JPH08218020A - Recording solution, method for ink-jet recording using the same and recording device therefor - Google Patents

Abstract

PURPOSE: To obtain a recording solution for ink-jet recording, having excellent fastness of an image, responsiveness of high-frequency wavelength and duration stability of delivery, providing a clear cyanic color by dispersing blue dye and blue pigment into a specific dispersant. CONSTITUTION: This recording solution contains (A) blue dye preferably C.I. Direct Blue 199 and/or a compound of formula I [Pc is a phthalocyanine nucleus; R<1> to R<3> are each H, alkyl, etc.; L is a bifunctional organic bond group; X is carbonyl or a group of formula II (Z is SR<6> , OR<6> , etc.; R<6> is H, aryl, etc.); G is a colorless organic group substituted with one or two groups selected from COSH and COOH; t+q is 3-4]}, (B) blue pigment (preferably C.I. Pigment Blue 15:3 and/or C.I. Pigment Blue 16), (C) a dispersant composed of a water-soluble surfactant (preferably an anionic surfactant such as an alkyl sulfate) and (D) water (preferably ion exchange water).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording liquid, an ink jet recording method and a recording apparatus using the same, and more particularly, a recording liquid suitable for an ink jet printer, and further ejecting the recording liquid by the action of thermal energy from an orifice of a recording head. The present invention relates to a recording method and a recording device for recording on a recording material.

[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, as an ink, a solution in which various water-soluble dyes are dissolved in water or a mixed liquid of water and an organic solvent is used. However, when a water-soluble dye is 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 ink is water-soluble, the water resistance of the recorded image often becomes a problem. That is, the recorded image is rain,
When it comes into contact with sweat or water for eating and drinking, the recorded image may bleed or disappear. In particular, it is difficult for a dye having a cyan color to satisfy both the color tone, light resistance and water resistance, and although various attempts have been made, sufficient performance has not been obtained at present.

On the other hand, stationery using a dye for ink such as a ballpoint pen has the same problem, and various aqueous pigment inks for stationery have been proposed in order to solve the problems of light resistance and water resistance. Examples of studies on dispersion stability, prevention of ink solidification at a pen tip, prevention of abrasion of balls of a ballpoint pen, etc. for practical use of an aqueous pigment ink are disclosed in JP-A-58-80368 and JP-A-58-80368. 61-20018
No. 2, JP 61-247774, and JP 6
1-272278, JP-A-62-568,
JP-A-62-101671, JP-A-62-101
No. 672, Japanese Patent Application Laid-Open No. 1-249869, Japanese Patent Application Laid-Open No. 1-301760.

Recently, ball-point pens and markers using water-based pigment inks have begun to appear on the market as products. Further, an example of a water-based pigment ink using a blue pigment is disclosed in Japanese Patent Laid-Open No.
It is shown in JP-A 1-220082, JP-A 61-247774, JP-A 62-568, and the like.

[0006]

However, when the conventional pigment ink using the blue pigment is used for ink jet recording, the fastness of the printed matter is remarkably improved as compared with the case where the dye ink is used. However, as a result of the subsequent research, there was an inconvenience that the vividness of the printed matter, which is one of the characteristics of inkjet recording, was inferior to that printed using dye ink.

In addition, some relatively vivid pigments are difficult to disperse, and when a pigment ink that has not been sufficiently dispersed is used in an ink jet printer, the ejection stability is significantly impaired. There was a flaw. Also, when using a dispersion system called pigment ink for inkjet recording, preventing solidification at the tip of the head due to leaving it for a long time is an important technical issue, and in particular, the composition of the ink is designed to be a reliable pigment ink. This is an important point to do. Furthermore, among the conventional pigment inks, although the ejection property in a relatively short time is excellent, the ejection becomes unstable when the driving conditions of the recording head are changed or when the continuous ejection is performed for a long time, Finally, there is a problem that the discharge is stopped.

The present invention solves the above-mentioned problems of the prior art, satisfies not only the water resistance and light resistance of a recorded image, but also the high frequency response capable of withstanding high-speed printing and the fluctuation of driving conditions and the like. An object of the present invention is to provide a recording liquid capable of always performing stable ejection even when used for a long time, an inkjet recording method and a recording apparatus using the recording liquid. It is another object of the present invention to provide a recording liquid in which the color tone of a recorded image can produce a clear cyan color even on plain paper.

