JP3387544B2 - Recording liquid, inkjet recording method, ink cartridge, recording unit, and inkjet recording apparatus - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording liquid suitable for an ink jet printer, and further, a recording method and recording in which the recording liquid is ejected from the orifice of the recording head by the action of energy, preferably thermal energy, to perform recording on paper. Involved in the device. More specifically, copy paper, report paper, notebooks, which are commonly used in offices and homes,
The present invention relates to a recording liquid and a recording method capable of recording on non-coated paper such as letter paper, bond paper, and continuous slip paper without bleeding.

[0002]

2. Description of the Related Art The ink jet recording system has an advantage that noise is not generated during recording and a high resolution recording image can be obtained at a high speed by using a highly integrated head. In such an ink jet recording system, a recording liquid in which various water-soluble dyes are dissolved in water or a mixed liquid of water and an organic solvent is used.

However, when water-soluble dyes are used, these water-soluble dyes are originally inferior in light resistance, so that the light resistance of a recorded image often becomes a problem.

Since the recording liquid is water-soluble, the water resistance of the recorded image often becomes a problem. That is, when the recorded image is exposed to rain, sweat, or water for eating and drinking, the recorded image may be blurred or disappear.

On the other hand, in stationery such as a ballpoint pen,
Similarly, since mainly water-soluble dyes are used, problems of light resistance and water resistance occur, and various aqueous pigment recording solutions for stationery have been proposed to solve these problems. As an example of studying dispersion stability, prevention of solidification of the recording liquid at the pen tip, and prevention of abrasion of the ball of the ballpoint pen for practical use of the aqueous pigment recording liquid, JP-A-58-80368 and JP-A-6-68368 are cited.
1-200182, JP 61-247774, JP 61-272278, JP 62-
568, JP-A-62-101671, JP-A-62-101672, JP-A-1-249869.
Japanese Patent Laid-Open No. 1-301760, and the like. Recently, ballpoint pens using water-based pigment recording liquid,
Markers are being marketed as products.

Further, as a recording liquid for a recording liquid jet using an aqueous pigment recording liquid, a specific water-soluble solvent and polymer dispersion are described in JP-A-56-147859 and JP-A-56-147860. Pigment recording liquids using agents have been proposed. Further, JP-A-4-57859 and JP-A-4-57859.
Japanese Patent Laid-Open No. 57860 has proposed a recording liquid using a pigment and a dye in combination.

In the ink jet recording method, it is extremely important that the non-volatile components in the ejected recording liquid rapidly aggregate on the recording paper in order to satisfy the printing quality. However, when the above-mentioned conventional aqueous pigment recording liquid is used for ink jet recording, the non-volatile components aggregated on the recording paper are present as solids on the recording paper even after the recording liquid is fixed, so that strong rubbing or highlighting may occur. There is a problem that the printed surface is contaminated by the tracing.

Further, when a conventional recording liquid is recorded by an ink jet recording method on plain paper on which no special ink receiving layer is formed, there is a problem that bleeding occurs although there are some differences depending on the composition. . Therefore, a method of adding a high-viscosity solvent to the recording liquid in order to suppress bleeding has been proposed. However, by increasing the viscosity, bleeding can be suppressed, but since a considerable amount of high-viscosity organic solvent is required for that, the viscosity of the recording liquid becomes too high, and the recording liquid ejection speed at the nozzle decreases. Or, there is a problem that the ejection becomes unstable due to the decrease in the surface tension. Further, there is a problem in that the print density and the degree of bleeding differ depending on the type of recording paper.

As an attempt to solve such a problem, a technique of adding iodine or the like to the ink to improve the printing quality on a specific recording paper is disclosed in JP-B-60-50054.
No. 0, JP-A-63-159485 and the like. However, with the techniques disclosed in these publications, a sufficient effect cannot be obtained on a wide variety of recording papers.

[0010]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide an aqueous pigment recording liquid which eliminates the variation in printing quality due to the difference in recording paper, and which also satisfies the fixing speed and quickness. The purpose of this is also to obtain a stable recorded image without lowering the printing density.

Another object of the present invention is to perform recording without bleeding on any recording paper without excessively increasing the viscosity of the recording liquid, and to have various recording characteristics. It is to provide a recording liquid and a recording method. That is, bleeding of the recording liquid when recording is performed on uncoated paper such as copy paper, report paper, notebook, notepaper, bond paper, and continuous slip paper that are generally used in offices, so-called plain paper, and An object of the present invention is to solve the problem of slow drying property of a recorded matter and to provide a recording liquid excellent in print quality.

Another object of the present invention is to provide a recording liquid which is highly safe for use in offices and homes.

[0013]

The above object can be achieved by the present invention described below.

