JP2002235020A - Recording solution, recording solution cartridge, recorder, recording method and recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a recording solution having excellent discharge stability in high-speed printing and after long-term stop and improved color development, preventing blurring, exhibiting excellent characteristics as a color recording solution and to provide a recording solution cartridge, a recording method, a recorder and a recording medium. SOLUTION: This recording solution is obtained by formulating a recording solution containing a colorant to be dispersed or dissolved in water, water and a water-soluble organic solvent with an azo dye represented by formula 1 and a xanthene dye represented by formula 2 or an azo dye represented by formula 3 [R1, R3 and R4 are each H, an alkyl group or an aryl group; R2 is H or an alkyl group; M is a cation; (n) is an integer of 2-4; R21 to R24 are each H, a 1-4C alkyl group or a halogen; X1 and X2 are H, sulfonic acid group, sulfonamide group, carboxylic acid group or a carboxylic acid group- containing arylsulfonamide group; Y21 is SO3- or COO-]. The recording solution cartridge holds the recording solution. The recorder or recording method uses the recording solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a recording liquid, a recording liquid cartridge, a recording apparatus, a recording method, and a recording medium.
More specifically, it is used for aqueous writing implements, recorders, pen plotters, ink jet recordings, and the like.Especially in ink jet recording, it has good ejection stability at high speed printing, prevents bleeding on paper, and is a color recording liquid. , A recording liquid cartridge containing the recording liquid, a recording apparatus and a recording method capable of giving a robust image excellent in color tone and independent of a storage environment using the recording liquid, and the recording method. The present invention relates to a recording apparatus using a liquid or a recording medium used in a recording method.

[0002]

2. Description of the Related Art Ink-jet printers have advantages such as low noise and low running cost. Therefore, in recent years, ink-jet printers have rapidly spread and color printers capable of printing on plain paper have come to market. A recording liquid used in such a color printer is generally formed of a colorant dispersible or soluble in water, a wetting agent (polyhydric alcohol or ethers thereof) and water, and if necessary, a fungicide or the like. An additive is added.

However, it is not possible to obtain a color recording liquid which satisfies all required characteristics such as color reproducibility of an image, water resistance, moisture resistance, light resistance, image drying property, image bleeding, and ejection reliability. Extremely difficult. In particular, in the case of a color printer, even if the image quality is not degraded in a single color printing portion of yellow, magenta, and cyan, two colors of red, green, and blue are used.
The image quality is likely to be deteriorated in the color overlapping portion. In particular, when drying is performed without using a fixing device, the drying property is improved by increasing the permeability (Japanese Patent Laid-Open No. 55-2).
9546), which causes a disadvantage that the recording liquid significantly bleeds into the paper.

Further, it has been proposed to use a dialkyl sulfosuccinic acid as a surfactant to improve drying properties and prevent image quality deterioration (Japanese Patent Publication No. 60-23793).
Publication), the pixel diameter of the paper is significantly different, the image density is significantly reduced, and the activator is decomposed on the alkaline side,
There is a problem that the active effect is lost during storage.

Further, a recording liquid to which a strongly basic substance is added is disclosed (Japanese Patent Application Laid-Open No. 56-57862, etc.), but although it is effective for rosin-sized acidic paper, alkyl ketene dimer and alkenyl sulfo succinate are effective. There was no effect on paper using acid as a sizing agent. In addition, even with acidic paper, there is a problem that the effect is not exhibited in the two-color overlapping portion.

Further, a recording liquid containing a polyhydric alcohol derivative and pectin has been disclosed (Japanese Patent Laid-Open No. 1-20).
No. 3483), this recording liquid uses pectin as a thickening agent to prevent bleeding. Since pectin is a nonionic compound having a hydroxyl group as a hydrophilic group, the recording stability is maintained after printing is stopped. There was a problem that it was inferior.

On the other hand, color reproduction on a recording medium, water resistance,
Although the dye itself has been improved in order to achieve both image fastness such as moisture fastness and light fastness, it is difficult to obtain a dye having high image fastness and high reliability. As the magenta dye, for example, a recording liquid using an ammonium salt of a xanthene dye into which a carboxylic acid group is introduced has been disclosed (JP-A-5-194476).
Although it is excellent in water resistance and light resistance, there is a problem that the reliability of a stationary head in a printer cannot be secured.

There are many proposals for magenta dyes having a specific structure (JP-A-11-29730,
JP-A-11-320921, JP-A-2000-16
No. 38, JP-A-2000-86955, JP-A-2
000-109464), fastness, color tone, and reliability were not all satisfactory.

[0009] Furthermore, it has been proposed to use a specific azo dye [Japanese Patent Laid-Open No. 10-504856 (W
O96 / 24636)], although it has high image fastness, it is problematic that the color tone is low in chroma and strong in red.

Further, azo dyes and C.I. I. It has been proposed that acid red 52 (AR52) be mixed and used as a magenta recording liquid (JP-A-10-3294).
No. 30, US Pat. No. 6,053,969). However,
AR52 has poor light resistance, and also has the disadvantage that, depending on the recording medium, it bleeds under high humidity and the color of the image changes.

As a mixed dye, a combination of a gold-containing azopyrazolone dye and a dye having a xanthene skeleton has been proposed (Japanese Patent Application Publication No. 11-343439), but it is used for forming a color filter. Yes,
Lack of discharge stability at high speed IJ printing, poor reliability,
The color saturation on plain paper was also low.

In order to obtain water resistance, moisture resistance, and light resistance, pigments may be used, and various attempts have been made. However, since there is a problem in color development, other than a large plotter which requires fastness. Are not currently adopted. In addition, there is also a problem of clogging to cope with high resolution. Therefore, in order to further improve color development and reliability, it has been attempted to mix a pigment and a dye (Japanese Patent Publication No. 60-45669, Japanese Patent Application Laid-Open No. 6-100812). However, the former has a problem that the light resistance of the dye is insufficient, the permeability of the recording liquid to plain paper and the color development are not always sufficient, and especially the color development of blue is dull.

The applicant of the present invention has been studying improvement of various magenta dyes or magenta recording liquids for a long time (JP-B-6-4794, JP-A-64-62371).
JP, JP-A-64-62372, JP-A-7-1
No. 79796, Japanese Patent Application Laid-Open No. 10-36331, etc.). As a recording medium and a recording method, a recording medium containing a specific water-soluble metal salt or a cationic organic substance has been proposed as one for improving the image fastness (Japanese Patent Application Laid-Open No. 59-96988, JP-A-59-133273, JP-B-4-75140, US Pat. No. 4,740,420). However, it has been demanded that the recording liquid has sufficient reliability and that it maintains a high level of color tone and image fastness on any kind of IJ-specific media such as plain paper. However, it was not enough to satisfy them.

[0014]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks and problems of the prior art and provides an aqueous writing instrument, a recorder,
Used for pen plotter or ink jet recording, etc.
In particular, in ink jet recording, it has good ejection stability in high-speed printing or after a long pause, is rich in coloring properties, is prevented from bleeding on paper, and has excellent properties as a color recording liquid. A recording liquid cartridge containing a recording liquid, a recording apparatus and a recording method capable of giving a robust image excellent in color tone using the recording liquid and independent of a storage environment, and a recording apparatus or a recording method using the recording liquid. It is an object of the present invention to provide a recording medium that can be used.