[0009]

That is, according to the present invention, in a recording liquid containing at least a blue dye, a blue pigment, a dispersant and water, the dispersant is a water-soluble surfactant. It is a liquid.

Further, the present invention is an ink jet recording method in which ink droplets formed by an ink jet method are adhered to a recording material for recording, and the above recording liquid is applied as the ink. Is.

Further, the present invention is an ink cartridge having an ink containing portion containing ink, wherein the recording liquid is applied as the ink.

Further, according to the present invention, in a recording unit having both an ink containing portion containing ink and a head portion for ejecting the ink as an ink droplet, the above-mentioned recording liquid is applied as the ink. And the ink cartridge.

Further, according to the present invention, there is provided an ink jet recording apparatus for recording by causing ink droplets formed by an ink jet method to adhere to a recording material, the ink jet recording apparatus having the above ink cartridge or recording unit. is there.

The present invention will be described in detail below. The recording liquid of the present invention is a recording liquid containing at least a blue dye, a blue pigment, a dispersant, and water, wherein the dispersant is a water-soluble surfactant, and the present invention further provides heat energy to the recording liquid. This is an inkjet recording method in which recording is performed by ejecting ink droplets from fine holes (orifices).

The recording liquid and recording method of the present invention have particularly good compatibility with ink jet printers that use thermal energy. In order to apply a cyan-based water-based ink to an ink jet printer using thermal energy, the present inventors have dispersed blue pigments having various structures in compositions conventionally proposed for stationery and the like, and have them dispersed on various recording papers. It was applied to and the fastness and color tone were evaluated.
C. I. Pigment Blue 15: 3 and C.I. I. Pigment Blue 16 was found to exhibit good fastness and cyan shades. However, when inks containing these pigments were used in an ink jet recording apparatus utilizing heat energy, there was a problem that a remarkable obstacle was caused in ejection and a good printed matter could not be obtained.

The present inventor investigated this cause and found some factors. One is that when a pulse is applied to such conventional stationery ink, a deposit is formed on the thin-film heating resistor due to the effect of the heat, and the ink foaming is incomplete, which causes ejection disturbance or ejection failure. It is to be. Furthermore, even if no deposit is generated on the thin film resistor, foaming is incomplete, and ejection of droplets may not respond to the applied pulse, resulting in ejection failure. That is, in order to stably eject the ink from the tip of the nozzle, the ink must have the ability to foam on the thin-film resistor in a desired volume and to repeat foaming and defoaming at a desired time. I have to.

The other is ejection failure due to a pool of ink generated around the ejection port when the recording head is used. That is, when the recording head is used, the recording liquid wraps around the outer peripheral surface of the ejection port, and liquid pools occur around the ejection port. When the recording liquid is ejected from the ejection port, its flight direction is normal. In this case, the recording medium becomes separated from the direction (predetermined direction), and good recording cannot be performed. Furthermore, if the entire circumference of the discharge port is covered with the recording liquid film,
A so-called splash phenomenon occurs and the recording liquid is scattered, and stable recording cannot be performed. Alternatively,
If the liquid pool covering the ejection port becomes large, it may even become impossible to eject liquid droplets from the recording head. As described above, the conventional stationery ink does not satisfy these performances. Therefore, when the ink is filled in the ink jet recording apparatus to perform recording, various inconveniences as described above occur.

Therefore, the present inventor has conducted extensive studies to solve the above-mentioned inconveniences, and as a result, at least C.I.
I. Direct Blue 199 and / or a blue dye selected from the compounds represented by the following general formula (I), and C.I.
I. Pigment Blue 15: 3 and / or C.I. I. The object of the present invention has been achieved by using a recording liquid containing a blue pigment dispersion liquid in which a blue pigment of Pigment Blue 16 is dispersed with a water-soluble surfactant and water.

[0019]

Embedded image

(In the formula, Pc represents a phthalocyanine nucleus containing a metal, and R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group or a substituted alkenyl group, an aralkyl group or It represents a substituted aralkyl group, L represents a divalent organic bonding group, and X represents a carbonyl group or a group represented by the following formulas (1) to (3).