That is, the present invention is at least (a) pigment, (b)
Water-soluble resin having carbonyl group, (c) aqueous medium, and (d) compound represented by the following general formula [1], compound represented by the following formula [2], styrene-malein containing two or more hydrazide groups A recording liquid for inkjet recording, comprising an acid resin and at least one selected from the group consisting of polyacrylic acids containing two or more hydrazide groups.

[0015]

[Chemical 5] (R represents (CH ₂ ) n or C ₆ H ₄ , where n is 0 to 1
It is an integer of 0. )

[0016]

[Chemical 6] Further, the present invention is an inkjet recording method, which comprises a step of applying energy to the recording liquid to eject the recording liquid from the fine holes, wherein the recording liquid described above is used as the recording liquid. It is a recording method.

The present invention also provides (a) a dye having at least a carbonyl group, (b) an aqueous medium, and (c) the following general formula:
Selected from the group consisting of a compound represented by [1], a compound represented by the following chemical formula [2], a styrene-maleic acid resin containing two or more hydrazide groups, and a polyacrylic acid containing two or more hydrazide groups. A recording liquid for inkjet recording, comprising:

[0018]

[Chemical 7] (R represents (CH ₂ ) n or C ₆ H ₄ , where n is 0 to 1
It is an integer of 0. )

[0019]

[Chemical 8] Further, the present invention is an inkjet recording method, which comprises a step of applying energy to the recording liquid to eject the recording liquid from the fine holes, wherein the recording liquid described above is used as the recording liquid. It is a recording method.

The present invention also provides an ink containing ink.
In an ink cartridge provided with a container, the ink
Is an ink described above.
It is Tridge.

The present invention also provides an ink containing ink.
Ink jet method for ink in storage unit and ink storage unit
Therefore, in a recording unit equipped with a recording head for discharging
In addition, the ink is the ink described above.
Is a recording unit.

The present invention also provides an ink containing ink.
Ink cartridge having a containing portion and the ink
A recording head for ejecting by a jet method
In the ink jet recording apparatus, the ink is the same as described above.
Inkjet recording device characterized by being ink
Is.

The present invention also provides an ink containing ink.
The container and the ink are ejected by an inkjet method.
A recording unit having a recording head
In the ink jet recording apparatus, the ink is the same as described above.
Inkjet recording device characterized by being ink
Is.

The present invention will be described in detail below.

The present inventors have found that in an aqueous pigment recording liquid,
By using a compound having a particular structural formula,
The inventors have found that the problems described above can be solved while improving the quickness of the printed matter and maintaining the printing quality, and reached the present invention. That is, the compound represented by the general formula [1] and the chemical formula [2], a styrene-maleic acid resin having two or more hydrazide groups, and two hydrazide groups are used.
The polyacrylic acid having at least one thereof (hereinafter, these compounds are collectively referred to as a dihydrazide compound) has a property of being uniformly dissolved in an aqueous solution and reacting with a compound having a carbonyl group when water is removed. Utilizing this property, this compound is added to an aqueous recording liquid to crosslink with a carbonyl group such as a dispersant contained in the recording liquid on a recording paper to increase the film thickness of a non-volatile component. It is possible to improve the quickness of the product. Furthermore, since the crosslinking reaction occurs uniformly regardless of the type of paper, it is possible to eliminate the dependence of print quality on recording paper.

Further, the inventors of the present invention have conducted extensive studies on various recording liquid compositions in order to improve the bleeding, the drying property and the penetrability of the recording liquid on plain paper, and as a result, the above-mentioned dihydrazide compound was found to prevent bleeding. It gives good results, and also has no adverse effect in preventing clogging,
Moreover, they have found that the present invention is highly reliable and has no problem in terms of safety, and the present invention has been completed.

That is, according to the research conducted by the present inventors, regarding the bleeding and penetrability of the recording liquid on plain paper, when a surfactant as used in ordinary recording liquid is used, Depending on the type of recording paper, good recording and non-correct recording may be mixed, and stable recording may be difficult to obtain.On the other hand, when a dihydrazide compound is used, it may be used in combination with a penetrant such as a surfactant. However, it is possible to obtain a very good result that stable recording can be obtained with little difference in quality depending on the type of recording paper.

The reason for this is that when the dihydrazide compound dissolves uniformly in the aqueous solution and the water disappears,
It has a property of reacting with a dye having a carbonyl group. By utilizing this property, a dihydrazide compound can be added to an aqueous recording liquid, and a crosslinking reaction with a dye on the recording paper can eliminate the recording paper selectivity of the print density and further improve the fixing speed. .

Each component constituting the recording liquid of the present invention will be described below.

First, the first recording liquid will be described.

The pigment is not particularly limited as long as it fulfills the function of an ordinary ink jet recording liquid, but particularly preferable examples are shown below.

