JPH06107991A - Recording liquid, ink-jet recording method and recording apparatus using the liquid - Google Patents

Abstract

PURPOSE:To provide a water-base pigment ink giving satisfiable printing image quality by ink-jet recording apparatus and usable without forming a liquid stagnation near the ejection nozzle. CONSTITUTION:The recording liquid contains a water-soluble solution, a pigment, a water-soluble resin, water and a surfactant selected from among phosphoric acid ester-type surfactant, fluorine-containing surfactant, boron-containing surfactant and polyoxyethylene alkyl ether-type or polyoxyethylene alkenyl ether-type surfactant.

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 a recording device for recording the recording liquid on the paper by ejecting the recording liquid from the orifice of the recording head by the action of energy, preferably thermal energy. Regarding

[0002]

2. Description of the Related Art The ink jet recording system produces less noise during recording, and by using a highly integrated head,
It has an advantage that a high-resolution recorded image can be obtained at high speed. In such an ink jet recording system, in many cases, a dye obtained by dissolving various water-soluble dyes in water or a mixed liquid of water and an organic solvent is used as an ink. However, when a water-soluble dye is used, the light resistance of the recorded image often becomes a problem later because the light resistance of these water-soluble dyes is poor. Further, since the ink is water-soluble, the water resistance of the recorded image often becomes a problem. That is, when the recorded image is exposed to rainwater, sweat, water for drinking, or the like, the recorded image may blur or disappear.

On the other hand, stationery using a dye such as a ballpoint pen as an inkjet dye also has the same problem. In order to solve the problems of light resistance and water resistance, various aqueous pigment inks for stationery have been proposed. . For practical use of water-based pigment inks, JP-A-58-80368 and JP-A-61-20 are examples of studying dispersion stability, prevention of ink solidification at the pen tip, and prevention of abrasion of balls of a ballpoint pen.
0182, JP-A-61-247774, JP-A-61-2
72278, JP-A-62-568, JP-A-62-101
671, JP-A-62-101672, JP-A-1-249
869, JP-A-1-301760 and the like. Recently, ballpoint pens and markers using water-based pigment ink have come to the market as products. As an ink jet ink using a water-based pigment ink, pigment inks using a specific water-soluble solvent and a polymer dispersant have been proposed in JP-A-56-147859 and JP-A-56-147860. In addition, JP-A-4-57859 and JP-A-4-57859
For example, -57860 has been proposed as an ink using a pigment and a dye in combination.

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

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.
In other words, when the recording liquid is used around the outer surface of the ejection port when the recording head is used and liquid pools are generated even in a part around the ejection port, when the recording liquid is ejected from the ejection port, the flight direction of the recording liquid is reduced. 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 a 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 be impossible to eject liquid droplets from the recording head.

In order to solve such a drawback, the outer surface surrounding the discharge port is treated with silicone oil, arabic rubber or the like to make it water-repellent or oil-repellent (liquid repellent).
Further, as described in, for example, JP-A-64-31642, a cured film of a composition for forming a polymerization-curable coating film mainly containing a fluorine-based polymer and a specific polymerization-curable monomer and / or oligomer is used. Many methods for coating the part have been reported. However, when a long-term printing durability test is performed using a conventional water-based pigment ink, liquid pool of the water-based pigment ink is generated around the ejection port even when the liquid repellent treatment is performed around the ejection port as described above. As a result, problems such as the ink flying direction deviating from the predetermined direction and the ink ejection failure occur. However, such a problem did not occur particularly in the aqueous dye ink.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aqueous pigment ink that satisfies the printing quality and does not cause liquid pool in the peripheral area of the discharge port. That is, it is possible to obtain a stable recorded image without lowering it.

[0008]

The above objects are achieved by the present invention described below.

That is, the present invention relates to a surfactant containing a pigment, a water-soluble resin, a phosphoric acid ester-based surfactant represented by the following general formula (1), and a fluorine represented by the following general formula (2) in an aqueous medium. A surfactant containing boron represented by the following general formula (3), and a surfactant containing polyoxyethylene alkyl ether or polyoxyethylene alkenyl ether represented by the following general formula (4). An ink jet recording method in which the ink is ejected as droplets from the fine pores by applying energy corresponding to a recording signal, preferably thermal energy, to such ink to perform recording.