[0021]

[Chemical 4]

In the formula, Z represents NR ⁴ R ⁵ , SR ⁶ and OR ⁶ , Y represents a hydrogen atom, a chlorine atom, Z, SR ⁷ and OR ⁷ , and E represents a chlorine atom or a cyano group. R ⁴ , R
⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group or a substituted aralkyl group, or a nitrogen atom to which R ⁴ and R ⁵ are bonded. Together they form a 5 or 6 membered ring.
G is a colorless group (not having a color developing property) substituted by one or two groups selected from -COSH and -COOH.
Represents an organic group, and (t + q) is 3 to 4. )

Next, the first important point of the present invention is to use a water-soluble surfactant as a dispersant for the pigment. That is, when a polymer dispersant is used, the viscosity of the ink as a whole generally tends to be high, which tends to hinder the ejection performance, and is particularly preferable for high frequency response that is essential for high-speed printing. Absent. Further, as a matter of course, it is difficult to increase the print density on the recording material by increasing the pigment content from the above point. On the other hand, if a water-soluble surfactant having a relatively low molecular weight range and effective as a dispersant is used, the above problems can be solved, so that it is possible to sufficiently withstand high-speed printing. It becomes possible to record the cyan color of the density. In addition, the deposits generated on the heating resistor of the recording head are easily peeled off during printing, and this phenomenon is repeatedly peeled and removed before the foaming of the ink is adversely affected. It has been found that such discharge is possible.

The second point is that C.I. I. Direct Blue 1
99 and / or a blue dye represented by the general formula (I),
C. I. Pigment Blue 15: 3 and / or C.I.
I. Pigment Blue 16 blue pigment. As described above, this is closely related to the ejection failure due to the liquid pool of the ink generated around the ejection port of the recording head during printing. Under the driving frequency within the range of the prior art, that is, in the printing condition equivalent to 2 to 4 KHz, this problem can be avoided by the optimum selection and combination of the blue pigment, the dispersant, the main solvent, and the additive. 5K by using a water-soluble surfactant as a dispersant
Printing became possible even at a driving frequency of Hz or higher, but this time, the inconvenience occurred that the continuous stability of ejection in the high frequency region could not be satisfied due to the above problems. However,
C. I. When Direct Blue 199 and / or a blue dye represented by the general formula (I) is used in combination with the above-mentioned blue pigment, the amount of ink liquid pool generated around the ejection port of the recording head during printing is unknown, although the reason is not clear. Since the frequency of occurrence is reduced, in an inkjet recording device in which a blade is provided as a wiping member,
Since it is possible to easily remove the liquid pool of ink around the ejection port by automatic wiping under the conditions specified as a sequence or forced wiping operation, it is possible to perform well even under high-frequency driving conditions. It has become possible to maintain stable dischargeability. Moreover, the C.I. I. Since the dye represented by Direct Blue 199 and / or the general formula (I) expresses a vivid cyan color, it was found that an ink jet recording liquid having a better color tone can be obtained than when a pigment alone is used. Completed

The blue pigment used in the present invention includes
C. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 16 is a phthalocyanine pigment.

The blue dye used in the present invention is C.I. I.
A dye selected from Direct Blue 199 and / or a compound represented by the general formula (I), and specific examples of particularly preferable compounds among the compounds represented by the general formula (I) include the following formula 1). ~ 3).

[0027]

Embedded image

The total content of the blue dye and the blue pigment contained in the recording liquid of the present invention is usually preferably in the range of 1 to 20% by weight based on the total weight of the recording liquid. If it is less than 1% by weight, the density of the image becomes insufficient, and if it exceeds 20% by weight, the viscosity becomes too high and the ejection becomes unstable, which is not preferable. Further, it is preferably from 2 to 15% by weight, more preferably from 3 to 10% by weight, and in this range, there is an advantage that good images and ejection properties can be obtained.

The ratio of the blue dye to the blue pigment is preferably in the range of 10: 1 to 1:10 by weight, and if it is out of this range, good fastness and chromaticity cannot be balanced, which is not preferable. Further, it is preferably blue dye: blue pigment = 2: 1 to 1: 5, and more preferably 1: 1.
It is ˜1: 3, and in this range, there are advantages that high fastness and clear cyan color can be obtained.