The carbon black used in the black recording liquid is a carbon black produced by a furnace method or a channel method, and has a primary particle size of 15 to 40 mμ and BET.
Specific surface area by the method is 50-300 square m / g, DBP oil absorption is 40-150 ml / 100g, and volatile content is 0.5-
Those having a pH value of 10% and a pH value of 2 to 9 are preferable. 2300, NO. 900, MCF88, N
O. 33, NO. 40, NO. 45, NO. 52, MA
7, MA8, NO. 2200B (Made by Mitsubishi Kasei), R
AVEN125 (made in Colombia), REGAL400
R, REGAL330R, REGAL660R, MOG
UL L (made by Cabot), Color Black
FW1, COLOR Black FW18, Colo
r Black S170, Color Black S
150, Printex35, Printex U
It is preferable to use a commercial product such as (manufactured by Degussa).

As the pigment used in the yellow recording liquid, C.I. I. Pigment Yellow 1,
C. I. Pigment Yellow 2, C.I. I.
Pigment Yellow 3, C.I. I. Pigm
ent Yellow 13, C.I. I. Pigment
Yellow 16, C.I. I. Pigment Ye
Low 83 and the like can be preferably used.

As the pigment used as the magenta recording liquid, C.I. I. Pigment Red 5, C.I. I.
Pigment Red 7, C.I. I. Pigment
Red 12, C.I. I. Pigment Red 4
8 (Ca), C.I. I. Pigment Red 48
(Mn), C.I. I. Pigment Red 57 (C
a), C.I. I. Pigment Red 112, C.I.
I. Pigment Red 122 and the like can be preferably used.

Pigments used as a cyan recording liquid include C.I. I. Pigment Blue 1, C.I. I.
Pigment Blue 2, C.I. I. Pigmen
tBlue 3, C.I. I. Pigment Blue
15: 3, C.I. I. Pigment Blue 16,
C. I. Pigment Blue 22, C.I. I. V
at Blue 4, C.I. I. Vat Blue 6 and the like can be preferably used.

The pigment of the recording liquid of the present invention is not limited to the above commercial products, but may be a newly manufactured pigment.

The water-soluble resin having a carbonyl group functions as a dispersant for the pigment. Examples of the characteristic group having a carbonyl group include a carbonyl group, a carboxyl group, an ester bond, an amide bond, a ketone group, and a urethane bond. Any water-soluble resin having a -C = O bond can be used, but it has a weight average molecular weight of 1,000 to 30,000, and more preferably 3,000.
What is -15000 is preferable. Specifically, styrene, styrene derivatives, vinylnaphthalene, vinylnaphthalene derivatives, α, β-ethylenically unsaturated carboxylic acid aliphatic alcohol esters, acrylic acid, acrylic acid derivatives, maleic acid, maleic acid derivatives, itaconic acid ,
Consists of at least two monomers (at least one of which is a hydrophilic monomer) selected from itaconic acid derivatives, fumaric acid, fumaric acid derivatives, vinyl acetate, vinylpyrrolidone, acrylamide, and their derivatives Examples thereof include block copolymers, random copolymers, graft copolymers, and salts thereof. Further, natural resins such as rosin, shellac and starch can also be used. These natural resins are alkali-soluble resins that are soluble in an aqueous solution in which a base is dissolved.

The water-soluble resin is 0.
It is preferably contained in the range of 1 to 5% by weight. Furthermore, it is preferable that the entire recording liquid is adjusted to be neutral or alkaline, since the solubility of the water-soluble resin can be improved and the recording liquid can be further excellent in long-term storage stability. However, in this case, since it may cause corrosion of various members used in the inkjet recording apparatus, it is preferable that the pH range is 7 to 10.

The pH adjusting agent used for the above purpose includes
For example, various organic amines such as diethanolamine and triethanolamine, inorganic alkali agents such as hydroxides of alkali metals such as sodium hydroxide, lithium hydroxide and potassium hydroxide, organic acids and mineral acids can be mentioned. .

As described above, the pigment and the water-soluble resin are dispersed or dissolved in the aqueous medium.

The aqueous medium is preferably a mixed solvent of water and a water-soluble organic solvent.

The water is not ordinary water containing various ions, but ion-exchanged water (deionized water) is preferable.

Examples of the water-soluble organic solvent used by mixing with water include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol and the like. Alkyl alcohols having 1 to 4 carbon atoms; amides such as dimethylformamide and dimethylacetamide; ketones or keto alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyalkylenes such as polyethylene glycol and polypropylene glycol Glycols; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol,
1,2,6-hexanetriol, thiodiglycol,
Alkylene glycols having an alkylene group of 2 to 6 carbon atoms such as hexylene glycol and diethylene glycol; glycerin; ethylene glycol monomethyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) Lower alkyl ethers of polyhydric alcohols such as ethers; N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like can be mentioned. Among these many water-soluble organic solvents, polyhydric alcohols such as diethylene glycol and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl (or ethyl) ether are particularly preferable.

