ink 21 in contact with the area. The ink 23 is ejected from the orifice 22 and flies toward the recording medium (for example, paper) 25, adheres to the image recording area of the recording medium 25, and an image is recorded.

FIG. 3 is an external view of a multi-head in which many heads shown in FIG. 1 are arranged. The multi-head is manufactured by closely contacting a glass plate 27 having a multi-groove 26 and a heating head 28 similar to that described with reference to FIG.

In the above-described head configuration, the size of the orifice is not particularly limited, and may be appropriately set according to desired image quality. However, with the recent demand for higher image quality, miniaturization of the orifice size has been studied. Specifically, for example, miniaturization of the orifice such that the amount of ink ejected from the orifice by one ejection operation is 0.1 to 40 picoliters (pl), particularly 0.1 to 30 pl has been studied. In the orifice of such a size, it is one of the technical goals particularly preferable to form a high-quality image by stably re-discharging the ink after the recording is temporarily stopped. The inks according to the various embodiments of the present invention described above, particularly the inks according to the second embodiment, can be cited as one of extremely effective techniques capable of overcoming this technical goal.

Even if the orifice is not miniaturized as described above, the use environment is diversified with the spread of the ink jet recording apparatus, specifically, for example, the environment where the ambient temperature is 5 ° C. or less (for example, cold) When the ink jet recording apparatus is used under indoor or outdoor conditions where heating is not effective, ink may not be ejected due to clogging of the orifice as described above. Therefore, this point is also one of the important technical goals to be overcome. The ink according to each of the above embodiments, particularly the ink according to the second embodiment, can be cited as one of the extremely effective techniques capable of overcoming this technical goal.

(Ink Jet Recording Apparatus) An example of an ink jet recording apparatus incorporating the head according to FIG. 4 is shown. In FIG. 4, reference numeral 61 denotes a blade as a wiping member, one end of which is held by a blade holding member to become a fixed end, and forms a cantilever. The blade 61 is disposed at a position adjacent to a recording area of the recording head, and in this example, is held in a form protruding into the movement path of the recording head. Reference numeral 62 denotes a cap, which is provided at a home position adjacent to the blade 61, and has a configuration in which the cap moves in a direction perpendicular to the direction in which the print head moves and comes into contact with the ejection port surface to perform capping. Further, an absorber 63 is provided adjacent to the blade 61 and, like the blade 61, is held in a form protruding into the movement path of the recording head. The blade 61, the cap 62, and the absorber 63 constitute an ejection recovery unit 64, and the blade 61 and the absorber 63 remove water, dust, and the like from the ink ejection port surface. Reference numeral 65 denotes a recording head which has ejection energy generating means and performs recording by discharging ink on a fabric facing the ejection port surface provided with the ejection port, and 66 carries the recording head 65 and moves the recording head 65. Carriage. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected to a belt 69 driven by a motor 68 (not shown). As a result, the carriage 66 can move along the guide shaft 67, and the recording head 65 can move the recording area and the adjacent area. Reference numeral 51 denotes a paper feed unit for inserting recording paper, and 52 denotes a paper feed roller driven by a motor (not shown). With these configurations, the recording paper is fed to a position facing the discharge port surface of the recording head, and is discharged to a paper discharge unit provided with a discharge roller 53 as the recording proceeds.

In the above configuration, when the recording head 65 returns to the home position at the end of recording or the like, the cap 62 of the head recovery unit 64 is retracted from the moving path of the recording head 65, but the blade 61 projects into the moving path. I have. As a result, the ejection port surface of the recording head 65 is wiped. When capping is performed with the cap 62 in contact with the ejection surface of the recording head 65, the cap 62 moves so as to protrude into the movement path of the recording head.

When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are at the same position as the position at the time of wiping described above. As a result, the ejection port surface of the recording head 65 is also wiped during this movement. The above-described movement of the print head to the home position is performed not only at the end of printing and at the time of ejection recovery, but also at predetermined intervals while the print head moves through the printing area for printing to the home position adjacent to the printing area. Then, the wiping is performed along with this movement.