[0015]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have focused on a dye to be incorporated in a recording liquid containing a colorant and water, and as a result of intensive studies, as a result, a specific azo dye was obtained. By using a mixed dye of a dye and a specific xanthene dye or a specific azo dye, it has good ejection stability in high-speed printing or after a long pause, and is rich in color development and prevents bleeding on paper A recording liquid exhibiting excellent characteristics as a color recording liquid is obtained, and a recording apparatus and a recording method capable of giving a robust image that is excellent in color tone using the recording liquid and independent of a storage environment are provided. In addition to finding that the recording liquid can be stored, a recording liquid cartridge containing the recording liquid and a recording medium used in a recording apparatus or a recording method using the recording liquid are found, and the present invention is completed based on this finding. Led was.

That is, according to the present invention, first, a azo dye represented by the following general formula (1) is added to a recording liquid containing a colorant which is dispersed or dissolved in water, water and a water-soluble organic solvent. There is provided a recording liquid (hereinafter, sometimes referred to as an ink) characterized by containing a xanthene dye represented by the following general formula (2) or an azo dye represented by the following general formula (3).

Embedded image [In the formula (1), R ¹ represents hydrogen, an alkyl group or an aryl group, R ² represents a hydrogen or an alkyl group, R ³ and R ⁴ each represent a hydrogen, an alkyl group or an aryl group, and M represents a salt. And n represents an integer of 2 to 4. ]

Embedded image [In formula (2), R ²¹ , R ²² , R ²³ , and R ^{24 each} independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom; X ¹ and X ^{2 each} independently represent a hydrogen atom; It represents a sulfonic acid group, a sulfonamide group, a carboxylic acid group or an arylsulfonamide group having a carboxylic acid group, and Y ²¹ represents —SO ₃ ⁻ or —COO ⁻ . ]

Embedded image [In the formula (3), M represents a cation forming a salt. ]

Second, there is provided a recording liquid cartridge provided with a recording liquid storage section for storing a recording liquid, wherein the recording liquid uses the first recording liquid. Is done.

Thirdly, there is provided a recording liquid cartridge including a recording liquid storing section for storing a recording liquid and a head for discharging recording liquid droplets, wherein the first recording liquid is used as the recording liquid. A recording liquid cartridge is provided.

Fourthly, an ink jet recording apparatus including a recording liquid cartridge having a recording liquid storage section for storing a recording liquid and a recording head for discharging recording liquid droplets, or a recording liquid storage containing a recording liquid And a recording liquid cartridge having a recording head for discharging recording liquid droplets, wherein the recording liquid cartridge includes a second or third recording liquid cartridge. Is provided.

Fifthly, there is provided an ink jet recording method for ejecting a recording liquid in accordance with a recording signal to obtain an image on a recording medium, wherein the first recording liquid is used.

Sixth, a recording medium for recording using the first recording liquid, wherein the recording medium is treated with an aqueous solution containing a water-soluble metal salt having a valence of two or more and a cationic organic compound. A recording medium is provided.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention first provides a recording liquid containing a colorant which is dispersed or dissolved in water, water and a water-soluble organic solvent, with an azo dye represented by the following general formula (1): Provided is a recording liquid comprising a xanthene dye represented by the formula (2) or an azo dye represented by the following general formula (3).

Embedded image [In the formula (1), R ¹ represents hydrogen, an alkyl group or an aryl group, R ² represents a hydrogen or an alkyl group, R ³ and R ⁴ each represent a hydrogen, an alkyl group or an aryl group, and M represents a salt. And n represents an integer of 2 to 4. ]

The alkyl group represented by R ¹ preferably has 1 to 6 carbon atoms, and has --CN, --COO
_{M, -OH, -COCH 3, -COOCH} 2, it may be a substituted alkyl group having 2 to 6 carbon atoms having a -CH ₃ or -COCH _3. Further, the aryl group represented by R ¹ may be an unsubstituted aryl group or an aryl group substituted with —CH ₃ or halogen. The alkyl group represented by R ² preferably has 1 to 6 carbon atoms. The alkyl group represented by R ³ or R ⁴ preferably has 1 to 6 carbon atoms, and includes —OH,
C 2 having —OCH ₃ , —COOM, or —SO ₃ M
And a substituted alkyl group or an aralkyl group.
The aryl group represented by R ³ and R ⁴ may be an unsubstituted aryl group or an aryl group substituted with —COOOM or —SO ₃ . R ³ and R ⁴ may form a ring, and in this case, may or may not contain a hetero atom. The cation forming the salt represented by M is an alkali metal ion or a quaternary ammonium ion, a quaternary phosphonium ion or an alkanolamine ion derived from a compound represented by the following general formula (3). As the alkali metal, sodium and lithium are preferable.

[0024]

Embedded image [In the formula (2), R ²¹ , R ²² , R ²³ and R ²⁴ independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom, and X ¹ and X ^{2 each} independently represent a hydrogen atom, a sulfone acid group, a sulfonamide group, an aryl sulfonamide group having a carboxylic acid group or carboxylic acid group, Y ²¹ is -SO ₃ ^- or -
COO ^- is shown. ]

Embedded image [In formula (3), a cation forming M is shown. The cation forming a salt represented by M is the same as described above.

The recording liquid contains chloride ions or sulfate ions in a total amount of 1 to 100 pp in terms of sodium salt.
m is preferably added. This inorganic ion is
Usually, most of the dye impurities are removed during the purification of the dye. However, if the amount contained in the recording liquid is less than 1 ppm, the crystallinity of the dye becomes high, and inorganic salts and other impurities are removed. When mixed from the outside, a sudden increase in viscosity or aggregation is likely to occur. If it exceeds 100 ppm, the solubility of the dye is reduced, and the dye is liable to be precipitated when water evaporates. In addition, the filterability of the ink decreases. For this reason, nozzle clogging of the ink jet head is liable to occur, and reliability is reduced.

The counter ion of the dye represented by the general formula (1), (2) or (3) is sodium ion, lithium ion or quaternary represented by the following general formula (4). It is preferably an ammonium ion, a quaternary phosphonium ion or an alkanolamine ion. The dye represented by the general formula (1), the general formula (2) or the general formula (3) is a salt of this counter ion, so that the recording is performed by dissolving during storage and by applying thermal energy to eject. In the method, reliability can be improved.

[0027]

Embedded image [In the formula (4), Z represents nitrogen or phosphorus, and R ^{5 to} R ⁸ independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group or a halogenated alkyl group. And the general formula (1) and the general formula (2) or the general formula (3)
Is from 1: 9 to 9: 1 on a weight basis.
Is more preferable, more preferably 9: 1 to 1: 4, and still more preferably 9: 1 to 1: 1.