The content of the above water-soluble organic solvent in the recording liquid of the present invention is generally in the range of 3 to 50% by weight, preferably 3 to 40% by weight, based on the total weight of the recording liquid. ,
Water is 10 to 90% by weight of the total weight of the recording liquid, preferably 30
-80% by weight. In the present invention, the dihydrazide compound contained in the recording liquid in order to crosslink with the carbonyl group of the dispersant to increase the film thickness of the non-volatile component,
Specific examples thereof include adipic acid dihydrazide, oxalic acid dihydrazide, carbohydrazide, polyacrylic acid hydrazide (all manufactured by Otsuka Chemical Co., Ltd.), and ACRONAL (trade name, manufactured by Mitsubishi Yuka Birdishe ).

The content of the dihydrazide compound in the recording liquid is preferably 0.1 to 10% by weight, and 0.5 to 5% by weight.
Is more preferable. The content of these compounds is
If the amount is less than 0.1% by weight, it is impossible to improve the refreshing property of the printed matter, which is to be improved in the present invention. On the other hand, if the amount is more than 10% by weight, the ejection port due to an increase in the viscosity of the recording liquid may be generated. There are some adverse effects such as clogging.

The recording liquid of the present invention contains, in addition to the above components,
In order to obtain a recording liquid having a desired physical property value, a surfactant, an antifoaming agent, an antiseptic agent or the like can be added if necessary,
Furthermore, a commercially available water-soluble dye or the like can be added.

As a method of preparing the recording liquid of the present invention, first, a pigment is added to an aqueous solution containing at least a water-soluble resin having a carbonyl group and water, stirred, and then dispersed using a dispersing means described later. If necessary, centrifugation treatment is performed to obtain a desired dispersion liquid. Then, in this dispersion,
The above-mentioned dihydrazide compound is added and stirred to prepare a recording liquid. When an alkali-soluble resin such as a natural resin is used as the water-soluble resin having a carbonyl group, it is necessary to add a base to dissolve the resin.

As the bases added to the dispersion when the alkali-soluble resin is used, organic amines such as monoethanolamine, diethanolamine, triethanolamine, amine methyl propanol and ammonia, or water. Inorganic bases such as potassium oxide and sodium hydroxide are preferred.

Further, it is effective to carry out premixing for 30 minutes or more before the dispersion treatment of the aqueous solution containing the pigment. This premixing operation improves the wettability of the pigment surface and promotes adsorption on the pigment surface.

On the other hand, the disperser used in the present invention may be any disperser which is generally used, and examples thereof include a ball mill, a roll mill and a sand mill. Among them, a high speed type sand mill is preferable, for example, a super mill, a sand grinder, a bead mill,
Agitator mills, Glen mills, Dyno mills, Pearl mills, Cobol mills (all are trade names) and the like.

In the present invention, as a method for obtaining a pigment having a desired particle size distribution, the size of the pulverized media of the disperser is reduced, and the packing ratio of the pulverized media is increased.
Further, methods such as lengthening the treatment time, slowing the discharge speed, and classifying with a filter or a centrifugal separator after crushing are used. Or the combination of those methods is mentioned.

Next, the second recording liquid will be described.

The dye having a carbonyl group may be a dye having a carbonyl group, a carboxyl group, an ester bond, an amide bond, a ketone group, a urethane bond, etc., and examples thereof include a direct dye, an acid dye, an edible dye and a basic dye. Various dyes such as dyes, reactive dyes, disperse dyes, architectural dyes, soluble architectural dyes, reactive disperse dyes and oil dyes can be used. Among the above-mentioned dyes, the water-soluble dye is particularly preferable as the performance of the recording liquid.

The content of the dye in the recording liquid is determined depending on the kind of the liquid medium component, the characteristics required for the recording liquid, etc., but is generally about 0.2 to the total amount of the recording liquid. 20
wt. %, Preferably 0.5 to 10%, more preferably 1 to 5%.

The same aqueous medium as the first recording liquid can be used, but the most preferable aqueous medium composition in the second recording liquid is water and at least one organic solvent. The solvent is at least one water-soluble high-boiling point organic solvent, for example, diethylene glycol, triethylene glycol, glycerin, 1,2,6-hexanetriol, polyhydric alcohol such as thiodiglycol, and 2-pyrrolidone.

The contents of the above aqueous organic solvent and water in the recording liquid are the same as those in the first recording liquid.

As the dihydrazide compound, those similar to the first recording liquid can be used.

In addition to the above components, the second recording liquid of the present invention contains various dispersants, surfactants, viscosity modifiers, surface tension modifiers, optical brighteners, etc. depending on the intended use. Good.