(Ink Cartridge) FIG. 5 is a diagram showing an example of an ink cartridge containing ink supplied to the head via an ink supply member, for example, a tube. Here, reference numeral 40 denotes an ink storage portion that stores the supply ink, for example, an ink bag, and a rubber stopper 42 is provided at the tip thereof. By inserting a needle (not shown) into the stopper 42, the ink in the ink bag 40 can be supplied to the head. Reference numeral 44 denotes an absorber for receiving the waste ink. It is preferable for the present invention that the ink container has a surface in contact with the ink made of polyolefin, particularly polyethylene. The ink jet recording apparatus used in the present invention is not limited to the one in which the head and the ink cartridge are separated as described above, and may be suitably used in an integrated one as shown in FIG.

(Recording Unit) In FIG. 6, reference numeral 70 denotes a recording unit, in which an ink storage portion for storing ink, for example, an ink absorber is stored, and the ink in the ink absorber is stored. The ink is ejected as ink droplets from a head 71 having a plurality of orifices. As the material of the ink absorber, it is preferable for the present invention to use polyurethane. Reference numeral 72 denotes an atmosphere communication port for communicating the inside of the recording unit with the atmosphere. The recording unit 70 is used in place of the recording head shown in FIG. 4, and is detachable from the carriage 66.

(Ink Set) By the way, the inks according to the various embodiments described above can be, for example, yellow, magenta, cyan, red, green, blue or black inks by selecting a color material. Each of the inks may be used alone for image recording. Alternatively, an ink set that can be suitably used for forming a color image can be provided by combining two or more different color inks. Also, by combining two or more inks of the same color and containing different color materials, or by combining two or more inks of the same color but having different densities, it is suitable for forming a high gradation image. An ink set that can be used can be provided. When an image is formed using these ink sets, for example, a recording apparatus in which four recording heads shown in FIG. 3 are arranged on a carriage can be used. FIG. 8 shows one embodiment, in which 86, 87, 88 and 89 are respectively yellow,
This is a recording head for ejecting magenta, cyan, and black inks. The print head is disposed in the above-described printing apparatus, and discharges ink of each color according to a print signal. FIG. 8 shows an example in which four recording heads are used. However, the present invention is not limited to this. For example, as shown in FIG. There is also an embodiment in which image recording is performed.

The case where the ink according to the present invention is used in an apparatus for applying thermal energy corresponding to a recording signal to ink and discharging ink from the thermal energy and an image recording method using the apparatus has been described. . However, the ink of the present invention can also be used in an ink jet recording apparatus of a type in which ink is ejected by mechanical energy and an image recording method using the same, whereby the same excellent effects can be obtained.

[0089]

Examples (Examples 1 to 14) Inks having the compositions shown in Table 1 below were prepared. That is, each material is mixed, stirred for 2 hours, adjusted to a desired pH with 4N-lithium hydroxide (LiOH), and then pressure-filtered with a membrane filter having a pore size of 0.2 μm to obtain each recording ink. Obtained. In the table below, FB2 is C.I. I. Food Black 2, DY8
6 is C.I. I. Abbreviation for direct yellow 86.

Compound 1 is represented by the structural formula (V):
“L” is the structural formula (15), and “X” is the structural formula (1)
6), “R1” and “R2” are dyes having a structure represented by a hydrogen atom, —NH2.

[0091]

[Table 1]

Reference Examples 1 to 3 Inks having the compositions shown in Table 2 below were prepared in the same manner as the inks prepared in the examples.

[0093]

[Table 2]

The inks of Examples 1 to 14 and Reference Examples 1 to 3 were prepared by using an ink jet recording head configured so that the amount of ink ejected from one nozzle in one ejection operation was 20 pl. × 108 ejections were made, and then the following items were evaluated. The results are shown in Table 3 below.

[Evaluation Items] (1) Droplet Size (Discharge Amount Change) The ink discharge amount per nozzle after 6 × 10 ⁸ discharges was measured and compared with the initial ink discharge amount of the nozzle. ：: The ink ejection amount after the ejection test was 95 compared to the initial stage.
%that's all. Δ: The ink ejection amount after the ejection test was 80 compared to the initial stage.
% To less than 95%. ×: The ink ejection amount after the ejection test was 80 compared to the initial stage.
%Less than.