Next, specific examples of the water-soluble surfactant used as a dispersant for the pigment include, for example, anionic surfactants such as higher fatty acid salts, alkyl sulfates, alkyl ether sulfates, alkyl ester sulfates, and alkylaryls. There are ether sulfates, alkyl sulfonates, sulfosuccinates, alkylallyl and alkylnaphthalene sulfonates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, alkyl aryl ether phosphates and the like.

As the cationic surfactant, alkylamine salt, dialkylamine salt, tetraalkylammonium salt, benzalkonium salt, alkylpyridinium salt,
As the amphoteric surfactant such as imidazolinium salt, betaine type, aminocarboxylic acid, etc.,

As the nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene polyoxypropylene glycol, glycerin ester, sorbitan ester, sucrose ester, polyoxyethylene ether of glycerin ester, Polyoxyethylene ether of sorbitan ester, polyoxyethylene ether of sorbitol ester, fatty acid alkanolamide, polyoxyethylene fatty acid amide, amine oxide and the like can be used.

Among these, the water-soluble surfactant preferably used in the present invention is an anionic surfactant. The water-soluble surfactant is contained in the recording liquid in an amount of 0.1 to 2% by weight, preferably 0.2 to 1% by weight.

A suitable aqueous medium for the recording liquid of the present invention is a mixed solvent of water and a water-soluble organic solvent, and the water is not ordinary water containing various ions but ion-exchanged water (deionized water). Is preferably used. The content of water in the recording liquid is usually 20 to 90% by weight,
It is preferably in the range of 30 to 80% by weight.

As other optional solvent components that can be used in combination, water-soluble organic solvents used by mixing with water include, for example, methyl alcohol, ethyl alcohol, n.
-Propyl alcohol, isopropyl alcohol, n-
Butyl alcohol, sec-butyl alcohol, ter
C1-C4 alkyl alcohols such as t-butyl alcohol: amides such as dimethylformamide and dimethylacetamide: ketones such as acetone and diacetone alcohol or ketone alcohols:

Ethers such as tetrahydrofuran and dioxane: Polyalkylene glycols such as polyethylene glycol and polypropylene glycol: ethylene glycol, propylene glycol, butylene glycol,
Alkylene glycols having an alkylene group of 2 to 6 carbon atoms such as triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol and diethylene glycol: glycerin, ethylene glycol monomethyl (or ethyl) ether , Diethylene glycol methyl (or ethyl) ether,
Lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl (or ethyl) ether:
N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3
-Dimethyl-2-imidazolidinone and the like.

Among many of these water-soluble organic solvents,
Preferred are polyhydric alcohols such as diethylene glycol and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl (or ethyl) ether.

Further, in order to obtain stable ejection, it is effective to add ethanol, isopropyl alcohol, or lower alkyl ethers of polyhydric alcohol. By adding these solvents, it is possible to more stably foam the recording liquid on the thin film resistor.

The content of the water-soluble organic solvent in the recording liquid in the present invention is in the range of 5 to 60% by weight, preferably 10 to 50% by weight based on the total weight of the recording liquid.

In addition to the above components, the recording liquid of the present invention may further contain a surfactant, an antifoaming agent, a preservative and the like other than those mentioned above in order to obtain a recording liquid having desired physical properties. can do. Further, urea, thiourea, ethylene urea or a derivative thereof may be contained as a nozzle drying inhibitor.

The bases added to the dispersion when an alkali-soluble surfactant is used as the dispersant include organic substances such as monoethanolamine, diethanolamine, triethanolamine, amine methyl propanol and ammonia. Amine or an inorganic base such as potassium hydroxide or sodium hydroxide is preferable.

On the other hand, the disperser used in the present invention may be any disperser generally used, and examples thereof include a ball mill, a roll mill and a sand mill. Among them, a high speed sand mill is preferable, For example, a super mill, a sand grinder, a bead mill, an agitator mill, a grain mill, a dyno mill, a pearl mill, a cobol mill (all are trade names) and the like can be mentioned.

In the present invention, as a method for obtaining a dispersion of a pigment having a desired particle size distribution, the size of the grinding media of the disperser is reduced, the packing ratio of the grinding media is increased, and the processing time is lengthened. Techniques such as slowing down the discharge speed and classifying with a filter or a centrifuge after crushing are used. Alternatively, a combination of these methods can be cited.