Polyvinyl alcohol, celluloses, water-soluble resins and the like are suitable as the viscosity modifier, various cationic, anionic or nonionic surfactants can be used as the surfactant, and the surface tension modifier is Diethanolamine, triethanolamine and the like are preferable,
Other examples include a pH adjusting agent using a buffering agent and a fungicide.

In the case of a recording liquid used in an ink jet recording method of charging the recording liquid, an inorganic salt resistivity adjusting agent such as lithium chloride, ammonium chloride or sodium chloride is added.

Further, the second recording liquid of the present invention solves the problems of bleeding in the recording liquid and the drying and penetrability of the recorded matter when recorded on plain paper, and at the same time, good matching with the ink jet recording head is achieved. Therefore, the recording liquid itself has a physical property of having a surface tension of 30 to 68 at 25 ° C.
dyne / cm, viscosity less than 15 cp, more preferably 5 cp
It is preferably adjusted as follows.

A recording apparatus suitable for recording using the recording liquid of the present invention is a device for applying thermal energy corresponding to a recording signal to the recording liquid in the chamber of the recording head and generating droplets by the energy. Is mentioned. An example of the head configuration, which is the main part, is shown in FIGS. The head 13 is made of glass, ceramics, a plastic plate, or the like having a groove 14 for passing a recording liquid, and a heating head 15 used for heat-sensitive recording (a thin head is shown in the drawing, but is not limited to this. It can be obtained by gluing and). The heating head 15 includes a protective film 16 formed of silicon oxide or the like, aluminum electrodes 17-1 and 17-.
2. A heating resistor layer 18 made of nichrome, a heat storage layer 19, and a substrate 20 having a good heat dissipation property such as alumina.

The recording liquid 21 has a discharge orifice (fine hole) 2
2, the meniscus 23 is formed by the pressure P.

Now, 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 heats up, and bubbles are generated in the recording liquid 21 in contact therewith. The meniscus 23 is projected by the pressure, the recording liquid 21 is ejected, and the recording liquid 21 is ejected from the orifice 22 to become a recording droplet 24 and fly toward the recording medium 25. FIG. 2 shows an external view of a multi-head having a large number of heads shown in FIG. The multi-head includes a glass plate 27 having a multi-groove 26,
A heating head 28 similar to that described with reference to FIG.

Incidentally, FIG. 1A is a sectional view of the head 13 along the recording liquid flow path, and FIG. 1B is a sectional view taken along line A- of FIG.
It is a cross section at line B.

FIG. 3 shows an example of an ink jet recording apparatus incorporating such a head. In FIG. 3, 61 is
A blade as a wiping member, one end of which is held by a blade holding member to become a fixed end.
It takes the form of a lever . The blade 61 is arranged at a position adjacent to the recording area by the recording head, and in the case of this example,
The recording head is held in a protruding form in the moving path of the recording head.
Reference numeral 62 denotes a cap, which is arranged at a home position adjacent to the blade 61, and has a configuration in which it moves in a direction perpendicular to the moving direction of the recording head and comes into contact with the ejection surface to perform capping. Further, 63 is a recording liquid absorber provided adjacent to the blade 61, and like the blade 61, is held in a form protruding in the moving path of the recording head. The blade 61, the cap 62, and the absorber 63 constitute a discharge recovery unit 64, and the blade 61 and the absorber 63 remove water, dust, and dust on the surface of the recording liquid discharge port. Reference numeral 65 denotes a recording head having ejection energy generating means, which ejects a recording liquid onto a recording material facing an ejection port surface having ejection ports to perform recording, and 66 denotes a recording head 65 in which the recording head 65 is mounted. It is a carriage for moving. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected (not shown) to a belt 69 driven by a motor 68. As a result, the carriage 66 can move along the guide shaft 67, and the recording head 65 can move the recording area and its adjacent area.

Reference numeral 51 is a paper feed section for inserting a recording material, and 52 is a paper feed roller driven by a motor (not shown). With these configurations, the recording material is fed to the position facing the ejection opening surface of the recording head, and is ejected to the ejection portion provided with the ejection roller 53 as the recording progresses.

In the above structure, when the recording head 65 returns to the home position after recording is completed, the head recovery unit 64
The carriage 62 is retracted from the movement path of the recording head 65, but the blade 61 is projected in the movement path. As a result, the ejection port surface of the recording head 65 is wiped. When the cap 62 comes into contact with the ejection surface of the recording head 65 to perform capping , the cap 62 moves so as to project into the moving 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 above-mentioned position during wiping . As a result, even during this movement, the ejection port surface of the recording head 65 is wiped.

The above-mentioned movement of the recording head to the home position is performed not only at the time of completion of recording or recovery of ejection, but also at the home adjacent to the recording area at a predetermined interval while the recording head moves in the recording area for recording. The wiper is moved to the position, and the wiping is performed along with the move.