(2) Heater Surface Observation The head after ejecting 6 × 10 ⁸ shots was disassembled, and the heater surface was observed with an optical microscope. ：: Almost no kogation is observed. ：: Some kogation is observed, but the level does not affect ejection. Δ: Many kogation are observed.

(3) Deterioration of image (landing accuracy) After ejection of 6 × 10 ⁸ shots, coated paper (trade name: HR101;
A straight line having a resolution of 600 dpi was recorded on a Canon Inc.), and the positional relationship (landing position) of each dot was taken into a video image, and the deviation from the lattice point of 600 dpi (± μ).
m) was measured. ：: Landing accuracy is less than ± 10 μm. Δ: The landing accuracy is ± 10 μm or more and less than 15 μm. ×: The landing accuracy is ± 15 μm or more.

[0098]

[Table 3]

From the results shown in Table 3 above, for example, when an ink jet recording head configured to reduce the amount of ink ejected from one nozzle by one ejection operation is used, for example, 6
It was found that the generation of kogation on the surface of the heating heater was effectively suppressed even after severe recording such as ejection of × 108.

From the results of Examples 1 to 3 and 12 and Reference Example 1, and the results of Examples 4 to 5 and 13 and Reference Example 2, bishydroxyethyl sulfone and dicarboxylic acid, salts thereof, and tricarboxylic acid and salts thereof were used. The combined use with at least one selected one can further improve the three of the change in the ejection amount, the kogation property, and the landing accuracy. In particular, the combined use of bishydroxyethyl sulfone and citric acid could further suppress the generation of kogation on the heater surface.

(Examples 15 to 20) The above Examples 6 to 11
Inks having the same composition as in Examples 15 to 20 were prepared.
Ink. An ink jet printer of the type that discharges ink by applying thermal energy to the ink by a heating heater using each ink (product name: BJ
130; manufactured by Canon Inc.), printing was performed on a commercially available copy sheet at a driving frequency of 2 kHz, and the re-discharge property of the ink when the discharge operation was performed again after the recording was temporarily stopped was evaluated. The printer head used here was configured so that the amount of ink ejected from one nozzle in one ejection operation was about 60 pl. The evaluation conditions were as follows. After printing each of the above inks for 1 minute continuously in an environment of room temperature 0 ° C. and humidity 25 ± 5% using the above printer, printing was stopped for 30 seconds, When the alphanumeric characters were printed again, the printing defects such as blurred or missing characters were observed. At this time, the head temperature was 35 ± 5 ° C. The results are shown in Table 4 below. The evaluation criteria are as follows. ：: No blurring or chipping is recognized from the first character at the time of re-recording. Δ: Part of the first character at the time of re-recording is faint or missing. X: The first character at the time of re-recording cannot be printed at all.

[0102]

[Table 4]

Examples 21 to 24 Inks having the compositions shown in Table 5 below were prepared in the same manner as the inks of Examples 1 to 14.

[0104]

[Table 5]

Reference Examples 4 to 7 Inks having the compositions shown in Table 6 below were prepared in the same manner as the inks of Examples 1 to 14.

[0106]

[Table 6]

For the inks of Examples 21 to 24 and Reference Examples 4 to 7, a bubble jet card printer (trade name:
Using a head for P-400CII (manufactured by Canon Inc.), kogation property, discharge stability, and presence / absence of heater disconnection were evaluated. The recording head used at this time ejects about 50 pl of ink in one ejection operation per nozzle. The results are shown in Table 7 below. The evaluation criteria are as follows.

(1) Kogation After continuous printing of 2 × 108 pulses was performed with 10 nozzles, when the head was disassembled and the heater surface was observed with an optical microscope, the kogation on the heater surface was determined based on the following criteria. evaluated. ：: No kogation on the heater surface was observed. C: Some kogation is observed on the edge of the heater. ×: kogation is observed on the entire surface of the heater.