Next, the method for preparing the recording liquid of the present invention comprises:
First, a pigment dispersion liquid in which a high-concentration blue pigment is dispersed is prepared, and then a specific blue dye, a water-soluble medium and water are added to prepare a recording liquid so as to have a predetermined composition.

In the ink jet recording method using ink as the recording liquid of the present invention, a recording head having a plurality of ink ejection ports applies ink to a recording material having no ink permeability to form a recorded image. An ink jet recording method, which comprises: a first step of cleaning the surface of the recording medium; and ink droplets are ejected from a discharge port of the recording head in accordance with an image recording signal to cause the ink droplets to reach a predetermined position on the recording medium. And a third step of curing the ink applied on the recording material.

Further, in the ink jet recording method of the present invention, the second step is preferably performed by a bubble jet recording method. As a method and apparatus suitable for performing recording using ink as the recording liquid of the present invention, a method of applying a thermal energy corresponding to a recording signal to the ink in the chamber of the recording head and generating a droplet by the thermal energy And devices.

An example of the head structure which is the main part of the apparatus is shown in FIGS. 1, 2 and 3. The head 13 is a glass, ceramic, or plastic plate having a groove 14 through which ink passes, and a heating head 15 used for heat-sensitive recording (a head is shown in the drawing, but is not limited to this).
It can be obtained by closely attaching and. The heating head 15 includes a protective film 16 for forming silicon oxide and the like, and an aluminum electrode 17-1.
17-2, heating resistor layer 1 formed of nichrome or the like
8, a heat storage layer 19, and a substrate 20 having a good heat dissipation property such as alumina.

The ink 21 has a discharge orifice (fine hole) 2
2, the meniscus 23 is formed by a pressure (not shown). Now, when an electric signal is applied to the electrodes 17-1 and 17-2, a region indicated by n of the heating head 15 rapidly generates heat, and bubbles are generated in the ink 21 in contact therewith,
The meniscus 23 is projected by the pressure, the ink 21 is ejected, becomes a recording droplet 24 from the orifice 22, and is ejected toward the recording material 25.

FIG. 3 shows an external view of a multi-head in which a large number of the heads shown in FIG. 1 are arranged. The multi-head is manufactured by closely contacting a glass plate 27 having a multi-groove 26 and a heating head 28 similar to that described in FIG. FIG.
2 is a cross-sectional view of the head 13 taken along the ink flow path, and FIG. 2 is a cross section taken along the line AB of FIG.

FIG. 4 shows an example of an ink jet recording apparatus incorporating such a head. In FIG. 4, reference numeral 61 denotes a blade as a wiping member, one end of which is held by a blade holding member to become a fixed end, which is in the form of a cantilever. The blade 61 is arranged at a position adjacent to the recording area of the recording head.

Further, in the case of this example, the recording head is held in a protruding form in the moving path. 62 is a cap,
It is arranged at the home position adjacent to the blade 61,
The recording head is moved in a direction perpendicular to the moving direction to come into contact with the ejection port surface to perform capping. 6 more
Reference numeral 3 denotes an ink absorber arranged 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 an ejection recovery unit 64, and the blade 61 and the absorber 63 remove water, dust, and the like on the ink ejection port surface.

Reference numeral 65 denotes a recording head which has an ejection energy generating means and ejects ink to a recording material facing the ejection port surface where the ejection ports are arranged to perform recording, and 66 is equipped with this recording head 65. And a carriage for moving the recording head 65. The carriage 66 slidably engages 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 a position facing the ejection port surface of the recording head, and is ejected to a paper ejection unit provided with a paper ejection roller 53 as the recording progresses.

In the above structure, when the recording head 65 returns to the home position after the recording is completed, the head recovery unit 6
The fourth cap 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 movement path of the recording head.

When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are in the same positions as the above wiping positions. 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 end of recording and at the time of ejection recovery, 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. 5 is a diagram showing an example of an ink cartridge in which the ink is supplied to the head through an ink supply member, for example, a tube. Here, reference numeral 40 is an ink containing portion containing the supply ink, for example, an ink bag, and a rubber stopper 42 is provided at the tip thereof. By inserting a needle (not shown) into this stopper 42,
The ink in the ink bag 40 can be supplied to the head. An ink absorber 44 receives the waste ink. It is preferable for the present invention that the liquid contact surface of the ink containing portion is made of polyolefin, particularly polyethylene.