[0010]

[Chemical 5] However, M = hydrogen, ammonium, Na, Li, K m = 1 to 18, x = 8 to 18, y + z = 8 to 18 (m,
x, y, z are integers),

[0011]

[Chemical 6] However, M = Na, K, Li, ammonium, hydrogen n = 1 to 15 integer

[0012]

[Chemical 7] However, R = C _{7 to} C ₂₁ alkyl group n, m = 1 to 20 integer

[0013]

[Chemical 8] However, x = 12 to 18 y = ± 1 z = 10 to 20 The present inventors use the compound having a specific structural formula in the aqueous pigment ink to generate a liquid pool around the ejection port of the recording head. In addition, it is possible to solve the problems that the ink is separated from the predetermined flight direction and the ink is not ejected. As a result, it becomes possible to obtain a stable recorded image. Further, it has been found that various other problems can be solved without deteriorating other characteristics such as ink ejection stability, solidification at the head of the head, deterioration of quality of printed matter, and the present invention has been completed. It was

In the present invention, the compound having a specific structure is a phosphate ester type surfactant having a structure represented by the above general formula (1). Specific examples thereof include sodium polyoxyethylene lauryl ether phosphate, sodium polyoxyethylene cetyl ether phosphate, sodium polyoxyethylene oleyl ether phosphate, and the like. Product name: Toho Chemical Co., Ltd. PHOSPHA
Examples thereof include NOL series and NIKKOL series manufactured by Nikko Chemicals Co., Ltd., but are not particularly limited thereto.

In the present invention, the compound having a specific structure is a perfluoroalkylsulfonic acid compound having a structure represented by the above general formula (2). Trade names include Florard FC-93, Florard FC-95, Florard FC-98, Florard FC-129 (above 3M), Unidyne DS-101, Unidyne DS-10.
2 (all manufactured by Daikin), Surflon S-111, Surflon S-113 (all manufactured by Asahi Glass Co., Ltd.), MEGAFA
CF-144 (manufactured by Dainippon Ink and Chemicals, Inc.) can be mentioned, but the invention is not limited thereto.

In the present invention, the compound having a specific structure is an organic boron compound having a structure represented by the above general formula (3). A compound having a structure of n + m = 20 to 30 is particularly preferable. Specifically, polyoxyethylene glycerol borate-laurate, polyoxyethylene glycerol borate-palmitate, polyoxyethylene glycerol borate-stearate, polyoxyethylene glycerol borate-oleate, polyoxyethylene glycerol borate-isostearate, etc. Can be mentioned. The product name may be Emalbon T series manufactured by Toho Chemical Industry Co., Ltd., but is not particularly limited thereto.

In the present invention, the compound having a specific structure is a polyoxyethylene alkyl ether or a polyoxyethylene alkenyl ether having a structure represented by the above general formula (4). Specific examples thereof include polyoxyethylene oleyl ether and polyoxyethylene lauryl ether. These are generally used as nonionic anionic surfactants.
The trade names are Neugen ET series manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., such as Neugen ET-140E and -150E,
Same-180E, Same-149, Same-160, and Kao Corporation's Emulgen series, such as Emulgen 12
No. 0, No. 147, No. 123P, No. 130K, No. 430, etc., but not particularly limited thereto.

The content of the compound used in the present invention in the ink is preferably 0.001 to 10% by weight, and 0.01
The range of 5 wt% is more preferable. When the content of this compound is less than 0.001% by weight, the effect of preventing liquid pool around the discharge port, which is to be improved in the present invention, is somewhat insufficient, and when it is more than 10% by weight, the image quality deteriorates. In addition, adverse effects such as a decrease in print density occur.