When the amount of the dye represented by the formula (2) or (3) is less than 1/10, the saturation of the image on plain paper or the like is low, and the hue is too reddish. In addition, there is much light fading, resulting in poor image fastness. The content of the mixed dye represented by the general formula (1) and the general formula (2) or the general formula (3) with respect to the recording liquid is 0.1% by weight.
~ 7%, more preferably 0.1 ~
5%. If it is less than 0.1%, the coloring property as a colorant is poor, and if it exceeds 7%, when the moisture of the recording liquid is lost in the vicinity of the recording head nozzle or the like, the dye precipitates or the liquid rapidly thickens. And so on, which is not preferable because it causes clogging.

The following are specific compounds of the azo dye represented by the above general formula (1), but are not limited thereto.

Compound Example (1) -1

Embedded image

Compound Example (1) -2

Embedded image

Compound Example (1) -3

Embedded image

Compound Example (1) -4

Embedded image

In the following, specific examples of the compound of the general formula (2) are shown in the form of sodium and lithium salts, but are not limited thereto.

Compound Example (2) -1

Embedded image

Compound Example (2) -2

Embedded image

Compound Example (2) -3

Embedded image

Compound Example (2) -4

Embedded image

Compound Example (2) -5

Embedded image

Compound Example (2) -6

Embedded image

Further, specific examples of the compound of the general formula (3) are shown below in the form of sodium and lithium salts, but are not limited thereto.

Compound Example (3) -1

Embedded image

Compound Example (3) -2

Embedded image

The recording liquid of the present invention contains 2-ethyl-
0.1 to 8% by weight of 1,3-hexanediol and / or 2,2,4-trimethyl-1,3-pentanediol
It is preferable to contain, more preferably, 0.1 to
5% by weight. These diols having 8 carbon atoms serve as a penetrating agent that lowers the surface tension of the recording liquid and increases the wettability and permeability of recording media such as plain paper. These may be used alone or as a mixture, but since they have a low solubility in water of less than 5% by weight at 20 ° C., they are preferably contained together with a water-soluble organic solvent having good compatibility. .

Further, the recording liquid of the present invention contains a polyoxyethylene alkyl ether acetate represented by the following general formula (5) and / or a dialkyl sulfosuccinate represented by the following general formula (6): It is preferable to contain 0.01 to 4% by weight. More preferably, the content is 0.1 to 2% by weight or less.

[0046]

Embedded image

Embedded image [In the formulas (5) and (6), R ⁹ represents an alkyl group having 8 to 14 carbon atoms which may be branched, and R ¹⁰ and R ¹¹ represent 5 to 8 carbon atoms.
And M represents an alkali metal, a quaternary ammonium, a quaternary phosphonium or an alkanolamine, and m represents an integer of 3 to 12. The anionic compounds of formulas (5) and (6) not only assist the dissolution stability of the colorant but also lower the surface tension of the recording liquid,
It functions as a penetrant to improve the wettability and permeability of recording media such as plain paper.

The recording liquid of the present invention preferably contains 0.01 to 4% by weight of a compound represented by the following general formula (7) and / or the following general formula (8). More preferably, it is 0.1 to 2% by weight.

[0048]

Embedded image

Embedded image [In the formula (7), R ¹² represents a propyl group or a butyl group;
p and q each represent an integer of 0 or more, and p + q represents an integer of 0 to 20. [In formula (8), R ¹³ represents an alkyl group having 8 to 14 carbon atoms which may be branched, and r represents an integer of 2 to 30. The nonionic compounds of formulas (7) and (8) also function as penetrants that lower the surface tension of the ink and increase the wettability and permeability of recording media such as plain paper.

These equations (5), (6), (7) and (8)
When the compound of the formula (1) is contained together with the above-mentioned 2-ethyl-1,3-hexanediol and / or 2,2,4-trimethyl-1,3-pentanediol, a high permeability can be obtained due to a synergistic effect thereof. Therefore, it can be suitably used. In this case, equations (5), (6), (7),
0.1 to 2% by weight of one selected from the compounds of (8) is added to the above-mentioned 2-ethyl-1,3-hexanediol or 2,2,4-trimethyl-1,3-pentanediol 0.1 Combinations containing up to 5% by weight are most preferred.

The recording liquid of the present invention uses water as a liquid medium. The recording liquid has a desired physical property or a wetting agent for preventing drying of the recording liquid.
For the purpose of improving the dissolution stability of the compound of the present invention, a water-soluble organic solvent can be used. Examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, and polypropylene glycol. , 1,5-pentanediol, 1,6-hexanediol, glycerol,
Polyhydric alcohols such as 1,2,6-hexanetriol, 1,2,4-butanetriol, 1,2,3-butanetriol, petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether,
Polyhydric alcohol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether and propylene glycol monoethyl ether; polyhydric alcohol aryl such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether Ethers; nitrogen-containing heterocyclic compounds such as N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam; formamide, N-methylformamide Amides such as N, N, N-dimethylformamide; monoethanolamine, diethanolamine, triethanolamine, monoethylamine Amine, diethylamine, amines such as triethylamine, dimethyl sulfoxide, sulfolane, sulfur-containing compounds such as thiodiethanol, propylene carbonate, ethylene carbonate, and γ- butyrolactone. These solvents are used alone or in combination with water.

Of these, particularly preferred are diethylene glycol, thiodiethanol, polyethylene glycol 200 to 600, triethylene glycol, glycerol, 1,2,6-hexanetriol,
2,4-butanetriol, ぺ triol, 1,5-pentanediol, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 2-pyrrolidone,
1,3-dimethylimidazolidinone, which is used to provide an excellent effect on the high solubility of the present compound and the prevention of poor jet characteristics due to evaporation of water. In particular, in the present invention, a preferable solvent for obtaining the dispersion stability of the compound of the general formula (1) is a pyrrolidone derivative such as N-hydroxyethyl-2-pyrrolidone.

In the present invention, the general formula (5):
In addition to (6), (7) and (8), a penetrant may be added for the purpose of adjusting the surface tension. Specifically, diethylene glycol monophenyl ether, ethylene glycol monophenyl ether, ethylene glycol Monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether,
Alkyl and aryl ethers of polyhydric alcohols such as propylene glycol monobutyl ether and tetraethylene glycol chlorophenyl ether, polyoxyethylene polyoxypropylene block copolymers, fluorine-based surfactants, lower alcohols such as ethanol and 2-propanol. No. Particularly preferred is diethylene glycol monobutyl ether.

The surface tension in the present invention is an index indicating permeability to paper, and particularly indicates a dynamic surface tension in a short time of 1 second or less after the surface is formed, and a static surface tension measured in a saturation time. Different from surface tension. As a measuring method,
Any method can be adopted as long as it can measure a dynamic surface tension of 1 second or less by a conventionally known method described in JP-A-31237. The value of the surface tension is preferably 50 mN / m or less, more preferably 40 mN / m or less, whereby excellent drying properties can be obtained.

As the colorant of the present invention, in addition to the compounds of the general formulas (1), (2) and (3), a mixture with other colorants can be used if necessary. As the water-soluble dye used, acid dyes, direct dyes, basic dyes, reactive dyes, dyes classified as food dyes in color indexes, and those having excellent water resistance and light resistance are used. It is added to the extent that the effect is not alienated.

