JPH06116522A - Recording liquid and ink jet recording using the liquid - Google Patents

Abstract

PURPOSE:To provide a recording liquid containing a water-soluble solvent, a pigment, a specific water-soluble resin, a specific compound and water, capable of forming a stable recorded image, having excellent ejection stability and suitable for ink-jet printer, etc. CONSTITUTION:The recording liquid contains (A) preferably 3-40wt.% of a water-soluble solvent (e.g. ethyl alcohol), (B) preferably 2-12wt.% of a pigment (e.g. carbon black), (C) preferably 0.1-5wt.% of a water-soluble resin having an acid value of 30-150 (e.g. acrylic acid polymer), (D) preferably 30-80wt.% of water and (E) preferably 0.02-5wt.% of a compound of formula (R1 to R4 are alkyl; m=0 and n=0 or 1<=m+n<=30; m or n is 0 when m+n=1).

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. Regarding the device.

[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 the 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, when the recorded image is rained, sweated, or has water for eating and drinking, the recorded image may be blurred or disappear.

On the other hand, stationery using a dye 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. As an example of studying dispersion stability, prevention of ink solidification at a pen tip, and prevention of abrasion of balls of a ballpoint pen for practical use of an aqueous pigment ink, Japanese Patent Laid-Open No. 58-80.
No. 368, No. 61-200182, No. 61-247774, and No. 61-27227.
No. 8, JP-A-62-568, JP-A-62-1.
No. 01671, 101672, Japanese Patent Laid-Open No. 1-2498
69, 1-301760, etc. are mentioned. Recently, ballpoint pens and markers using water-based pigment ink have come on the market as products. As an inkjet ink using a water-based pigment ink, a pigment ink using a specific water-soluble solvent and a polymer dispersant has been proposed in JP-A-56-147859 and 56-147860. In addition, JP-A-4-57859,4
-57860 and the like propose an ink that uses a pigment and a dye together.

Various methods have been proposed for this ink jet recording method, some of which have been improved and commercialized, and some of which are still being put into practical use.

In the recording head of this ink jet recording apparatus, the physical properties of the surface around the ejection port are extremely important for constantly and stably ejecting the recording liquid from the ejection port. That is, when the recording liquid flows around the outer peripheral surface of the ejection port when the recording head is used, and liquid pool occurs even in a part around the ejection port, when the recording liquid is ejected from the ejection port,
The flying direction is separated from the normal direction (predetermined direction), and good recording cannot be performed. Further, if the entire circumference around the ejection port is covered with the film of the recording liquid, a so-called splash phenomenon occurs and the recording liquid scatters, 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. In order to solve such drawbacks, the outer surface surrounding the discharge port is treated with silicone oil, arabic rubber or the like to make it water repellent or repellent (repellent liquid). As described in 31642, there have been reported many methods such as a method of coating with a cured film of a polymerization-curable coating film forming composition mainly composed of a fluorine-based polymer and a specific polymerization-curable monomer and / or oligomer. ing.

However, when the conventional water-based pigment ink is used, when a long-term printing durability test is performed, and even when the peripheral portion of the discharge port is repelled as described above, the water-based pigment ink around the discharge port is used. The above-mentioned liquid pool has occurred, and problems such as detachment of the ink from the predetermined direction and ink ejection failure have occurred. Such a problem does not occur particularly in the aqueous pigment ink. Further, conventionally, JP-A-58-67
52, JP-A-1-158083, JP-A-3-15744
Many proposals have been made to contain various acetylene glycol compounds for the purpose of improving the drying property of the recorded matter such as No. 64, but these are referred to for solving the problem of ink accumulation around the ejection port. Further, the addition of the acetylene glycol compound to the water-based pigment ink can improve the drying property and the prevention of ink accumulation, but results in a marked deterioration in the quality of the printed matter.

[0008]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a water-based pigment ink that satisfies the solved printing quality and does not cause liquid pool in the peripheral portion of the ejection port. This makes it possible to obtain a stable recorded image without lowering the print density.

[0009]

[Means and Actions for Solving the Problems]
The following is achieved by the present invention.