Further, in particular, in the present invention, the nozzle surface of the recording head may be untreated with ink repellent, but it is more desirable and effective to have treated it. In the case where the ink repellent treatment is not performed, even in the dye-based ink, the liquid pool around the ejection port is remarkably generated. Especially, when the ink according to the present invention is used, it is effective for the head subjected to the ink repellent treatment. The ink repellent method is not limited to a particular method, and examples thereof include treating the head surface with silicon oil, fluorine-containing low molecular weight compounds, high molecular weight compounds, and the like. Specific examples of such an ink repellent agent include KP-801.
(Trade name, manufactured by Shin-Etsu Silicon Co., Ltd.), Defencer (trade name, manufactured by Dainippon Ink Co., Ltd.), CTX-105,805 (trade name, manufactured by Asahi Glass Co., Ltd.), Teflon AF (trade name, manufactured by DuPont), and many others. Is mentioned. The treatment method can be performed 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. As the pigment used in the present invention, any pigment can be used as long as it satisfies the above performance, but the carbon black used in the black ink is a carbon black produced by the furnace method or the channel method. , Primary particle size is 15-40m
μ, specific surface area by BET method is 50 to 300 m ² / g,
It 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. 2
300, No.900, MCF88, No.33, No.40, No.45, No.52, MA
7, MA8, No.22008 (Made by Mitsubishi Kasei), RAVEN1255
(Made in Colombia), REGAL400R, REGAL33OR, REGAL660R,
MOGULL (made by Cabot), Color Black FW1, Color
Black FW18, Color Black S170, Color Black S150, Pri
Commercially available products such as ntex 35 and Printex U (manufactured by Degussa) can be used.

As the pigment used in the yellow ink,
CI Pigment Yellow 1, CI Pigment Yellow 2, CI P
igment Yellow 3, CI Pigment Yellow 13, CI Pigm
entYellow 16, CI Pigment Yellow 83, CI Pigment Red 5, as a pigment used as magenta ink
CI Pigment Red 7, CI Pigment Red 12, CI Pig
ment Red 48 (Ca), CI Pigment Red 48 (Mn), CI
Pigment Red 57 (Ca), CI Pigment Red 112, CI Pig
ment Red 122, CI Pigment Blue 1, CI Pigment Blue 2, CI
Pigment Blue3, CI Pigment Blue 15: 3, CI Pigme
nt Blue 16, CI Pigment Blue 22, CI Vat Blue 4,
Examples include CI Vat Blue 6 but are not limited to these. In addition, those newly manufactured for the present invention can also be used. As the dispersant for the pigment of the recording liquid used in the present invention, any water-soluble resin can be used, but the weight average molecular weight is preferably in the range of 1000 to 30000, more preferably 3000 to 15000.
Is the range. Specifically, styrene, styrene derivatives,
Vinylnaphthalene, vinylnaphthalene derivative, α, β-
At least 2 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, etc.
Block copolymer consisting of one or more monomers (at least one of which is a hydrophilic monomer), or random
Examples thereof include graft copolymers and salts thereof.
These resins are alkali-soluble resins that are soluble in an aqueous solution in which a base is dissolved. Further, a homopolymer composed of a hydrophilic monomer or a salt thereof may be used. In addition, polyvinyl alcohol, carboxymethyl cellulose,
Water-soluble resins such as naphthalene sulfonic acid formaldehyde condensate can also be used. However, when an alkali-soluble resin is used, there is an advantage that the viscosity of the dispersion liquid can be reduced and the dispersion is easy. Further, a resin which starts aggregation at pH 6 or less is particularly preferable for improving the printing density. The water-soluble resin is preferably contained in the recording liquid in an amount of 0.1 to 5% by weight.

Furthermore, the recording liquid of the present invention is preferably adjusted so that the entire recording liquid is neutral or alkaline, thereby improving the solubility of the water-soluble resin and providing a recording liquid having further excellent long-term storage stability. So desirable. However, in this case,
Since it may cause corrosion of various members used in the inkjet recording apparatus, it is preferably pH 7 to 1.
The range of 0 is desirable.

Examples of the pH adjusting agent include various organic amines such as diethanolamine and triethanolamine, inorganic alkali agents such as sodium hydroxide, lithium hydroxide, potassium hydroxide and other alkali metal hydroxides, and organic acids. And mineral acids. The pigment and water-soluble resin as described above are dispersed or dissolved in an aqueous medium. The preferred aqueous medium of the recording liquid of the present invention is a mixed solvent of water and a water-soluble organic solvent, and the water used is not ordinary water containing various ions but ion-exchanged water (deionized water). Is preferred.