Acid dyes and food dyes include C.I. I.
Acid Yellow 17, 23, 42, 44, 79, 14
2, C.I. I. Acid Red 1,8,13,14,1
8, 26, 27, 35, 37, 42, 52, 82, 8
7, 89, 92, 97, 106, 111, 114, 11
5,134,186,249,254, C.I. I. Acid Blue 9, 29, 45, 92, 249, C.I. I. Acid Black 1, 2, 7, 24, 26, 94, C.I. I.
Food yellow 3, 4, C.I. I. Food red 7,9,
14, C.I. I. Food Black 1, 2 and the like.

Examples of direct dyes include C.I. I. Direct Yellow 1,12,24,26,33,44,50,8
6,120,132,142,144, C.I. I. Direct Red 1,4,9,13,17,20,28,3
1,39,80,81,83,89,225,227,
C. I. Direct Orange 26, 29, 62, 10
2, C.I. 1. Direct Blue 1,2,6,15,2
2,, 25,71,76,79,86,87,90,9
8,163,165,199,202, C.I. I. Direct Black 19, 22, 32, 38, 51, 56, 7
1, 74, 75, 77, 154, 168, 171 and the like.

As the basic dye, C.I. I. Basic Yellow 1, 2, 11, 13, 14, 15, 19, 2
1,23,24,25,28,29,32,36,4
0, 41, 45, 49, 51, 53, 63, 64, 6
5, 67, 70, 73, 77, 87, 91, C.I. I. Basic Red 2,12,13,14,15,18,2
2,23,24,27,29,35,36,38,3
9, 46, 49, 51, 52, 54, 59, 68, 6
9, 70, 73, 78, 82, 102, 104, 10
9, 112, C.I. I. Basic Blue 1,3,5
7, 9, 21, 22, 26, 35, 41, 45, 47,
54, 62, 65, 66, 67, 69, 75, 77, 7
8,89,92,93,105,117,120,12
2,124,129,137,141,147,15
5, C.I. I. Basic Black 2, 8 and the like.

As the reactive dye, C.I. I. Reactive black 3, 4, 7, 11, 12, 17, C.I. I. Reactive yellow 1,5,11,13,14,20,
21, 22, 25, 40, 47, 51, 55, 65, 6
7, C.I. I. Reactive Red 1,14,17,2
5,26,32,37,44,46,55,60,6
6, 74, 79, 96, 97, C.I. I. Reactive Blue 1,2,7,14,15,23,32,35,3
8, 41, 63, 80, 95 and the like. Particularly, acid dyes and direct dyes are preferably used.

As the pigment, azo-based organic pigments,
Phthalocyanine type, anthraquinone type, dioxazine type, indigo type, thioindigo type, perylene type, isoindolenone type, aniline black, azomethine type, rhodamine B lake pigment, carbon black and the like,
Examples of the inorganic pigment include iron oxide, titanium oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, dark blue, cadmium red, chrome yellow, and metal powder.

As the pigment dispersant, as a hydrophilic polymer which is a polymer having a hydrophobic portion and a hydrophilic portion, natural materials include gum arabic, gum tragan, guar gum, karaya gum, locust bean gum, arabinogalactone,
Vegetable polymers such as pectin and quince seed starch,
Algalic acid, carrageenan, seaweed-based polymers such as agar, gelatin, casein, albumin, animal-based polymers such as collagen, xanthene gum, microbial polymers such as dextran, and semi-synthetic systems include methylcellulose, ethylcellulose, hydroxyethylcellulose, and hydroxy. Propylcellulose, fibrous polymers such as carboxymethylcellulose, sodium starch glycolate, starch polymers such as sodium starch phosphate, sodium alginate, seaweed polymers such as propylene glycol alginate; Vinyl polymers such as alcohol, polyvinyl pyrrolidone and polyvinyl methyl ether, non-crosslinked polyacrylamide, polyacrylic acid and its alkali metal salts, water-soluble styrene acrylic resin Acrylic resin, water-soluble styrene maleic acid resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl naphthalene maleic resin, polyvinylpyrrolidone, polyvinyl alcohol, alkali metal salt of 6-naphthalenesulfonic acid formalin condensate, quaternary ammonium and Examples include a polymer compound having a salt of a cationic functional group such as an amino group in a side chain, and a natural polymer compound such as shellac. The above surfactants may be used in combination with these. The amount of these polymer dispersants added is
At a weight ratio of 1 to 10.

In the recording liquid of the present invention, conventionally known additives can be added in addition to the coloring agent and the solvent.

Examples of the preservative and fungicide include sodium dehydroacetate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, sodium benzoate and sodium pentachlorophenol.

As the pH adjuster, any substance can be used as long as it can adjust the pH to 7 or more without adversely affecting the prepared ink. Examples thereof include amines such as diethanolamine and triethanolamine, hydroxides of alkali metal elements such as lithium hydroxide, sodium hydroxide and potassium hydroxide, ammonium hydroxide, quaternary ammonium hydroxide, and quaternary. Examples thereof include alkali metal carbonates such as phosphonium hydroxide, lithium carbonate, sodium carbonate, and potassium carbonate. pH
The upper limit varies depending on the liquid contact member used, etc.
It is preferably set to 11 or less. However, when the pH is 9 or more, physical properties change due to the decomposition of the compound of the general formula (4) tends to occur. Therefore, it is preferable to adjust the pH to 6 to 9 only when the compound of the formula (4) is contained.

Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate and sodium uramil diacetate. As a rust inhibitor, for example,
Acid sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite,
Examples include pentaerythritol tetranitrate and dicyclohexylammonium nitrite. In addition, a water-soluble ultraviolet absorber and a water-soluble infrared absorber can be added according to the purpose.

Next, the present invention relates to a recording liquid cartridge for ink jet recording containing a recording liquid or a recording liquid container containing a recording liquid and a head part for discharging recording droplets. Thus, there is provided a recording liquid cartridge characterized by using the above recording liquid as the recording liquid.

The present invention is also directed to an ink jet recording apparatus including a recording liquid cartridge having a recording liquid storage section and a recording head for discharging recording liquid droplets, or a recording liquid storage section and a recording head for discharging recording liquid droplets. An ink jet recording apparatus provided with a recording liquid cartridge having the following, wherein the recording liquid is used as the recording liquid and the recording liquid cartridge according to the second invention is provided. I do.

A recording liquid cartridge containing a recording liquid and an ink jet recording apparatus provided with the recording liquid cartridge of the present invention will be described with reference to the accompanying drawings.
The following is only one of the configuration examples, and does not limit the present invention in any way.

FIG. 1 is a schematic front view of a mechanism section of a serial type ink jet recording apparatus equipped with a recording liquid cartridge having a recording liquid storing section for storing a recording liquid according to the present invention. The mechanism of the ink jet recording apparatus has a main support guide rod 3 and a sub support guide rod 4 laid in a substantially horizontal positional relationship between the side plates 1 and 2 on both sides. The carriage unit 5 is slidably supported in the main scanning direction by the rod 4.

The carriage unit 5 has four heads 6 for discharging yellow (Y) ink, magenta (M) ink, cyan (C) ink, and black (Bk) ink, respectively. 4) A recording liquid supply member for supplying a recording liquid to each of the four heads 6 is provided above the heads 6 of the carriage unit 5. The cartridges 7y, 7m, 7c, and 7k are exchangeably mounted.