The ink jet recording apparatus used in the present invention is not limited to the one in which the head and the ink cartridge are separately provided as described above, but is also suitable for the one in which they are integrated as shown in FIG. Used.

In FIG. 6, reference numeral 70 denotes a recording unit, in which an ink containing portion containing ink, for example, an ink absorber is contained, and the ink in the ink absorber has a plurality of orifices. Head portion 71
It is configured to be ejected as an ink droplet from. For the present invention, it is preferable to use polyurethane as the material of the ink absorber.

Reference numeral 72 denotes an atmosphere communication port for communicating the inside of the recording unit with the atmosphere. This recording unit 70 is
It is used in place of the recording head shown in FIG. 4, and is detachable from the carriage 66.

[0061]

EXAMPLES Examples of the present invention will be described in detail below. The parts shown below are parts by weight.

Example 1 ( Preparation of Pigment Dispersion) Polyoxyethylene alkyl ether phosphoric acid 4.0 parts Monoethanolamine 1.0 part Ion-exchanged water 69.0 parts Diethylene glycol 5.0 parts The above components are mixed and water is added. Heat to 70 ℃ in a bath,
The surfactant was completely dissolved.

C. was added to this solution. I. Pigment Blue 1
After adding 20 parts of 5: 3 and 1.0 part of isopropyl alcohol and performing premixing for 30 minutes, dispersion treatment was performed under the following conditions.

Disperser: Sand grinder Grinding media: Glass beads 1 mm diameter Filling ratio of grinding media: 50% (volume) Grinding time: 3 hours Further centrifugal separation (12000 rpm, 20 minutes) was performed to remove coarse particles. It was a dispersion liquid.

(Preparation of Ink) 15 parts of the above pigment dispersion C.I. I. Direct Blue 199 2.0 parts Glycerin 15 parts Diethylene glycol 25 parts Ion-exchanged water 43 parts The above components were mixed and stirred for 1 hour to obtain an ink [A].

Example 2 ( Preparation of Ink) Pigment Dispersion of Example 1 20 parts Dye of Example 1) 2.0 parts Glycerin 15 parts Diethylene glycol 25 parts Ion-exchanged water 38 parts Mix the above ingredients and stir for 1 hour. To obtain ink [B].

Example 3 ( Preparation of ink) Pigment dispersion of Example 1 15 parts C.I. I. Direct Blue 199 1.0 part Dye of Specific Example 2) 2.0 parts Glycerin 15 parts Diethylene glycol 25 parts Ion-exchanged water 42 parts The above components were mixed and stirred for 1 hour to obtain an ink [C].

Example 4 ( Preparation of Pigment Dispersion) Polyoxyethylene alkyl ether phosphoric acid 4.0 parts Monoethanolamine 1.0 part Ion-exchanged water 69.0 parts Diethylene glycol 5.0 parts The above components are mixed and water is added. Heat to 70 ℃ in a bath,
The surfactant was completely dissolved.

C. was added to this solution. I. Pigment Blue 1
20 parts of 6 and 1.0 parts of isopropyl alcohol are added,
After premixing for 30 minutes, dispersion treatment was performed under the following conditions.

Disperser: Sand grinder Grinding media: Glass beads 1 mm diameter Packing ratio of grinding media: 50% (volume) Grinding time: 3 hours Further centrifugal treatment (12000 rpm, 20 minutes) is performed to remove coarse particles. It was a dispersion liquid.

(Preparation of Ink) 15 parts of the above pigment dispersion C.I. I. Direct Blue 199 2.0 parts Glycerin 15 parts Diethylene glycol 25 parts Ion-exchanged water 43 parts The above components were mixed and stirred for 1 hour to obtain an ink [G].

Example 5 ( Preparation of Ink) Pigment Dispersion of Example 4 20 parts Dye of Specific Example 1) 2.0 parts Glycerin 15 parts Diethylene glycol 25 parts Deionized water 38 parts Mix the above ingredients and stir for 1 hour. To obtain an ink [H].

Example 6 ( Preparation of Ink) Pigment Dispersion Liquid of Example 1 8 parts Pigment Dispersion Liquid of Example 4 7 parts Dye of Specific Example 2) 2.0 parts Glycerin 15 parts Diethylene glycol 25 parts Ion-exchanged water 43 parts The above components were mixed and stirred for 1 hour to obtain an ink [I].