(2) Ejection stability When continuous printing of 2 × 108 pulses was performed with ten nozzles, the amount of ejected liquid and the decrease in ejection speed were measured and evaluated according to the following criteria. ：: No decrease in discharge amount occurs at all. Δ: The discharge amount after the durability decreased from 10% to less than 50% of the initial discharge amount. X: The discharge amount after the durability was reduced by 50% or more with respect to the initial discharge amount, or the discharge became impossible.

(3) Disconnection of Heater When continuous printing of 5 × 107 pulses was performed with 16 nozzles, the degree of disconnection of the heater was evaluated according to the following criteria. ：: No disconnection was observed. X: Disconnection was observed in one or more nozzles.

[0111]

[Table 7]

[0112]

As described above, according to the embodiment of the present invention, the occurrence of kogation on the heating heater can be effectively prevented even for a long time recording, and the ejection stability can be improved. Further, by improving the ejection stability, it is possible to stably record a high-quality image.

In addition, the occurrence of kogation on the heating heater can be effectively prevented, the ejection stability can be improved, and the re-ejection property of the ink after the recording is temporarily stopped can also be improved.

Further, high quality images can be stably recorded on various recording media, and high quality images can be stably formed even in various use environments. In addition, even if the image quality is improved by miniaturizing the orifice to further improve the quality of the recorded image, the kogation on the heating heater is suppressed, and the re-discharge property of the ink is also improved, so that high definition is achieved. Stable images can be stably recorded.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view showing one embodiment of a head of an ink jet recording apparatus.

FIG. 2 is a sectional view taken along line AA of FIG.

FIG. 3 is a schematic explanatory diagram of a multi-head.

FIG. 4 is a schematic perspective view showing one embodiment of an ink jet recording apparatus.

FIG. 5 is a longitudinal sectional view showing one embodiment of an ink cartridge.

FIG. 6 is a schematic perspective view showing another example of the configuration of the ink jet recording head.

FIG. 7 is a schematic explanatory view of a recording head to which four ink cartridges are attached.

FIG. 8 is a schematic explanatory view showing a configuration in which four recording heads are arranged on a carriage.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 13 Head 14 Ink groove 15 Heating head 16 Protective film 17-1, 17-2 Electrode 18 Heating resistor tank 19 Heat storage layer 20 Substrate 21 Ink 22 Discharge orifice 23 Meniscus 24 Ink droplet 25 Recording material 26 Multi-groove 27 Glass plate 40 Ink bag 42 Plug 44 Ink absorber 45 Ink cartridge 51 Paper feeder 52 Paper feed roller 53 Paper discharge roller 61 Blade 62 Cap 63 Ink absorber 64 Discharge recovery unit 65 Recording head 66 Carrier 67 Guide shaft 68 Motor 69 Belt 70 Recording unit 71 head part 72 atmosphere communication port 80 ink flow path 81 orifice plate 82 diaphragm 83 piezoelectric element 84 substrate 85 discharge port 86, 87, 88, 89 recording head

 ──────────────────────────────────────────────────続 き Continued on front page (72) Inventor Yutaka Kurabayashi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Mikifumi Ogasawara 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside the corporation

Claims (28)