The carriage unit 5 is connected to a timing belt 11 stretched between a driving pulley (driving timing pulley) 9 rotated by a main scanning motor 8 and a driven pulley (idler pulley) 10, and By controlling the driving of the scanning motor 8, the carriage 5, that is, the four heads 6, is moved in the main scanning direction.

Further, sub-frames 13 and 14 are erected on the bottom plate 12 connecting the side plates 1 and 2, and
A transport roller 15 for feeding the paper 16 in the sub-scanning direction orthogonal to the main scanning direction is held between the rollers 3 and 14 in a rotatable manner. The sub-scanning motor 17 is provided on the side of the sub-frame 14.
And the rotation of the sub-scanning motor 17 is
5, a gear 18 fixed to the rotation shaft of the sub-scanning motor 17 and a gear 19 fixed to the shaft of the transport roller 15.
And Further, a reliability maintenance / recovery mechanism (hereinafter, referred to as a “subsystem”) 21 of the head 6 is disposed between the side plate 1 and the subframe 12.

The subsystem 21 includes four cap means 22 for capping the ejection surface of each head 6 and the holder 2.
3, the holder 23 is swingably held by a link member 24, and when the carriage unit 5 moves in the main scanning direction, the carriage unit 5 comes into contact with an engaging portion 25 provided on the holder 23. The holder 23 is lifted up in accordance with the movement of the carriage unit 5, and the cap means 22 is lifted.
Capping the ejection surface 6a of the ink jet head 6, and moving the carriage unit 5 toward the printing area, the holder 23 is lifted down according to the movement of the carriage unit 5, and the cap unit 22 is moved to the ejection surface of the ink jet head 6. 6a.

The cap means 22 is connected to a suction pump 27 via a suction tube 26, forms an air opening port, and communicates with the atmosphere via an air opening tube and an air opening valve. The suction pump 27 discharges the sucked waste liquid to a waste liquid storage tank (not shown) via a drain tube or the like.

Further, on the side of the holder 23, a wiper blade 28, which is a wiping means composed of an elastic member such as a fiber member, a foam member or rubber, for wiping the ejection surface 6a of the ink jet head 6, is provided with a blade arm 29.
The blade arm 29 is pivotally supported so as to be pivotable, and is pivoted by rotation of a cam which is rotated by a driving means (not shown).

Next, the recording liquid cartridge 7 will be described with reference to FIGS. Here, FIG. 2 is an external perspective view of the recording liquid cartridge before being loaded into the recording apparatus, and FIG. 3 is a front sectional view of the recording liquid cartridge. The recording liquid cartridge 7 is, as shown in FIG.
A recording liquid absorber 42 in which a recording liquid of a required color has been absorbed in 1
Will be accommodated. The cartridge body 41 is formed by bonding or welding an upper lid member 44 to an upper opening of a case 43 having a wide opening at an upper portion, and is made of, for example, a resin molded product. The recording liquid absorber 42 is made of a porous material such as a urethane foam body, and absorbs the recording liquid after being compressed and inserted into the cartridge main body 41.

A recording liquid supply port 45 for supplying a recording liquid to the recording head 6 is formed at the bottom of the case 43 of the cartridge body 41, and a seal ring 46 is fitted on the inner peripheral surface of the recording liquid supply port 45. I'm wearing The upper lid member 44 has an air opening 47. In the cartridge main body 41, before the loading, the recording liquid supply port 45 is closed, and the case 43 is compressed and deformed by the pressure applied to the wide side wall at the time of handling the cartridge at the time of loading or transportation, or at the time of vacuum packaging. In order to prevent the recording liquid inside from leaking out, a cap member 50 is attached.

As shown in FIG. 2, a film sealing member 55 having an oxygen permeability of 100 ml / m ² or more is adhered to the upper lid member 44 to seal the air opening port 47. The sealing member 55 is sized to seal the plurality of grooves 48 formed around the opening 47 together with the atmosphere opening port 47. In this way, the atmosphere opening port 47 has an oxygen permeability of 10
By sealing with a sealing member 55 of 0 ml / m ² or more, the recording liquid cartridge 7 is wrapped under reduced pressure using a wrapping member such as an air-permeable aluminum laminate film, so that the recording liquid can be filled or absorbed. Due to the atmosphere in the space A (see FIG. 3) generated between the body 42 and the cartridge body 41, even when the gas is dissolved in the recording liquid,
The air in the recording liquid is discharged to the space between the cartridge body 41 having a high degree of vacuum and the packaging member via the seal member 55, and the degree of deaeration of the recording liquid is improved.

FIG. 4 shows an example of the configuration of a recording cartridge provided with a recording liquid storage section for storing the recording liquid of the present invention, and a head section for discharging recording liquid droplets. That is, the recording unit 30 is of a serial type, and includes an inkjet head 6 and a recording liquid tank 41 for storing the recording liquid supplied to the inkjet head 6.
And a lid member for sealing the inside of the recording liquid tank 41 to constitute a main part. The inkjet head 6 has a large number of nozzles 32 for discharging the recording liquid.
The recording liquid is guided from a recording liquid tank 41 to a common liquid chamber (not shown) via a recording liquid supply pipe (not shown), and is supplied from a nozzle 32 according to an electric signal input from the electrode 31 from the recording apparatus main body. Discharged.

Such a type of recording unit has a structure suitable for a head which can be manufactured at a low cost due to its configuration, that is, a so-called thermal type or bubble type head which uses heat energy as a driving power source. In the recording liquid of the present invention, the addition of the component (A) improves the wettability to a thermal element in a recording method such as a bubble method or a thermal method. Highly safe and highly safe, very suitable.

Here, the serial type ink jet recording apparatus as described above has been described. However, the recording liquid of the present invention may have nozzles arranged in an arbitrary arrangement such as a staggered pattern, having the same resolution as that of the target image or about a fraction of that. It is also possible to apply the present invention to a recording apparatus having a so-called line head, which is integrated at a density of not less than the width of the recording medium. In addition, the recording device here is not only an output printer for a PC or a digital camera, but also a printing device.
It may be a device having a complex function combined with a fax, a scanner, a telephone, or the like.

The present invention also relates to an ink jet recording method for forming an image on a recording medium by ejecting a recording liquid in response to a recording signal, wherein the recording liquid or the recording liquid cartridge is used as the recording liquid. Provided is a recording method characterized by using.

The present invention further provides a recording medium for recording using the above-mentioned recording liquid, wherein the recording medium is treated with an aqueous solution containing a water-soluble metal salt having an ionic valence of 2 or more and a cationic organic compound. A recording medium is provided.

The recording liquid of the present invention can be suitably used for an ink jet recording method for ejecting a recording liquid in accordance with a recording signal to obtain an image on a recording medium. As an action for ejecting the recording liquid, a volume fluctuation of the pressure liquid chamber due to a fine actuator or thermal energy, and the like can be cited. In particular, in the method in which thermal energy is applied to the recording liquid, the phenomenon of recording liquid residue accumulating on the heating element called kogation often causes nozzle clogging and ejection failure.
These problems can be prevented by using the recording liquid of the present invention.