Any other solvent component which can be used in combination is a water-soluble organic solvent used by mixing with water, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
C1-C4 alkyl alcohols such as sec-butyl alcohol and tert-butyl alcohol; amides such as dimethylformamide and dimethylacetamide; ketones or ketone alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane. Polyalkylene glycols such as polyethylene glycol and polypropylene glycol; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol,
Alkylene glycols in which the alkylene group such as diethylene glycol contains 2 to 6 carbon atoms; glycerin; ethylene glycol monomethyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether, etc. Lower alkyl ethers of polyhydric alcohols; 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 preferable.

Further, in order to obtain the ejection stability, it is effective to add ethanol or isopropyl alcohol in an amount of 1% or more. It is considered that the reason is that the addition of these solvents makes it 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 of the present invention is generally in the range of 3 to 35% by weight, preferably 3 to 40% by weight, based on the total weight of the recording liquid. The amount of water used is 10 to 90% by weight, preferably 30 to 80% by weight, based on the total weight of the recording liquid.

Further, in order to make the recording liquid of the present invention into a recording liquid having desired physical properties, a surfactant, an antifoaming agent, a preservative and the like can be added as necessary in addition to the above components. ,
Further, a commercially available water-soluble dye or the like can be added. As the surfactant, the organic phosphoric acid compound used in the present invention also plays this role, but it is also possible to use another surfactant in combination. These surfactants are not particularly limited as long as they do not have an adverse effect on the ink such as storage stability. For example, fatty acid salts,
Anionic surfactants such as higher alcohol sulfate ester salts, liquid fatty oil sulfate ester salts, alkylallyl sulfonates, polyoxyethylene alkyl ethers,
There are nonionic surfactants such as polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, acetylene alcohol, and acetylene glycol, and one or more of these can be appropriately selected and used. The amount used depends on the dispersant,
0.01 to 5% by weight is desirable with respect to the total amount of ink.

As a method for producing the ink of the present invention, a dispersion resin is dissolved in water or a mixed solvent containing water, a pigment is further added, and after stirring, dispersion is carried out using a dispersion means described later,
Centrifugation treatment is performed as necessary to obtain a desired dispersion liquid. Next, the compound used in the present invention and the above components are added to this dispersion, and the mixture is 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 pre-micking operation improves the wettability of the pigment surface and promotes adsorption on the pigment surface.

As the bases added to the dispersion when an alkali-soluble resin is used, monoethanolamine,
Organic amines such as diethanolamine, triethanolamine, amine methyl propanol and ammonia, and inorganic bases such as potassium hydroxide and sodium hydroxide are 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 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 decreased, the packing ratio of the grinding media is increased, the processing time is lengthened, and the discharge speed is decreased. A method such as classifying with a filter or a centrifuge after crushing is used. Alternatively, a combination of those methods may be used.

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. .

FIG. 1 shows an example of the configuration of the head, which is the main part
(A), (b), it shows in FIG. The head 13 is made by adhering glass, ceramics, or a plastic plate having a groove 14 through which ink is passed, and a heating head 15 (thin film head is shown in the figure, but not limited to this) used for thermal recording. Obtained. The heating head 15 includes a protective film 16 made of silicon oxide, 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. Has become

The ink 21 is a discharge orifice (fine hole) 2
2 and the pressure P forms the meniscus 23.

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 ink 21 which is in contact with the area. The meniscus 23 protrudes, the ink 21 is ejected, and the recording droplet 2 becomes a recording droplet 24 from the orifice 22.
Fly toward 5. 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 multi-grooves 26, and FIG.
The heating head 28 similar to that described in FIG.