That is, the present invention is an ink characterized by containing a pigment in an aqueous medium, a water-soluble resin having an acid value of 30 to 150, and a compound represented by the following general formula (1). On the other hand, it is an inkjet recording method and apparatus for recording by ejecting ink as droplets from fine holes by applying energy, preferably heat energy, according to a recording signal.

[0011]

[Chemical 2] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent an alkyl group, m and n each represent an integer, and m = 0 and n = 0.
Alternatively, when 1 ≦ m + n ≦ 30 and m + n = 1, m or n is 0. ) R ₁ , R ₂ , R ₃ and R ₄ are preferably alkyl groups having 1 to ₄ carbon atoms.

The present invention will be described in detail below.

The inventors of the present invention used a compound having a specific structural formula in an aqueous pigment ink to prevent liquid pooling around the ejection openings of the recording head and to separate the ink from the predetermined direction in which the ink flies. It was found that the problems such as non-ejection of ink can be solved, a stable recorded image can be obtained, and various problems such as ink ejection stability can be solved. However, on the other hand, the addition of this compound increases the penetrability of the recording liquid into recording paper, especially plain paper,
The density and the print quality of the printed matter are significantly lowered, which is a disadvantage. Therefore, as a result of diligent studies on the relationship between the other constituents of the recording liquid, the printing density, and the printing quality, the present inventors have found that the acid value of the water-soluble resin used as the dispersant for the pigment falls within a certain range. By prescribing, it was found that preferable printing quality can be obtained even if the above compound is contained, and the present invention has been completed. In other words, a water-soluble resin with a low acid value easily aggregates on paper,
Even when this compound is contained, it is possible to improve the disturbance of the printing quality along the fiber of the paper and the remarkable reduction of the printing density due to the permeation. However, if the acid value is too low, a stable dispersion cannot be obtained. Therefore, the preferable acid value for obtaining preferable dispersion stability and printing quality is 30 to 15
It is 0. More preferably, it is 60 to 150.

In the present invention, the compound having a specific structure is an acetylene glycol compound having a structure represented by the above general formula (1). Trade names include Surfynol 440, Surfynol 465, Surfynol 4
85 (above, manufactured by Nissin Chemical Industry), acetylenol EH,
Acetylenol EL (above, Kawaken Fine Chemicals)
Etc., but not limited thereto.

The content of the compound used in the present invention in the ink is preferably 0.01 to 10% by weight, and 0.0
A more preferred range is from 2 to 5% by weight. When the content of this compound is less than 0.01% by weight, the effect of preventing liquid pool around the discharge port, which is to be improved in the present invention, is not sufficient, and when it is more than 10% by weight, the image quality is improved. And a negative effect such as a decrease in print density occurs.

Further, particularly in the present invention, the nozzle surface of the recording head may not be treated with ink, but it is more desirable and effective to treat it. When the repellant ink is not treated, the occurrence of liquid pools around the ejection openings is remarkable even in the dye-based ink. Particularly when the ink according to the present invention is used, the effect of the repellant ink-treated head is obtained. Target. The repellent ink method is not particularly limited,
For example, the head surface may be treated with silicone oil, fluorine-containing low molecular weight compounds, high molecular weight compounds and the like. As such a repellent ink agent, specifically, KP-801
(Product name, Shin-Etsu Silicon), Defencer (Product name, Dainippon Ink), CTX-105,805 (Product name, Asahi Glass), Teflon AF (Product name, DuPont) and many others. Regarding the processing method, for example,
It can be carried out by a known method such as JP-A-64-31642.