FIG. 4 shows an ink cartridge 4 containing a recording liquid supplied to the head through a recording liquid supply tube.
It is a figure which shows an example of 5. Here, 40 is an ink bag containing the recording liquid for supply, and a rubber stopper 42 is provided at the tip thereof.
Is provided. By inserting a needle (not shown) into the stopper 42, the recording liquid in the ink bag 40 can be supplied to the head. An ink absorber 44 receives the waste recording liquid.

The ink jet recording apparatus used in the present invention is not limited to the above-described head and ink cartridge which are separate bodies, and those in which the head and the ink cartridge are separate bodies as shown in FIG. 5 are also preferable. Used.

In FIG. 5, reference numeral 70 denotes an ink jet cartridge in which an ink absorber impregnated with a recording liquid is stored, and the recording liquid in the ink absorber has a head portion having a plurality of orifices. It is configured to be ejected as recording liquid droplets from 71. Reference numeral 72 is an atmosphere communication port for communicating the inside of the cartridge with the atmosphere.

The ink jet cartridge 70 is
It is used in place of the recording head 65 shown in FIG. 3 and is detachable from the carriage 66.

[0075]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 (1) Preparation of recording liquid a. Preparation of pigment dispersion

[0077]

[Table 1] Mix the above ingredients and heat to 70 ° C in a water bath,
The resin component was completely dissolved. To this solution, 10 parts of carbon black (trade name MCF88, manufactured by Mitsubishi Kasei) and 1 part of isopropyl alcohol were added, and after premixing for 30 minutes, dispersion treatment was performed under the following conditions.

[0078]

[Table 2] Further, a centrifugal separation treatment (1200 RPM, 20 minutes) was performed to remove coarse particles to obtain Dispersion Liquid 1.

B. Preparation of recording liquid

[0080]

[Table 3] The above components were mixed to obtain a recording liquid. (2) Recording The recording liquid prepared as described above was tested using an inkjet recording apparatus having an on-demand type multi-recording head that ejects the recording liquid by applying thermal energy according to a recording signal.

Example 2 (1) Preparation of recording liquid a. Preparation of pigment dispersion

[0082]

[Table 4] Mix the above ingredients and heat to 70 ° C in a water bath,
The resin component was completely dissolved. Add 15 parts of carbon black (trade name MCF88, manufactured by Mitsubishi Kasei) to this solution, and add 3
After premixing for 0 minutes, dispersion treatment was performed under the following conditions.

[0083]

[Table 5] Further, a centrifugal separation treatment (12000 RPM, 20 minutes) was performed to remove coarse particles to obtain a dispersion liquid 2.

B. Preparation of recording liquid

[0085]

[Table 6] The above ingredients were mixed and aminomethyl propanol was added to adjust the pH to 8-10. (2) Recording The recording liquid thus prepared was tested using an inkjet recording apparatus having an on-demand type multi-recording head that ejects the recording liquid by applying thermal energy according to a recording signal. Example 3 (1) Preparation of recording liquid a. Preparation of pigment dispersion

[0086]

[Table 7] Mix the above ingredients and heat to 70 ° C in a water bath.
Completely dissolve the resin component. To this solution, 11 parts of carbon black (S70, manufactured by Degussa) and 1 part of isopropyl alcohol were added, and after premixing for 60 minutes, dispersion treatment was carried out under the following conditions.

[0087]

[Table 8] Further, centrifugal separation treatment (12000 RPM, 20 minutes) was performed to remove coarse particles to obtain Dispersion Liquid 3.

B. Preparation of recording liquid

[0089]

[Table 9] The above components were mixed to prepare a recording liquid. (2) Recording The recording liquid prepared in this manner was tested using an inkjet recording apparatus having an on-demand type multi-recording head that ejects the recording liquid by applying thermoelectric energy according to the recording signal.

Comparative Examples 1 to 3 In Examples 1 to 3, no dihydrazide compound was added at the time of preparing the recording liquid, but ion-exchanged water was added instead, and the others were used. A recording test was conducted in the same manner as in.

Example 4 Evaluation of Recording Liquid and Printed Material The printed material obtained by printing on Canon NP-DRY copy paper by the above-mentioned method was evaluated in the following manner. The results are shown in Table 10. (1) Print density of printed matter The print density of the printed matter was measured by a Macbeth densitometer (TR918). (2) Fixing speed of recording liquid The printing part is printed with filter paper (trade name: No. 5C, Toyo Roshi Kaisha, Ltd.).
The product was rubbed and the time when no blur was generated was measured. (3) Rubbing the refreshing printed matter with a highlighter pen, the printing is not blurred even after rubbing 5 times. ○ The blurring occurs within 5 times, and the printing is not blurred even after rubbing 3 times. △ 1 time If it was rubbed, it was marked with X when it was printed or scratched.