1A is a sectional view of the head 13 taken along the ink flow path, and FIG. 1B is a sectional view taken along the line AB of FIG. 1A.
It is a cutting plane along a line. 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 the cantilever is held by the blade holding part and becomes a fixed end. The blade 61 is arranged at a position adjacent to a 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 an ink absorber provided adjacent to the blade 61, and is held in a form projecting in the moving path of the recording head like the blade 61. The blade 61, the cap 62, and the absorber 63 form an ejection recovery unit 64, and the blade 61 and the absorber 63 remove water, dust, and the like from the ink ejection port surface. Reference numeral 65 denotes a recording head which has 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 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected to a belt 69 (not shown) 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 the area adjacent to the recording area. Reference numeral 51 is a paper feed unit 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, the head recovery unit 6 is used when the recording head 65 returns to the home position after recording is completed.
The carriage 62 of No. 4 is retracted from the moving path of the recording head 65, but the blade 61 is projected in the moving path. Therefore, 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 positions as the above-described position during wyoing. As a result, even in this movement, the recording head 6
The ejection port surface of 5 is wiped. The above-described 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 position adjacent to the recording area at a predetermined interval while the recording head moves in the recording area for recording. The wiping is performed along with this movement.

FIG. 4 shows an ink cartridge 4 containing ink to be supplied to the head through an ink supply tube.
It is a figure which shows an example of 5. Reference numeral 40 in this figure is an ink bag containing the supply ink, and a rubber stopper 4 is provided at the tip thereof.
Two are 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 one in which the head and the ink cartridge are separately provided as described above, and those in which they are integrated as shown in FIG. 5 are also preferably used. .

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 such ink absorber has a head having a plurality of orifices. It is configured to be ejected as an ink droplet from the portion 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 attachable to and detachable from the carriage 66.

[0044]

Examples Example 1 (Preparation of recording liquid) (Preparation of pigment dispersion liquid) Styrene-acrylic acid-butyl acrylate copolymer 1.5 parts (Acid value 116, weight average molecular weight 3700) Monoethanolamine 1 part Ion-exchanged water 81.5 parts Diethylene glycol 5 parts The above components are mixed and heated to 70 ° C. in a water bath,
Dissolve the resin completely. 10 parts of carbon black (MCF88 manufactured by Mitsubishi Kasei) newly prototyped in this solution,
After adding 1 part of isopropyl alcohol and performing premixing for 30 minutes, dispersion treatment was performed under the following conditions.

Dispersing machine Sand grinder (Igarashi Machinery) Grinding media Zirconium beads 1 mm
Diameter Filling ratio of grinding media 50% (volume) Grinding time 3 hours Further centrifugal separation processing (12000 RPM, 20 minutes) was performed to remove coarse particles to obtain a dispersion liquid.

(Preparation of Ink) Dispersion 30 parts Glycerin 2 parts Diethylene glycol 15 parts N-Methylpyrrolidone 5 parts Isopropyl alcohol 3 parts PHOSPHANOL RS-710 (manufactured by Toho Chemical Co., Ltd.) 0.01 parts Ion-exchanged water 44.99 parts The ingredients are mixed and the pH is adjusted to 8 with monoethanolamine.
It was adjusted to 10.

The ink prepared in this manner was applied to the nozzle surface (face surface) with a water repellent CYTOP (trade name of Asahi Glass Co., Ltd.).
Was processed. The test was conducted using an inkjet recording apparatus having an on-demand type multi-recording head that ejects ink by applying thermal energy according to a recording signal.

Example 2 A head surface treatment agent (water repellent) was KP-801.
The test was conducted in the same manner as in Example 1 except that the product name was (Shin-Etsu Silicon Co., Ltd.).

Example 3 Example 1 except that the head surface treatment agent (water repellent) for the head was a defender (trade name of Dainippon Ink and Chemicals, Inc.)
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 200, weight average molecular weight 12000) aminomethyl propanol 2 parts ion-exchanged water 74 parts diethylene glycol 5 parts Mix the above ingredients and heat to 70 ° C in a water bath,
Dissolve the resin completely. To this solution, 15 parts of carbon black (MCF88, manufactured by Mitsubishi Kasei Co., Ltd.) was added, and after premixing for 30 minutes, dispersion treatment was carried out under the following conditions.

Dispersing machine Pearl mill (manufactured by Ashizawa) Grinding media Zirconium beads 1 mm
Diameter Filling ratio of grinding media 50% (volume) Discharge rate 100 ml / min. Further, centrifugal separation treatment (12000 RPM, 20 minutes) was performed to remove coarse particles to obtain a dispersion liquid.