The amount of the pigment contained in the ink used in the present invention is preferably 1 to 20% by weight, more preferably 2 to 12% by weight. The pigment used in the present invention may be any pigment as long as it satisfies the above performance, but the carbon black used in the black ink is a carbon black produced by a furnace method or a channel method, which is a primary particle. Diameter 15 to 40 mμ, B
Specific surface area by ET method is 50 to 300 square m / g,
Has a DBP oil absorption of 40 to 150 ml / 100 g, a volatile content of 0.5 to 10%, and a pH value of 2 to 9;
For example, No. 2300, No. 900, MCF88,
No. 33, No. 40, No. 45, No. 52, M
A7, MA8, No. 2200B (Made by Mitsubishi Kasei)
RAVEN1255 (made in Colombia), REGAL40
0R. REGAL330R, REGAL660R, MO
GUL L (made by Cabot), Color Black
FW1, GOLOR Black FW18, Colo
r Black S170, Color Black
S150, Printex 35, Printex U
Commercially available products such as (Degussa) can be used. As the pigment used in the yellow ink, C.I.
I. Pigment Yellow 1, C.I. I. Pi
gment Yellow 2, C.I. I. Pigmen
t Yellow 3, C.I. I. Pigment Ye
low 13, C.I. I. Pigment Yellow
w 16, C.I. I. Pigment Yellow 8
3. As the pigment used as the magenta ink,
C. I. Pigment Red 5, C.I. I. Pigm
ent Red 7, C.I. I. Pigment Red
12, C.I. I. Pigment Red 48 (C
a), C.I. I. Pigment Red 48 (M
n), C.I. I. Pigment Red 57 (C
a), C.I. I. Pigment Red 112, C.I.
I. Pigment Red 122 and a pigment used as a cyan ink include C.I. I. Pigment B
lue 1, C.I. I. Pigment Blue 2,
C. I. Pigment Blue 3, C.I. I. Pi
gment Blue 15: 3, C.I. I. Pigme
nt Blue 16, C.I. I. Pigment Bl
ue 22, C.I. I. Vat Blue 4, C.I. I.
Vat Blue 6 and the like can be mentioned, but the present invention is not limited to these. In addition, those newly manufactured for the present invention can also be used. As the dispersant for dispersing the pigment in the recording liquid used in the present invention, any acid-soluble resin having an acid value of 30 to 150 can be used.
The weight average molecular weight is preferably in the range of 1,000 to 30,000. Further, it is preferably in the range of 3000 to 15000. Specifically, styrene, styrene derivatives,
Vinylnaphthalene, vinylnaphthalene derivative, α, β-
At least two or more monocarboxylic acids selected from aliphatic alcohol esters of ethylenically unsaturated carboxylic acids, acrylic acid, acrylic acid derivatives, maleic acid, maleic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, fumaric acid derivatives. A block copolymer composed of a polymer (at least one of which is a hydrophilic monomer), or a random copolymer,
Examples thereof include graft copolymers and salts thereof.
These resins are alkali-soluble type resins that are soluble in an aqueous solution in which a base is dissolved. The water-soluble resin is preferably contained in the range of 0.1 to 5% by weight with respect to the total amount of the recording liquid.

Further, in the recording liquid of the present invention, it is preferable that the entire recording liquid is adjusted to be neutral or alkaline so that the solubility of the water-soluble resin is improved and the recording property is further excellent in long-term storage stability. It is desirable because it can be a liquid.
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 7-10.

Examples of the pH adjusting agent include various organic amines such as diethanolamine and triethanolamine, inorganic alkali agents such as alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide,
Examples include organic acids and mineral acids.

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

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.

Other optional solvent components that can be used in combination include water-soluble organic solvents that are used by mixing with water, such as methyl alcohol, ethyl alcohol,
n-propyl alcohol, isopropyl alcohol, n
-Butyl alcohol, sec-butyl alcohol, t
C.sub.1-4 alkyl alcohols such as ert-butyl alcohol; amides such as dimethylformamide and dimethylacetamide; ketones or keto alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyethylene glycol; Polyalkylene glycols such as polypropylene glycol; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol,
1,2,6-hexanetriol, thiodiglycol,
Alkylene glycols in which the alkylene group such as hexylene glycol and diethylene glycol contains 2-6 carbon atoms; 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. 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 preferable.

The content of the water-soluble organic solvent in the recording liquid of the present invention is generally in the range of 3-50% by weight, preferably 3-40% by weight, based on the total weight of the recording liquid.
The water used is in the range of 10-90% by weight, preferably 30-80% 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, an antiseptic agent, etc. in order to obtain a recording liquid having desired physical properties. In addition, a commercially available water-soluble dye or the like can be added.

As a method for producing the ink of the present invention, first, a pigment is added to an aqueous solution containing at least a dispersion resin and water, stirred, and then dispersed using a dispersing means described later, and if necessary, centrifuged. Separation treatment is performed to obtain a desired dispersion liquid. Next, the compound used in the present invention and the components mentioned above are added to this dispersion liquid and stirred to prepare a recording liquid.