Examples of the recording medium used in the present invention include plain paper containing pulp as a main component, paper or a film exclusively for ink-jet, in which a recording liquid receiving layer is provided on a film substrate. Among them, a recording medium containing one or more water-soluble metal salts having an ionic valence of 2 or more and one or more cationic organic compounds is excellent in image fastness such as light fastness and water fastness. Can be preferably used.

Water-soluble metal having an ionic valence of 2 or more
AlCl as salt_Three, Al (SO_Four)_Two, Al (NO _Three)_Three, ZnCl_Two, ZnS
O_Four, SnCl_Four, CaCl_Two, MgCl_Two, Mg (NO_Three)_Two, InCl_ThreeIs preferably used
Can be used. As the cationic organic compound, dicyandiene
Amido-formalin polycondensate, dicyandiamide-diechi
Lentriamin polycondensate, epichlorohydrin / dimethyl
Amine addition polymer, dimethyldiallylammonium chloride
-Ride / SO₂Copolymer, dimethyl diallyl ammonium
Um chloride polymer, diallylamine salt / SO ₂Both
Polymers of allylamine salts, dialkylaminoethyl
(Meth) acrylic acid quaternary salt polymer, polyallylaminate
Resin, cationic epoxy resin, polyethylene imine, poly
Acrylamide, poly (meth) acrylate,
Various cationic resins such as vinyl formamide
A thionic emulsion can be suitably used.

The water-soluble metal salt and the cationic organic compound having an ionic valence of 2 or more, even if they are not contained in the recording medium in advance, before the image is formed on the recording medium by ejecting the recording liquid. In addition, a pretreatment liquid to be applied to the recording medium by the application means that comes into contact with the recording medium may be suitably used. As a means for applying the pretreatment liquid, application using a roller or the like is preferably used.

The present invention still further provides a recording medium used in the above recording apparatus or the above recording method, wherein the aqueous medium contains a water-soluble metal salt having an ionic valence of 2 or more and a cationic organic compound. And a recording medium characterized by processing according to (1). For a water-soluble metal salt and a cationic organic compound having an ionic valence of 2 or more,
It is similar to the above, and the processing method is not different from the above.

[0088]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. Note that “%” is based on weight.

Example 1 After stirring and dissolving the composition having the following formulation, the pH was adjusted to 10 with a 10% aqueous solution of lithium hydroxide, and the solution was filtered through a 0.20 μm Teflon (registered trademark) filter. Then, a recording liquid (ink 1) was prepared. Compound of compound example (1) -1 2.0% Compound of compound example (2) -4 1.0% 2-ethyl-1,3-hexanediol 1.0% Compound of formula (5) (R ⁹ : Tridecyl group, m = 3) 1.0% diethylene glycol 20.0% glycerin 5.0% sodium dehydroacetate 0.2% ion exchanged water

Example 2 A recording liquid (ink 2) was prepared in the same manner as in Example 1 except that the following composition was used. Compound of compound example (1) -1 2.0% Compound of compound example (2) -1 1.0% 2-ethyl-1,3-hexanediol 1.0% Compound of formula (7) (R ¹² : Isobutyl group, p + q = 15) 1.0% diethylene glycol 15.0% 2-pyrrolidone 5.0% glycerin 5.0% sodium dehydroacetate 0.2% ion-exchanged water

Example 3 A recording liquid (ink) was prepared in the same manner as in Example 1 except that the following composition was stirred and dissolved, and then adjusted to a pH of 8.5 with a 10% aqueous solution of lithium hydroxide. 12) was prepared. Compound of compound example (1) -1 2.0% Compound of compound example (2) -6 1.0% 2-ethyl-1,3-hexanediol 1.0% Compound of formula (6) (R ¹⁰ = R ¹¹ : hexyl group) 1.0% ethylene glycol 20.0% glycerin 5.0% sodium dehydroacetate 0.2% ion exchange water

Example 4 A recording liquid (ink 4) was prepared in the same manner as in Example 1 except that the following composition was used. 3.5% of compound of compound example (1) -1 0.5% of compound of compound example (2) -4-6 1.0% of 2-ethyl-1,3-hexanediol 1.0% of compound (R) of formula (5) ⁹ : tridecyl group, m = 3) 1.0% diethylene glycol monobutyl ether 5.0% diethylene glycol 20.0% glycerin 5.0% sodium dehydroacetate 0.2% ion exchanged water

Example 5 A recording liquid (ink 5) was prepared in the same manner as in Example 1 except that the following composition was used. Compound of compound example (1) -1 2.0% Mixture of compound examples (2) -1 to 2.0% 2-ethyl-1,3-hexanediol 1.0% Compound of formula (5) (R ⁹ : tridecyl group, m = 3) 1.0% diethylene glycol 20.0% glycerin 5.0% 2-pyrrolidone 5.0% sodium dehydroacetate 0.2% ion-exchanged water

Example 6 A recording liquid (ink 6) was prepared in the same manner as in Example 1 except that the following composition was used. Compound Example (1) -1 Compound 2.0% Compound Example (3) -1 Compound 1.0% 2-Ethyl-1,3-hexanediol 1.0% Compound of Formula (5) (R ⁹ : Tridecyl group, m = 3) 1.0% diethylene glycol 20.0% glycerin 5.0% sodium dehydroacetate 0.2% ion exchange water

Example 7 A recording liquid (ink 7) was prepared in the same manner as in Example 1 except that the following composition was used. Compound Example (1) -1 Compound 2.0% Compound Example (3) -2 Compound 1.0% 2-Ethyl-1,3-hexanediol 1.0% Compound of Formula (7) (R ¹² : Isobutyl group, p + q = 15) 1.0% Diethylene glycol 15.0% 2-Pyrrolidone 5.0% Glycerin 5.0% Sodium dehydroacetate 0.2% Deionized water

Example 8 A recording liquid (ink 3) was prepared in the same manner as in Example 1 except that the following composition was stirred and dissolved, and then adjusted to a pH of 8.5 with a 10% aqueous solution of lithium hydroxide. ) Was prepared. Compound Example (1) -1 Compound 2.0% Compound Example (3) -2 Compound 1.0% 2-Ethyl-1,3-hexanediol 1.0% Compound of Formula (6) (R ¹⁰ = R ¹¹ : hexyl group) 1.0% ethylene glycol 20.0% glycerin 5.0% sodium dehydroacetate 0.2% ion-exchanged water

Example 9 A recording liquid (ink 9) was prepared in the same manner as in Example 1 except that the following composition was used. Compound of compound example (1) -1 3.5% Compound of compound example (3) -1 0.5% 2-ethyl-1,3-hexanediol 1.0% Compound of formula (5) (R ⁹ : Tridecyl group, m = 3) 1.0% diethylene glycol monobutyl ether 5.0% diethylene glycol 20.0% glycerin 5.0% sodium dehydroacetate 0.2% ion-exchanged water

Example 10 A recording liquid (ink 10) was prepared in the same manner as in Example 1 except that the following composition was used. Compound of compound example (1) -1 2.0% Compound of compound example (3) -2 2.0% 2-ethyl-1,3-hexanediol 1.0% Compound of formula (5) (R ⁹ : Tridecyl group, m = 3) 1.0% diethylene glycol 20.0% glycerin 5.0% 2-pyrrolidone 5.0% sodium dehydroacetate 0.2% ion-exchanged water

Comparative Example 1 Compound Example (2) -4 of Example 1 was replaced with C.I. I. Aci
A recording liquid (ink 11) was prepared in the same manner as in Example 1 except that d Red 52 was used.