(Preparation of Recording Liquid) Dispersion 25 parts Glycerin 8 parts Ethylene glycol 5 parts Ethanol 5 parts Isopropyl alcohol 3 parts PHOSPHANOL ML-220 (manufactured by Toho Kagaku) 0.1 parts Ion-exchanged water 56.9 parts The above components Were mixed and adjusted to pH 8-10 with aminomethyl propanol.

The ink prepared in this manner was treated with a water repellent CYTOP (trade name of Asahi Glass Co., Ltd.) on the nozzle surface (face surface).
Was processed. The test was conducted using an inkjet recording apparatus having an on-demand type multi-recording head that ejects ink by applying thermal energy according to a recording signal.

Example 6 (Preparation of recording liquid) (Preparation of pigment dispersion liquid) Roma D (manufactured by San Nopco, sodium salt of naphthalene sulfonic acid) 1.5 parts Deionized water 81.5 parts Ethylene glycol 5 parts The above components are mixed. And heat to 70 ° C in a water bath,
Dissolve the resin completely. To this solution, 11 parts of a newly produced carbon black (S170, manufactured by Degussa) was added, 1 part of isopropyl alcohol was added, and after premixing for 60 minutes, a dispersion treatment was performed under the following conditions.

Dispersing machine Sand grinder (Igarashi Kikai) Grinding media Zirconium beads 0.5
mm diameter Filling ratio of grinding media 70% (volume) Grinding time 10 hours Further centrifugal separation processing (12000 RPM, 20 minutes) was performed to remove coarse particles to obtain a dispersion liquid.

(Preparation of Ink) Dispersion 30 parts Glycerin 12 parts Diethylene glycol 15 parts 2-Pyrrolidone 5 parts Isopropyl alcohol 3 parts TLP-4 (manufactured by Nikko Chemicals) 0.05 parts Ion-exchanged water 34.95 parts Mix and adjust pH to 8 with monoethanolamine
It was adjusted to 10.

The nozzle surface (face surface) of the ink thus prepared was treated with a water repellent defencer (trade name of Dainippon Ink and Chemicals, Inc.). The test was conducted using an inkjet recording apparatus having an on-demand type multi-recording head that ejects ink by applying thermal energy according to a recording signal.

Comparative Examples Comparative Examples 1 to 6 In this Comparative Example, the phosphorus-containing compound according to the present invention was not added when the inks of Examples 1 to 6 were prepared, and ion-exchanged water was added instead, and the other inks were used. Was tested in the same manner as in Examples 1 to 6.

Evaluation Method (Evaluation 1) Printing Density of Printed Material Using the inkjet recording apparatus described above, 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 above-mentioned ink jet recording apparatus, and the number of sheets in which printing deviation occurred was checked.

(Evaluation 3) Continuous printing was performed using the above-mentioned ink jet recording apparatus, and the number of sheets in which no ink ejection occurred was checked.

(Evaluation 4) 10 sheets were continuously printed using the above-mentioned ink jet recording apparatus, and the face surface of the recording head was observed with a microscope. When the face surface was close to the initial state, it was marked as ○.

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

[0064]

[Table 1] Example 7 (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 0.5 parts Diethylene glycol 5 parts The above ingredients are mixed and heated to 70 ° C. in a water bath,
Dissolve the resin completely. 10 parts of carbon black (MCF88 manufactured by Mitsubishi Kasei) newly prototyped in this solution,
After adding 1 part of isopropyl alcohol and performing premixing for 30 minutes, dispersion treatment was performed under the following conditions.

Dispersing machine Sand grinder (made by Igarashi Machinery) Grinding media Zirconium beads 1 mm
Diameter Filling ratio of grinding media 50% (volume) Grinding time 3 hours Further centrifugal separation processing (12000 RPM, 20 minutes) was performed to remove coarse particles to obtain a dispersion liquid.

(Preparation of Recording Liquid) Dispersion 30 parts Glycerin 10 parts Ethylene glycol 5 parts N-Methylpyrrolidone 5 parts Isopropyl alcohol 2 parts Florard FC-93 0.2 parts Ion-exchanged water 47.8 parts Mix the above components Then, a recording liquid was prepared.