Comparative Example 1 ( Preparation of Ink) Pigment Dispersion of Example 1 20 parts Glycerin 15 parts Diethylene glycol 25 parts Ion-exchanged water 40 parts The above components were mixed and stirred for 1 hour to obtain an ink [D].

Comparative Example 2 ( Preparation of Pigment Dispersion) Styrene-acrylic acid copolymer 5.5 parts (acid value 200, average molecular weight 7000) Monoethanolamine 1.0 part Ion-exchanged water 67.5 parts Diethylene glycol 5. Copy 0

The above ingredients were mixed and mixed in a water bath to 70
The mixture was heated to 0 ° C. to completely dissolve the resin component. C. I. Pigment Blue 15: 3 (20 parts) and isopropyl alcohol (1.0 part) were added, and after premixing for 30 minutes, dispersion treatment was performed under the same conditions as in Example 1.

(Preparation of Ink) 15 parts of the above pigment dispersion C.I. I. Direct Blue 199 2.0 parts Glycerin 15 parts Diethylene glycol 25 parts Ion-exchanged water 43 parts The above components were mixed and stirred for 1 hour to obtain an ink [E].

Comparative Example 3 ( Preparation of Ink) C.I. I. Direct Blue 199 3 parts Glycerin 15 parts Diethylene glycol 25 parts Ion-exchanged water 57 parts The above components were mixed and stirred for 1 hour to obtain an ink [F].

A recording apparatus having an on-demand type multi-head (product name: BJC) which applies thermal energy and ejects ink using the recording liquids (inks) of Examples 1 to 6 and Comparative Examples 1 to 3 described above. Table 1 shows the results of the following examination conducted by ejecting ink under the conditions of -600 J, manufactured by Canon Inc.) at 25 ° C / 55% RH.

T ₁ : Drive condition and ejection stability The drive voltage of the printer is set to 25V and the frequency is 2K.
The frequency response was evaluated by observing the presence or absence of print disturbance, chipping, ejection failure, etc. when the frequency was changed to 4 kHz, 4 kHz, and 6 kHz.

Good: Even under the condition of a frequency of 6 KHz, the first character is ejected cleanly, and there is almost no ejection failure, chipping, or print disturbance during continuous printing. Δ: Up to the condition of frequency 4 KHz, the first character is ejected cleanly, and there is almost no ejection failure, chipping, or print disorder during continuous printing. X: Only the condition of frequency 2 KHz ejects cleanly from the first character, and there is almost no ejection failure, chipping, or print disturbance during continuous printing.

T ₂ : Continuous ejection stability for a long time When continuous printing was performed from 1 pulse to each applied pulse number, it was observed whether ejection failure occurred due to the following two reasons. Causes 1) A large pool of ink has formed around the discharge port. 2) A large amount of deposit is generated on the thin film resistor of the print head.

◯: Up to 2 × 10 ⁸ pulses (40 hours) Almost no ejection failure due to the above cause occurred. B: Good up to 1 × 10 ⁸ pulses, but 2 × 10 ⁸
Discharge failure due to the above causes occurred before the pulse (20 hours). X: Discharge failure due to the above causes occurred up to 5 × 10 ⁷ pulses (10 hours).

T ₃ : Water resistance A sample printed on plain paper (Xerox 4024 paper) was immersed in tap water for 5 minutes, and the change in the optical density of the printed matter before and after the treatment was measured. ◯: Residual concentration of 90% or more Δ: Residual concentration of 80 to 89% ×: Residual concentration of 79% or less

T ₄ : Light resistance A sample prepared by printing on bubble jet copier paper (manufactured by Canon Inc.) was exposed to a Canon fade meter (black panel 63 ° C., humidity in chamber 75%) for 100 hours,
Change in chromaticity before and after treatment (color difference; CIELab before and after treatment)
The distance on the chromaticity coordinate of the change in chromaticity by the color specification method was measured.

◯: Color difference is 3 or less Δ: Color difference is 2.9 to 10 ×: Color difference is 11 or more

T ₅ : Color tone The sample printed on Xerox 4024 paper was visually observed.