[Claims] 1. An aqueous medium containing at least one substance selected from dicarboxylic acids, salts of dicarboxylic acids, tricarboxylic acids and salts of tricarboxylic acids, bishydroxyethyl sulfone, and a water-soluble coloring material. ink. 2. The ink according to claim 2, wherein the total amount of the dicarboxylic acid, dicarboxylic acid salt, tricarboxylic acid and tricarboxylic acid salt in the ink is 0.7% or less based on the total weight of the ink. 3. An ink containing a dicarboxylic acid, a salt of a dicarboxylic acid, at least one substance selected from a tricarboxylic acid and a salt of a tricarboxylic acid, bishydroxyethyl sulfone, and a coloring material, wherein the ink contains An ink characterized in that the total amount of salts, tricarboxylic acids and salts of tricarboxylic acids is 0.7% or less based on the total weight of the ink. 4. The ink according to claim 1, wherein the substance is citric acid. 5. The ink according to claim 1, wherein the aqueous medium contains water. 6. The ink according to claim 1, wherein the aqueous medium contains water and a water-soluble organic solvent. 7. The ink of claim 1, wherein said ink further comprises urea.
The ink according to any one of the above. 8. The ink according to claim 1, wherein the coloring material is a dye having one or more —COOM (M represents an alkali metal or ammonium) in a molecule. 9. The ink according to claim 8, wherein the pH of the ink is 9.5 to 12. 10. The ink according to claim 1, wherein the coloring material is a water-soluble gold-containing dye. 11. The ink according to claim 10, wherein the pH of the ink is 3.5 to 7.5. 12. The ink according to claim 11, wherein the pH of the ink is 3.5 to 6.5. 13. An ink containing, in an aqueous medium, at least one substance selected from dicarboxylic acids, salts of dicarboxylic acids, tricarboxylic acids and salts of tricarboxylic acids, bishydroxyethyl sulfone, and a water-soluble coloring material. An ink cartridge characterized by comprising an ink storage section. 14. The ink cartridge according to claim 13, wherein the total amount of the dicarboxylic acid, dicarboxylic acid salt, tricarboxylic acid and tricarboxylic acid salt in the ink is 0.7% or less based on the total weight of the ink. 15. A composition comprising at least one substance selected from dicarboxylic acid, dicarboxylic acid salt, tricarboxylic acid and tricarboxylic acid salt, bishydroxyethyl sulfone, and a coloring material, wherein the dicarboxylic acid, dicarboxylic acid salt, tricarboxylic acid And an ink storage section containing an ink having a total amount of tricarboxylic acid salts of 0.7% or less based on the total weight of the ink. 16. An ink containing an aqueous medium containing at least one substance selected from dicarboxylic acid, a salt of dicarboxylic acid, tricarboxylic acid and a salt of tricarboxylic acid, bishydroxyethyl sulfone, and a water-soluble coloring material. 1. A recording unit comprising: an ink storage section; a means for applying the recording ink to a recording medium; 17. The recording unit according to claim 16, wherein the total amount of the dicarboxylic acid, dicarboxylic acid salt, tricarboxylic acid and tricarboxylic acid salt in the ink is 0.7% or less based on the total weight of the ink. 18. A composition comprising at least one substance selected from dicarboxylic acids, salts of dicarboxylic acids, tricarboxylic acids and salts of tricarboxylic acids, bishydroxyethyl sulfone, and coloring materials, wherein the dicarboxylic acids, salts of dicarboxylic acids, and tricarboxylic acids are used. And an ink container containing an ink in which the total amount of salts of tricarboxylic acid is 0.7% or less based on the total weight of the ink, means for applying the recording ink to a recording medium, and supplying the ink to the means A recording unit comprising means. 19. An ink comprising, in an aqueous medium, at least one substance selected from dicarboxylic acids, salts of dicarboxylic acids, tricarboxylic acids and salts of tricarboxylic acids, bishydroxyethyl sulfone, and a water-soluble first coloring material. And an ink containing a second color material, wherein the first and second color materials are respectively yellow, magenta, cyan, black, red, blue, and green. An ink set characterized by being one color material selected from the group consisting of: 20. The ink set according to claim 19, wherein the total amount of the dicarboxylic acid, dicarboxylic acid salt, tricarboxylic acid and tricarboxylic acid salt in the ink is 0.7% or less based on the total weight of the ink. 21. A salt of dicarboxylic acid and dicarboxylic acid, comprising at least one substance selected from dicarboxylic acids, salts of dicarboxylic acids, tricarboxylic acids and salts of tricarboxylic acids, bishydroxyethyl sulfone, and a first coloring material. Wherein the total amount of tricarboxylic acid and the salt of tricarboxylic acid is 0.7% or less based on the total weight of the ink, and an ink containing a second coloring material, An ink set, wherein each of the second color materials is one color material selected from yellow, magenta, cyan, black, red, blue, and green. 