[0092]

[Table 10] Examples 5 to 10 As recording liquids A to E, the components listed below were stirred for 5 hours, pH was adjusted to 7.5 with a 0.1% aqueous solution of sodium hydroxide, and the pore size was 0.22 μm. Pressure filtration was performed using a membrane filter (trade name: Fluoro Filter, manufactured by Sumitomo Electric Industries, Ltd.) to obtain recording liquids A to E of the invention.

[0093]

[Table 11]

[0094]

[Table 12]

[0095]

[Table 13]

[0096]

[Table 14]

[0097]

[Table 15]

[0098]

[Table 16] Comparative Examples 4-9 Examples 5-10 except that no dihydrazide compound was used.
Recording liquids G to L were produced in the same manner as in.

Example 11 Using the recording liquids prepared in Examples 5 to 10 and Comparative Examples 4 to 9, recording materials obtained by recording were evaluated in the following manner. The results are summarized in Table 17. (1) Evaluation of fixability 5 seconds after printing on commercially available copy paper and bond paper, 10
After 2 seconds, 20 seconds and 30 seconds, the printing part is printed with filter paper (Product name:
No. It was rubbed with 5C, manufactured by Toyo Roshi Kaisha, Ltd., and evaluated as follows. However, it was evaluated under the environment of 25 ° C. and 60% RH.

∘: No blur after 5 seconds ○: No blur after 10 seconds Δ: No blur after 20 seconds ×: Blurr after 30 seconds (2) Bleeding occurrence rate Regarding the bleeding occurrence rate, commercially available copy paper and bond are used. After printing 300 dots discontinuously on paper with a printer, leave it for 1 hour or more, then count the number of dots with bleeding with a microscope and display the ratio to the total number of dots in%, as shown below. Evaluated to. However, 25 ℃,
The evaluation was performed under the environment of 60% RH.

○: 10% or less Δ: 11 to 30% × ... 31% or more (3) Clogging property Clogging property refers to the clogging property at the time of reprinting after the temporary stop of printing, which is determined by the printer. After filling the recording liquid and printing alphanumeric characters continuously for 10 minutes, stop printing and leave it for 10 minutes without a cap etc., and then print alphanumeric characters again. It was evaluated by the presence or absence of defective parts such as. However, 25 ° C, 6
It was evaluated under the environment of 0% RH.

◯ ... No defective portion from the first character Δ ... One part is scratched or missing from the first character × ... The first character cannot be printed at all. (4) Frequency Responsiveness The printed matter obtained, that is, the blurred state, the white spot state, and the defective landing point state such as splash and twist, was visually observed and evaluated as follows.

⊚: The recording liquid follows the frequency well, and neither smearing, white spots, nor defective landing points are observed in both solid printing and character printing.

◯: The state of the recording liquid following the frequency is almost good, and in character printing, blurring, white spots,
No defective landing point is observed, but slight blurring is seen in solid printing.

Δ: No smearing or white spots are observed in character printing, but defective 1st spot impact point is observed. Further, in solid printing, blurring and white spots are seen in about 1/3 of the whole solid printing.

X: In solid printing, there are many blurs and white spots, and also in character printing, there are many blurs and landing point defects.

[0107]

[Table 17]

[0108]

As described above, when it is used in the recording liquid according to the present invention, the quickness and the fixing speed of the printed matter are improved, and further, the variation of the printing density due to the difference of the recording paper is eliminated and the printing stability is improved. The recorded image can be obtained. Further, there is an effect that various problems can be solved without deteriorating characteristics such as ejection stability of the recording liquid, prevention of solidification at the head tip, and maintenance of quality of printed matter.

It is excellent in quality and good in fixability without bleeding even on plain paper such as copy paper, report paper, notebook, notepaper, bond paper, and continuous slip paper which are generally used in offices and the like. It is possible to record.

Further, according to the present invention, it is possible to obtain a recording liquid having high safety even when used in the office or home.

Furthermore, according to the recording liquid of the present invention, various problems can be solved without deteriorating other characteristics such as ejection stability of the recording liquid, solidification at the head tip, and deterioration of quality of printed matter. Have.

[Brief description of drawings]

FIG. 1A is a side sectional view showing an example of a liquid flow path of a recording head suitable for the present invention, and FIG. 1B is a sectional view taken along the line AB.

FIG. 2 is a perspective view showing one aspect of a recording head having a large number of ink ejection ports.

FIG. 3 is a perspective view showing an aspect of an inkjet recording apparatus suitable for the present invention.

FIG. 4 is a side sectional view showing an aspect of an ink cartridge.

FIG. 5 is a perspective view showing one aspect of a recording unit.