Comparative Example 2 A compound of the formula (1) was prepared in the same manner as in Example 1 except for the compound example (2) -4.
A recording liquid (ink 12) was prepared in the same manner as in Example 1, except that the compound of No.-1 was changed to 3.0%.

Comparative Example 3 In Example 1, except for the compound of compound example (2) -1,
A recording liquid (ink 13) was prepared in the same manner as in Example 1, except that Compound Example (2) -4 was changed to 3.0%.

Comparative Example 4 The procedure of Example 1 was repeated except for the compounds of Compound Examples (1) -1 and (2) -4. I. Acid Red 52.
A recording liquid (ink 14) was prepared in the same manner as in Example 1 except that 0% was added.

Comparative Example 5 The same procedures as in Example 1 were carried out except for the compounds of Compound Examples (1) -1 and (2) -4. I. A recording liquid (ink 15) was prepared in the same manner as in Example 1 except that 3.0% of Acid Red 254 was added.

Comparative Example 6 Compound Example (3) -1 of Example 6 was replaced with C.I. I. Aci
A recording liquid (ink 16) was prepared in the same manner as in Example 1, except that d Red 52 was used.

Comparative Example 7 The compound of formula (1) was prepared in the same manner as in Example 6 except for the compound example (3) -1.
A recording liquid (ink 17) was prepared in the same manner as in Example 1, except that the compound of No.-1 was changed to 3.0%.

Comparative Example 8 In Example 6, except for the compound of compound example (2) -1,
A recording liquid (ink 18) was prepared in the same manner as in Example 1, except that Compound Example (3) -1 was changed to 3.0%.

Comparative Example 9 The same procedures as in Example 6 were carried out except that the compounds of Compound Examples (1) -1 and (3) -1 were used. I. Acid Red 52.
A recording liquid (ink 19) was prepared in the same manner as in Example 1 except that 0% was added.

Comparative Example 10 The procedure of Example 6 was repeated except that the compounds of Compound Examples (1) -1 and (3) -1 were used. I. A recording liquid (ink 20) was prepared in the same manner as in Example 1 except that 3.0% of Acid Red 289 was added. The following tests were performed on Examples 1 to 10 (Inks 1 to 10) and Comparative Examples 1 to 5 (Inks 11 to 20) thus obtained.

(1) Clarity of Image The nozzle diameter of the thermal ink jet system is 45 μm and the nozzle diameter is 30 μm.
Inkjet printer having a nozzle of 0 dpi;
Nozzle diameter 33μ using laminated PZT for pressurization of liquid chamber flow path
m, inkjet printing with 128 nozzles
Print, and visually check color tone, image bleeding and density
Decided. The evaluation levels are as follows. ：: Excellent in color tone, image bleeding and density. Δ: Not excellent in all, but acceptable. ×: Extremely poor. The recording media used for the evaluation are as follows. Recording medium: plain paper (My Paper manufactured by NBS Ricoh). Recording medium: IJ coated paper (Ricoh type J30
0). Recording medium: glossy paper (HP Premium Plus Photo Light)
Sawagami C6832A). Recording medium: Wet adhesion of pretreatment liquid of the following formulation
About 3.0 g / m in quantity^Two Immediately after roller application. Cellopol YM-500 (56% aqueous solution of dicyandiamide resin) 50.0% Glycerin 20.0% 1,5-Pentanediol 20.0% Magnesium nitrate 5.0% Ion-exchanged water

(2) Moisture Resistance of Image The image sample was left in a thermostat at 35 ° C. and 90% RH for 24 hours, and the bleeding due to magenta diffusion under high humidity was sensuously evaluated. The evaluation levels are as follows. 〇: Those with little change. Δ: Bleeding occurred but was acceptable. ×: Bleeding out, significant color change, unacceptable.

(3) Light fastness of image Using an Atlas weatherometer Ci35AW, 70
℃, 50% RH, black panel temperature 89 ℃ environment,
Xenon irradiance 0.35W / m, approx.
^{At 2} (@ 340 nm), discoloration and color change before and after the image sample was irradiated for 24 hours were evaluated. The evaluation levels are as follows. A: No fading or color change is visually observed. ：: little fading and color change X: Discoloration and color change are large and unacceptable. XX: Discoloration is so remarkable that the image cannot be recognized, and is not acceptable.

(4) Storage stability Each ink was placed in a polyethylene container and stored at -20 ° C, 5 ° C,
The samples were stored at 20 ° C. and 70 ° C. for 3 months, and the surface tension, viscosity, and the presence or absence of precipitates after storage were examined. No change in physical properties was observed regardless of the conditions of storage.

(5) Reliability at the time of printing suspension PZT having the recording liquid cartridge shown in FIGS. 2 and 3 filled with each ink and having 128 nozzles with a nozzle diameter of 30 μm.
Use a printer that has a head that is driven by a printer.Check how much the print direction can be recovered even after printing is stopped without performing capping, cleaning, etc. during operation. The reliability was evaluated based on the change in the weight of the droplet. A sample having no particular problem was marked with “○”.

Table 1 shows the above evaluation results.

[Table 1]

[0115]

According to the present invention, an aqueous writing instrument, a recorder, a pen plotter or an ink jet recording apparatus
It has good ejection stability in high-speed printing or after a long period of inactivity, is rich in color development, and prevents bleeding on paper,
A recording liquid exhibiting excellent characteristics as a color recording liquid, a recording liquid cartridge containing the recording liquid, a recording method and a recording apparatus capable of giving a robust image excellent in color tone using the recording liquid and independent of a storage environment A recording medium for recording using this recording liquid and a recording medium for use in a recording method or a recording apparatus are provided, and the contribution to these recording fields is extremely large.

[Brief description of the drawings]

FIG. 1 is a schematic front view showing a configuration example of a serial type ink jet recording apparatus equipped with an ink cartridge containing ink to which the present invention is applied.

FIG. 2 is an external perspective view of an ink cartridge before being loaded into a recording apparatus.

FIG. 3 is a front sectional view of the ink cartridge.