22. A recording medium containing an ink containing, in an aqueous medium, at least one substance selected from dicarboxylic acids, salts of dicarboxylic acids, tricarboxylic acids, and salts of tricarboxylic acids, bishydroxyethyl sulfone, and a water-soluble coloring material. An image recording method comprising the step of applying the image to an image forming area. 23. A dicarboxylic acid, a salt of a dicarboxylic acid, at least one substance selected from a tricarboxylic acid and a salt of a tricarboxylic acid, bishydroxyethyl sulfone, and a coloring material, wherein the dicarboxylic acid, a salt of the dicarboxylic acid, and a tricarboxylic acid And a step of applying an ink having a total amount of a salt of tricarboxylic acid of 0.7% or less based on the total weight of the ink to an image forming area of a recording medium. 24. An aqueous medium containing at least one substance selected from dicarboxylic acids, salts of dicarboxylic acids, tricarboxylic acids and salts of tricarboxylic acids, bishydroxyethyl sulfone, and a water-soluble coloring material, The total amount of dicarboxylic acid salt, tricarboxylic acid and tricarboxylic acid salt is 0.7% based on the total weight of the ink.
An ink storage unit that stores the following ink, a unit that applies the ink to a recording medium, and a recording unit that includes a unit that supplies the ink to the unit, and a recording unit that responds to a recording signal. An image recording apparatus comprising: means for operating a means for applying recording ink to a recording medium. 25. Dicarboxylic acid, salt of dicarboxylic acid, at least one substance selected from tricarboxylic acid and salt of tricarboxylic acid, bishydroxyethyl sulfone, and coloring material, wherein the dicarboxylic acid, salt of dicarboxylic acid, tricarboxylic acid And an ink containing section containing an ink in which the total amount of salts of tricarboxylic acid is 0.7% or less based on the total weight of the ink, means for applying the ink to a recording medium, and An image recording apparatus, comprising: a recording unit including a unit for supplying ink; and a unit for operating a unit for applying the recording ink to a recording medium in response to a recording signal. 26. An aqueous medium containing at least one substance selected from dicarboxylic acids, salts of dicarboxylic acids, tricarboxylic acids and salts of tricarboxylic acids, bishydroxyethyl sulfone, urea and a water-soluble coloring material, The total amount of dicarboxylic acid salt, tricarboxylic acid and tricarboxylic acid salt is 0.7% based on the total weight of the ink.
An ink storage unit for storing the following ink, a recording head having means for discharging the recording ink from an orifice to a recording medium, and a means for supplying the ink to the recording head; An image in which the head includes a recording unit configured to be able to eject 0.1 to 40 picoliters of ink from the orifice in one ejection operation, and a unit that operates the recording unit in response to a recording signal. An image recording method, comprising a step of attaching the ink to an image recording area of a recording medium using a recording device. 27. An aqueous medium containing at least one substance selected from dicarboxylic acids, salts of dicarboxylic acids, tricarboxylic acids and salts of tricarboxylic acids, bishydroxyethyl sulfone, urea and a water-soluble coloring material, The total amount of dicarboxylic acid salt, tricarboxylic acid and tricarboxylic acid salt is 0.7% based on the total weight of the ink.
An ink storage unit for storing the following ink, a recording head having means for discharging the recording ink from an orifice to a recording medium, and a means for supplying the ink to the recording head; The head includes a recording unit configured to be able to eject 0.1 to 40 picoliters of ink from the orifice in one ejection operation, and means for operating the recording unit in response to a recording signal. An image recording apparatus characterized by the above-mentioned. 28. An aqueous medium containing at least one substance selected from dicarboxylic acids, salts of dicarboxylic acids, tricarboxylic acids and salts of tricarboxylic acids, bishydroxyethyl sulfone, urea and a water-soluble coloring material, The total amount of dicarboxylic acid salt, tricarboxylic acid and tricarboxylic acid salt is 0.7% based on the total weight of the ink.
An ink storage unit for storing the following ink, a recording head having means for discharging the recording ink from an orifice to a recording medium, and a means for supplying the ink to the recording head; A recording unit, wherein the head is configured to be able to eject 0.1 to 40 picoliters of ink from the orifice in one ejection operation.