When an alkali-soluble resin is used,
It is necessary to add a base to dissolve the resin.

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.

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

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 type sand mill is preferable, and for example, a super mill, a sand grinder, a bead mill, an agitator mill, a grain mill, a dyno mill,
Examples include pearl mill and cobol mill (both are trade names).

In the present invention, as a method for obtaining a pigment having a desired particle size distribution, the size of the grinding media of the disperser is reduced, and the packing ratio of the grinding media is increased.
In addition, methods such as lengthening the processing 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.

A recording apparatus suitable for recording using the ink of the present invention is an apparatus for applying thermal energy corresponding to a recording signal to the ink in the chamber of the recording head and generating a droplet by the energy. To be

FIG. 1 shows an example of the head structure, which is the main part of the structure.
(A), FIG. 1 (b), and FIG. The head 13 is a glass, ceramics, or plastic plate having a groove 14 through which ink passes, and a heating head 15 used for thermal recording (thin-film head is shown in the figure, but not limited to this). It is obtained by bonding and. The heating head 15 has a protective film 1 formed of silicon oxide or the like.
6, aluminum electrodes 17-1 and 17-2, a heating resistor layer 18 formed of nichrome, a heat storage layer 19, and a substrate 20 having a good heat dissipation property such as alumina.

The ink 21 is 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 generates heat, and bubbles are generated in the ink 21 in contact therewith, and the pressure thereof is generated. Then, the meniscus 23 protrudes, the ink 21 is ejected, and becomes a recording droplet 24 from the orifice 22 and flies toward the recording medium 25. FIG. 2 shows an external view of a multi-head in which 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 ink flow path, and FIG. 1B is a cross section of FIG.
It is a cross section at line B.

FIG. 3 shows an example of an ink jet recording apparatus of the present invention incorporating such a head. In FIG. 3, reference numeral 61 denotes a blade as a wiping member, one end of which is held by a blade holding member to serve as 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, and in the case of this example, 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 an ink 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 an ejection recovery unit 64, and the blade 61 and the absorber 63 remove water, dust, and dust 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 for recording, and 66 denotes a recording head 65 mounted to move the recording head 65. It is a carriage for performing. 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 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 configuration, when the recording head 65 returns to the home position after recording is completed, the head recovery unit 64
The cap 62 is retracted from the moving path of the recording head 65, but the blade 61 is projected in the moving 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 in 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 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. 4 shows an ink cartridge 4 containing ink to be supplied to the head via an ink supply tube.
It is a figure which shows an example of 5. Here, 40 is an ink bag containing the supply ink, and a rubber stopper 42 is provided at the tip thereof.
Is provided. 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.

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 they are integrated as shown in FIG. 5 are also preferably used. To be

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

This 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.

[0046]

The present invention will be further described with reference to the following examples. In the text, parts or% are based on weight. Example 1 (Preparation of recording liquid) (Preparation of pigment dispersion liquid) Styrene-acrylic acid-ethyl acrylate copolymer 1.5 parts (Acid value 140, weight average molecular weight 5000) Monoethanolamine 1 part Ion-exchanged water 81 .5 parts Diethylene glycol 5 parts The above ingredients are mixed and heated to 70 ° C. in a water bath,
Completely dissolve the resin component. Carbon black (MCF88 manufactured by Mitsubishi Kasei) 10 newly prototyped in this solution
Parts and 1 part of isopropyl alcohol were added, premixed for 30 minutes, and then dispersed under the following conditions.

Dispersing machine Sand grinder (Igarashi Machinery Co., Ltd.) Grinding media Zirconium beads 1 mm diameter Grinding media filling rate 50% (volume) Grinding time 3 hours Further centrifugation (12000 RPM, 20 minutes) was performed to remove coarse particles. To obtain a dispersion. (Preparation of Recording Liquid) Dispersion 30 parts Glycerin 10 parts Ethylene glycol 5 parts N-methylpyrrolidone 5 parts Ethyl alcohol 2 parts Acetinol EH (manufactured by Kawaken Fine Chemicals Co., Ltd.) In the compound of formula (1),

[0048]

[Chemical 3] Compound in which m + n = 10 0.2 parts Ion-exchanged water 47.8 parts The above components were mixed to prepare a recording liquid.