[Explanation of symbols]

13 recording head 15 heating head 21 ink 22 Discharge port 23 Meniscus 24 ink drops 25 Recording material 40 ink bags 44 ink absorber 45 ink cartridge 61 Wiping member 65 recording head 66 carriage 70 recording unit 71 Head 72 atmosphere communication hole

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akio Kashiwazaki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) Reference JP 4-57860 (JP, A) JP JP 3 -68669 (JP, A) JP-A-63-289079 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C09D 11/00-11/20 B41J 2/01-2/21 B41M 5/00

Claims (21)

(57) [Claims] 1. A pigment, (b) a water-soluble resin having a carbonyl group, (c) an aqueous medium, and (d) a compound represented by the following general formula [1], and a compound represented by the following formula [2]: compound, a styrene having two or more hydrazide groups - maleic acid resins, and at least one, for ink jet recording, characterized by containing a hydrazide group selected from the group consisting of polyacrylic acid having two or more Recording liquid; (R represents (CH ₂ ) _n or C ₆ H ₄ , and n is an integer of 0 to 10.) 2. The weight average molecular weight of the component (b) is 1.00.
The recording liquid according to claim 1, which is 0 to 30,000. 3. The weight average molecular weight of the component (b) is 3,000.
The recording liquid according to claim 2, which is 0 to 15,000. 4. The component (b) is contained in the recording liquid in an amount of 0.
The recording liquid according to claim 1, wherein the recording liquid is contained in the range of 1 to 5% by weight. 5. The recording liquid according to claim 1, wherein the component (c) is a mixed solvent of water and a water-soluble organic solvent. 6. The component (d) is contained in an amount of 0.
The recording liquid according to claim 1, wherein the recording liquid is contained in a range of 1 to 10% by weight. 7. The component (d) is contained in an amount of 0.
The recording liquid according to claim 6, which is contained in a range of 5 to 5% by weight. 8. An ink jet recording method comprising the step of applying energy to a recording liquid to eject the recording liquid from the fine holes, wherein the recording liquid according to claim 1 is used as the recording liquid. Inkjet recording method. 9. A dye having at least a carbonyl group, (b) an aqueous medium, and (c) a compound represented by the following general formula [1], a compound represented by the following chemical formula [2], and a hydrazide group styrene containing FOB - recording liquid for ink jet recording, which comprises maleic acid resin, and one compound selected from the group consisting of polyacrylic acid hydrazide groups containing 2 or more, a; ## STR3 ] (R represents (CH ₂ ) _n or C ₆ H ₄ , and n is an integer of 0 to 10.) 10. The amount of the component (a) is 0.1 with respect to the total amount of the recording liquid.
The recording liquid according to claim 9 , wherein the recording liquid is contained in an amount of 2 to 20% by weight. 11. The amount of the component (a) is 0.1 with respect to the total amount of the recording liquid.
The recording liquid according to claim 10 , wherein the recording liquid is contained in an amount of 5 to 10% by weight. 12. The component (a) is 1 relative to the total amount of the recording liquid.
The recording liquid according to claim 10 or 11 , wherein the recording liquid is contained in an amount of -5% by weight. 13. The recording liquid according to claim 9 , wherein the component (b) is a mixed solvent of water and a water-soluble organic solvent. 14. The recording liquid according to claim 9 , wherein the surface tension of the recording liquid at 25 ° C. is 30 to 68 dyn / cm. 15. The recording liquid according to claim 9 , wherein the viscosity of the recording liquid is 15 cP or less. 16. The recording liquid according to claim 15 , wherein the recording liquid has a viscosity of 5 cP or less. 17. An ink jet recording method comprising the step of applying energy to the recording liquid to eject the recording liquid from the fine holes, wherein the recording liquid according to claim 9 is used as the recording liquid. Inkjet recording method. 18. An ink cartridge comprising an ink containing portion containing ink, wherein the ink is
An ink cartridge according to any one of 7 and 9 to 16 . 19. A recording unit comprising an ink containing portion containing ink and a recording head for ejecting the ink in the ink containing portion by an inkjet method, wherein the ink is any one of claims 1 to 7 and 9 to 16. A recording unit comprising the ink according to item 1. 20. An ink jet recording apparatus comprising an ink cartridge having an ink containing portion containing ink and a recording head for ejecting the ink by an ink jet method, wherein the ink is contained in any one of claims 1 to 7 and 9. 1
7. An ink jet recording apparatus, which is the ink according to any one of 6 above. 21. An ink jet recording apparatus comprising a recording unit having an ink containing portion containing ink and a recording head for ejecting the ink by an ink jet method, wherein the ink is contained in any one of claims 1 to 7 and 9. 1
7. An ink jet recording apparatus, which is the ink according to any one of 6 above.