FIG. 4 is an external perspective view of a recording unit integrated with a recording head.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Side plate 2 Side plate 3 Main support guide book 4 Sub support guide book 5 Carriage unit 6 Head 7 Recording liquid cartridge 8 Main scanning motor 9 Drive pulley 10 Follower pulley 11 Timing belt 12 Bottom plate 13 Subframe 14 Subframe 15 Transport roller 16 Paper 17 Sub-scanning motor 18 Gear 21 Subsystem 22 Cap means 23 Holder 24 Link member 25 Engaging part 26 Suction tube 27 Suction pump 29 Blade arm 31 Electrode 32 Nozzle 41 Cartridge main body 42 Recording liquid absorber 43 Case 44 Upper lid member 45 Recording liquid supply Port 46 Seal ring 47 Atmospheric release port 55 Seal part

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09B 11/28 B41J 3/04 101Y 29/30 102Z (72) Inventor Tetsuya Kaneko 1 Nakamagome, Ota-ku, Tokyo 3-6, Ricoh Co., Ltd.F-term (reference) 2C056 EA13 FA03 FA10 FC02 FC06 HA42 KC11 KC16 2H086 BA53 BA56 BA59 BA62 4H056 BB05 BC01 BF21 BF28F 4J039 BC09 BC10 BC11 BC13 BC14 BC15 BC20 BC33 BC35 BC36 BC39 BC40 BC40 BC68 BC73 BC75 BC77 BC79 BE02 BE12 BE15 BE22 BE28 BE29 CA03 CA06 EA21 EA34 EA41 EA44 EA46 EA47 GA24 GA26 GA27

Claims (17)

[Claims] 1. An azo dye represented by the following general formula (1) and a azo dye represented by the following general formula (2) in a recording liquid containing a colorant that is dispersed or dissolved in water, water and a water-soluble organic solvent. A recording liquid containing a xanthene dye or an azo dye represented by the following general formula (3). Embedded image [In the formula (1), R ¹ represents hydrogen, an alkyl group or an aryl group, R ² represents a hydrogen or an alkyl group, R ³ and R ⁴ each represent a hydrogen, an alkyl group or an aryl group, and M represents a salt. And n represents an integer of 2 to 4. [Chemical formula 2] [In formula (2), R ²¹ , R ²² , R ²³ , and R ^{24 each} independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom; X ¹ and X ^{2 each} independently represent a hydrogen atom; It represents a sulfonic acid group, a sulfonamide group, a carboxylic acid group or an arylsulfonamide group having a carboxylic acid group, and Y ²¹ represents —SO ₃ ⁻ or —COO ⁻ . [Chemical formula 3] [In the formula (3), M represents a cation forming a salt. ] 2. A method according to claim 1, wherein said recording liquid contains chloride ions or sulfate ions in a total amount of 1 to 100 ppm in terms of sodium salt.
The recording liquid according to claim 1, wherein the recording liquid is added. 3. The counter ion of the dye represented by the general formula (1), (2) or (3) is sodium ion, lithium ion or the following general formula (4). 2. A quaternary ammonium ion, a quaternary phosphonium ion or an alkanolamine ion.
Or the recording liquid according to 2. Embedded image [In the formula (4), Z represents nitrogen or phosphorus, and R ^{5 to} R ⁸ each represent hydrogen or an alkyl group. ] 4. The mixing ratio between the dye represented by the general formula (1) and the dye represented by the general formula (2) or the general formula (3) is 1: 9 to 9: 1 on a weight basis, and recording is performed. The recording liquid according to any one of claims 1 to 3, wherein a mixing amount with respect to the liquid is 0.1 to 7% by weight. 5. The method according to claim 1, wherein the recording liquid is 2-ethyl-1,3-
Hexanediol and / or 2,2,4-trimethyl-
0.1 to 8% by weight of 1,3-pentanediol
The recording liquid according to any one of claims 1 to 4, wherein the recording liquid is contained. 6. A polyoxyethylene alkyl ether acetate represented by the following general formula (5) and / or a dialkyl sulfosuccinate represented by the following general formula (6) are added to the recording liquid on a weight basis. The recording liquid according to any one of claims 1 to 5, which contains 0.01 to 4%. Embedded image Embedded image [In the formulas (5) and (6), R ⁹ , R ¹⁰ and R ¹¹ each represent an alkyl group, M represents a cation forming a salt,
n and m show the integer of 3-12. ] 7. The recording liquid containing 0.01 to 4% by weight of a compound represented by the following general formula (7) and / or the following general formula (8). 7. The recording liquid according to any one of claims 1 to 6. Embedded image [In the formula (7), R ¹² represents an alkyl group, p and q each represent an integer of 0 or more, and the sum of p and q is an integer of 0 to 20. Embedded image [In the formula (8), R ¹³ represents an alkyl group having 8 to 14 carbon atoms which may be branched, and r represents an integer of 2 to 30. ) 8. A recording liquid cartridge provided with a recording liquid storage section for storing a recording liquid, wherein the recording liquid according to claim 1 is used as the recording liquid. Recording liquid cartridge. 9. A recording liquid cartridge comprising a recording liquid storage section for storing a recording liquid and a head for discharging ink droplets, wherein the recording liquid is used as the recording liquid. A recording liquid cartridge characterized by using the above-mentioned recording liquid. 10. An ink jet recording apparatus including a recording liquid cartridge having a recording liquid storage section containing a recording liquid, and a recording head for discharging recording liquid droplets, or an ink storage section containing a recording liquid. An ink jet recording apparatus comprising a recording liquid cartridge having a recording head for discharging recording liquid droplets, wherein the recording liquid cartridge according to claim 8 or 9 is provided as the recording liquid cartridge. Recording device. 11. An ink jet recording method for ejecting a recording liquid in accordance with a recording signal to obtain an image on a recording medium, wherein the recording liquid according to claim 1 is used. Method. 12. The recording method according to claim 11, wherein heat energy corresponding to the recording signal is applied to the recording liquid, and the recording liquid is ejected to form an image on a recording medium. 13. The recording method according to claim 11, wherein the recording medium contains a water-soluble metal salt having an ionic valence of 2 or more and a cationic organic compound. 14. When a recording liquid is ejected to form an image on a recording medium, a pretreatment liquid applied to the recording medium by an application unit that comes into contact with the recording medium is an aqueous solution having an ionic valence of 2 or more. The recording method according to any one of claims 11 to 13, wherein the recording method comprises a cationic metal salt and a cationic organic compound. 15. A recording medium for recording using the recording liquid according to claim 1, comprising a water-soluble metal salt having an ionic valence of 2 or more and a cationic organic compound. A recording medium characterized by being treated with an aqueous solution. 16. A recording medium used in the recording apparatus according to claim 10 or the recording method according to claim 11, wherein the water-soluble metal salt has an ionic valence of 2 or more. A recording medium characterized by being treated with an aqueous solution containing a cationic organic compound. 17. The water-soluble metal salt having an ionic valence of 2 or more is AlCl ₃ , Al (SO ₄ ) ₂ , Al (NO ₃ ) ₃ , ZnCl ₂ , ZnSO
₄ , SnCl ₄ , CaCl ₂ , MgCl ₂ , Mg (NO ₃ ) ₂ and one or more compounds selected from InCl ₃ , wherein the cationic organic compound is dicyandiamide / formalin polycondensate, dicyandiamide / diethylenetriamine polycondensation things, epichlorohydrin-dimethylamine addition polymer, dimethyl diallyl ammonium chlorides, SO ₂ copolymer, dimethyl diallyl ammonium chlorides polymers, polymer, dialkylamino ethyl diallylamine salt-SO ₂ copolymer allylamine salt (meth) Acullate quaternary salt polymer,
1 selected from polyallylamine, cationic epoxy resin, polyethyleneimine, polyacrylamide, poly (meth) acrylate and polyvinylformamide
17. The recording medium according to claim 15, which is at least one kind of compound.