The nozzle surface (face surface) of the thus prepared recording liquid was treated with a water repellent CYTOP (Asahi Glass, trade name). The test was performed using an inkjet recording apparatus having an on-demand type multi-recording head that ejects a recording liquid by applying heat energy according to a recording signal. Example 2 A head surface treatment agent (water repellent) is KP-80.
The test was performed in the same manner as in Example 1 except that the product was 1 (Shin-Etsu Silicon, trade name). Example 3 Example 1 except that the face treatment agent (water repellent) for the head was Defencer (trade name, Dainippon Ink and Chemicals)
The test was conducted in the same manner as in. Example 4 A test was conducted in the same manner as in Example 1 except that the face surface of the head was not treated with a water repellent. Example 5 (Preparation of Pigment Dispersion) Styrene-maleic acid-maleic acid half ester copolymer 4 parts (acid value 70, weight average molecular weight 12000) aminomethyl propanol 2 parts ion-exchanged water 74 parts diethylene glycol 5 parts Mix and heat to 70 ° C in a water bath,
Completely dissolve the resin component. To this solution, 15 parts of carbon black (MCF88, manufactured by Mitsubishi Kasei) was added, premixed for 30 minutes, and then dispersed under the following conditions.

Disperser Pearl Mill (manufactured by Ashizawa) Grinding media Glass beads 1 mm diameter Grinding media filling rate 50% (volume) Discharge rate 100 ml / min. Further, centrifugation treatment (12000 RPM, 20 minutes) was performed to remove coarse particles to obtain a dispersion liquid. (Preparation of Recording Liquid) The above dispersion liquid 30 parts Glycerin 8 parts Ethylene glycol 5 parts Ethanol 5 parts Surfynol 485 (manufactured by Nissin Chemical Industry Co., Ltd.)

[0051]

[Chemical 4] Compound with m + n = 30 0.3 parts Ion-exchanged water 51.7 parts The above components were mixed and adjusted to pH 8 to 10 with aminomethyl propanol.

The recording liquid prepared in this manner was treated with a water repellent CYTOP (Asahi Glass, trade name) on the nozzle surface (face surface), and thermal energy was applied in accordance with the recording signal to obtain the recording liquid. The test was conducted using an inkjet recording apparatus having an on-demand type multi-recording head for ejection. Example 6 (Preparation of recording liquid) (Preparation of pigment dispersion liquid) α-methylstyrene-methyl acrylate-acrylic acid copolymer (molecular weight 8000, acid value 95) 2.0 parts KOH 0.5 part ion-exchanged water 80.5 parts Ethylene glycol 5 parts The above ingredients are mixed and heated to 70 ° C. in a water bath,
Completely dissolve the resin component. To this solution, 11 parts of a newly produced carbon black (S170, manufactured by Degussa) and 1 part of isopropyl alcohol were added, premixed for 60 minutes, and then dispersed under the following conditions.

Disperser Sand grinder (Igarashi Kikai) Grinding media Zirconium beads 0.5 mm diameter Grinding media filling rate 70% (volume) Grinding time 10 hours Further centrifugal treatment (12000 RPM, 20 minutes) was performed to remove coarse particles. It was removed to obtain a dispersion. (Preparation of Recording Liquid) Dispersion 30 parts Glycerin 12 parts Diethylene glycol 10 parts 2-Pyrrolidone 5 parts Surfynol 465 (manufactured by Nissin Chemical Industry) In the compound of formula (1),

[0054]

[Chemical 5] Compound with m + n = 10 0.3 parts Ion-exchanged water 42.7 parts The above components were mixed to prepare a recording liquid.