◯: Vivid cyan color Δ: Dark cyan color

[0089]

[Table 1]

[0090]

As described above, by using the recording liquid of the present invention and the inkjet recording method and recording apparatus using the same, it is possible to provide excellent image fastness and clear cyan color. Furthermore, it is possible to provide an inkjet recording excellent in high frequency response and continuous ejection stability.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a head portion of an inkjet recording device.

FIG. 2 is a vertical cross-sectional view of a head portion of an inkjet recording device.

FIG. 3 is an external perspective view of a head in which the heads shown in FIGS. 1 and 2 are multi-headed.

FIG. 4 is a perspective view showing an example of an inkjet recording apparatus.

FIG. 5 is a vertical sectional view of an ink cartridge.

FIG. 6 is a perspective view of a recording unit.

[Explanation of symbols]

 1 Ink Tank 2 Inkjet Recording Head 3 Inkjet Recording Device 13 Head 14 Groove 15 Heating Head 16 Protective Film 17-1, 17-2 Aluminum Electrode 18 Heating Resistor Layer 19 Thermal Storage Layer 20 Substrate 21 Ink 22 Ejection Orifice 23 Meniscus 24 Small Recording Droplet 25 Recording material 26 Multi-groove 27 Glass plate 28 Heating head 40 Ink storage section 42 Plug 44 Ink absorber 45 Ink cartridge 51 Paper feeding section 52 Paper feeding roller 53 Paper ejection roller 61 Wiping member 62 Cap 63 Ink absorbing body 64 Discharge Recovery unit 65 Recording head 66 Carriage 70 Recording unit 71 Orifice tip 72 Atmosphere communication port 73 Substrate

Claims (11)

[Claims] 1. A recording liquid containing at least a blue dye, a blue pigment, a dispersant, and water, wherein the dispersant is a water-soluble surfactant. 2. The blue dye is C.I. I. The recording liquid according to claim 1, which is a dye selected from Direct Blue 199 and / or a compound represented by the following general formula (I). Embedded image (In the formula, Pc represents a phthalocyanine nucleus containing a metal, and R ¹ , R ² and R ³ are each independently a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group or a substituted alkenyl group, an aralkyl group or a substituted aralkyl group. Represents L
Represents a divalent organic bonding group, and X represents a carbonyl group or a group represented by the following formulas (1) to (3). Embedded image In the formula, Z represents NR ⁴ R ⁵ , SR ⁶ and OR ⁶ , Y represents a hydrogen atom, a chlorine atom, Z, SR ⁷ and OR ⁷ , and E represents a chlorine atom or a cyano group. R ⁴ , R ⁵ , R ⁶ , R ⁷
Are each independently a hydrogen atom, an alkyl group, a substituted alkyl group,
It represents an aryl group, a substituted aryl group, an aralkyl group, a substituted aralkyl group, or forms a 5-membered ring or a 6-membered ring together with the nitrogen atom to which R ⁴ and R ⁵ are bonded. G is -COSH
And a colorless organic group substituted by one or two groups selected from —COOH, and (t + q) is 3 to 4
Is. ) 3. The blue pigment is C.I. I. Pigment Blue 15: 3 and / or C.I. I. Pigment Blue 1
The recording liquid according to claim 1, which is 6. 4. The recording liquid according to claim 1, wherein the water-soluble surfactant is an anionic surfactant. 5. The recording liquid according to claim 1, wherein the weight ratio of the blue dye to the blue pigment is in the range of 10: 1 to 1:10. 6. An inkjet recording method for recording by recording ink droplets formed by an inkjet method on a recording material, wherein the recording liquid according to any one of claims 1 to 5 is applied as the ink. An inkjet recording method characterized by the above. 7. The ink jet recording method according to claim 6, wherein the ink jet method is a method in which thermal energy is applied to the ink. 8. An ink cartridge having an ink containing portion containing ink, wherein the recording liquid according to any one of claims 1 to 5 is applied as the ink. 9. A recording unit having both an ink containing section containing ink and a head section for ejecting the ink as ink droplets, wherein the ink is the ink according to any one of claims 1 to 5. An ink cartridge characterized by applying a recording liquid. 10. The recording unit according to claim 9, wherein ink is ejected by applying thermal energy to the ink in the head portion. 11. An inkjet recording apparatus for recording by recording ink droplets formed by an inkjet method on a recording material, comprising the ink cartridge or the recording unit according to any one of claims 8 to 10. An inkjet recording device characterized by the above.