The recording liquid prepared as described above is treated by applying heat energy according to a recording signal, in which the nozzle surface (face surface) is treated with a water repellent defencer (Dainippon Ink and Chemicals, trade name). The test was conducted using an inkjet recording apparatus having an on-demand type multi-recording head for ejecting a liquid. (Comparative Example) (Comparative Example 1-5) In Example 1-5, the acetylene glycol-based compound according to the present invention was not added at the time of preparing the recording liquid, and instead, ion-exchanged water was added as a recording liquid. Other tests were performed in the same manner as in Example 1-6. (Comparative Example 6) In Example 6, the .alpha.-methylstyrene-methyl acrylate-acrylic acid copolymer contained in the pigment dispersion liquid was changed to one having a molecular weight of 8000 and an acid value of 210, and otherwise the same as in the recording liquid. It was created. (Evaluation 1) Printing Density of Printed Material Using the inkjet recording apparatus described above, Canon N
Printing was performed on P-DRY copy paper, and the print density of the print was measured with a Macbeth densitometer (TR918). (Evaluation 2) Continuous printing was performed using the inkjet recording apparatus described above, and the number of sheets in which printing deviation occurred was checked. (Evaluation 3) Continuous printing was performed using the inkjet recording apparatus described above, and the number of sheets in which ink ejection failure occurred was checked. (Evaluation 4) Using the above inkjet recording device, 1
0 sheets were continuously printed, and the face surface of the recording head was observed with a microscope. When the liquid pool was generated, x was given, and when the face surface was not generated and the face surface was close to the initial state, it was given as ◯.

The results of these evaluations 1-4 are summarized in Table 1.

[0057]

[Table 1]

[0058]

As described above, when the water-based pigment ink according to the present invention is used, liquid pool does not occur at the peripheral portion of the ejection port of the recording head, the ink is ejected from a predetermined direction, the ink is not ejected, and the like. Various problems can be solved without deteriorating the problems described above and obtaining stable recorded images, and further without deteriorating other characteristics such as ink ejection stability, solidification at the head of the head, and deterioration of print quality. Has the effect that can.

[Brief description of drawings]

FIG. 1A is a cross-sectional view illustrating a configuration example of a head that ejects ink by thermal energy. (B) It is sectional drawing explaining the cut surface in the AB line of (a).

FIG. 2 is an external view illustrating a multi-head in which a large number of heads in FIG. 1A are arranged.

FIG. 3 is a perspective view illustrating an example of an apparatus for performing the inkjet recording method of the present invention.

FIG. 4 is a cross-sectional view illustrating an example of an ink cartridge.

FIG. 5 is a perspective view illustrating a recording apparatus in which a head and an ink cartridge are integrated.

[Explanation of symbols]

 13 Head 14 Groove 15 Heating Head 16 Protective Film 17-1, 17-2 Aluminum Electrode 18 Heating Resistor Layer 19 Heat Storage Layer 20 Substrate 21 Ink 22 Ejection Orifice 23 Meniscus 24 Recording Droplet 25 Recorded Body 26 Multi-groove 27 Glass Plate 28 Heating Head 40 Ink Bag 42 Plug 44 Ink Absorber 45 Ink Cartridge 51 Paper Feed Section 52 Paper Feed Roller 53 Paper Ejection Roller 61 Blade 62 Cap 63 Ink Absorber 64 Ejection Recovery Section 65 Recording Head 66 Carriage 67 Guide Axis 68 Motor 69 Belt 70 Inkjet cartridge 71 Head 72 Atmosphere communication port

 ─────────────────────────────────────────────────── --Continued front page (72) Inventor Isao Ebisawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (3)

[Claims] 1. An inkjet recording liquid for performing recording by applying energy to the recording liquid to eject the recording liquid as droplets from fine pores, wherein the recording liquid is a water-soluble solvent, a pigment, and an aqueous solution having an acid value of 30 to 150. Recording liquid containing a water-soluble resin, water, and a compound represented by the following general formula. [Chemical 1] (In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent an alkyl group, m and n each represent an integer, and m = 0 and n = 0.
Alternatively, when 1 ≦ m + n ≦ 30 and m + n = 1, m or n is 0. ) 2. An inkjet recording method for recording by applying energy to a recording liquid to eject the recording liquid as droplets from fine pores, wherein the recording liquid is a water-soluble solvent, a pigment,
An inkjet recording method comprising a water-soluble resin, water, and a compound represented by the general formula (1) according to claim 1. 3. An ink jet recording apparatus for recording by applying energy to a recording liquid to eject the recording liquid as droplets from fine holes, the recording liquid being a water-soluble solvent, a pigment,
An inkjet recording device comprising a water-soluble resin, water, and a compound represented by the general formula (1) according to claim 1.