The recording liquid thus prepared was treated with a water repellent agent CYTOP (trade name of Asahi Glass Co., Ltd.) on the nozzle surface (face surface).
Was processed. 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 8 A head surface treating agent (water repellent) was KP-801.
The test was conducted in the same manner as in Example 1 except that the product name was (Shin-Etsu Silicon Co., Ltd.).

Example 9 Example 1 except that the head surface treatment agent (water repellent) for the head was a defender (trade name of Dainippon Ink and Chemicals, Inc.)
The test was conducted in the same manner as in.

Example 10 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 11 (Preparation of Pigment Dispersion) Styrene-maleic acid-maleic acid half ester copolymer 4 parts (acid value 200, weight average molecular weight 12000) aminomethyl propanol 2 parts ion-exchanged water 74 parts diethylene glycol 5 parts Mix the above ingredients and heat to 70 ° C in a water bath,
Dissolve the resin completely. To this solution, 15 parts of carbon black (MCF88, manufactured by Mitsubishi Kasei Co., Ltd.) was added, and after premixing for 30 minutes, dispersion treatment was carried out 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) Dispersion 25 parts Glycerin 8 parts Ethylene glycol 5 parts Ethanol 5 parts MEGAFAC F-144 0.3 parts Ion-exchanged water 56 parts The above components are mixed to give a pH of 8-10. As such, it was adjusted with aminomethyl propanol.

The recording liquid prepared in this manner was treated with a water repellent CYTOP (a product name of Asahi Glass Co., Ltd.) on the nozzle surface (face surface).
Was processed. 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 12 (Preparation of Recording Liquid) (Preparation of Pigment Dispersion) Orotane SN (manufactured by Rohm and Haas) 1.5 parts Ion-exchanged water 81.5 parts Ethylene glycol 5 parts The above components were mixed and mixed in a water bath. Heat to 70 ° C with
Dissolve the resin completely. To this solution, 11 parts of a newly produced carbon black (S170, manufactured by Degussa) was added, 1 part of isopropyl alcohol was added, and premixing was performed for 60 minutes, and then a dispersion treatment was performed under the following conditions.

Dispersing machine Sand grinder (Igarashi Kikai) Grinding media Zirconium beads 0.5
mm diameter Filling ratio of grinding media 70% (volume) Grinding time 10 hours Further centrifugal separation processing (12000 RPM, 20 minutes) was performed to remove coarse particles to obtain a dispersion liquid.

(Preparation of Ink) Dispersion 30 parts Glycerin 12 parts Diethylene glycol 10 parts 2-Pyrrolidone 5 parts Surflon S-111 0.3 parts Ion-exchanged water 42.7 parts The above components were mixed to prepare a recording liquid.

The ink thus prepared was treated on the nozzle surface (face surface) with a water repellent defencer (trade name of Dainippon Ink and Chemicals, Inc.). The test was conducted using an inkjet recording apparatus having an on-demand type multi-recording head that ejects ink by applying thermal energy according to a recording signal.

Comparative Examples Comparative Examples 7 to 12 In this comparative example, the inks of Examples 7 to 12 were prepared by adding the ion-exchanged water instead of adding the fluorine compound according to the present invention. Others were tested in the same manner as in Examples 7 to 12.

The evaluation methods are as follows: Examples 1 to 6 and Comparative Examples 1 to 1.
It is the same as the evaluation method of 6.

The results of these evaluations 1 to 4 are summarized in Table 2.

[0082]

[Table 2] Example 13 (Preparation of recording liquid) (Preparation of pigment dispersion liquid) Styrene-acrylic acid-butyl acrylate copolymer 1.5 parts (Acid value 116, weight average molecular weight 3700) Monoethanolamine 1 part Ion-exchanged water 81 0.5 parts Diethylene glycol 5 parts The above ingredients are mixed and heated to 70 ° C. in a water bath,
Dissolve the resin completely. To this solution, 10 parts of a newly produced carbon black (MCF88 manufactured by Mitsubishi Kasei) was added, 1 part of isopropyl alcohol was added, premixing was performed for 30 minutes, and then a dispersion treatment was performed under the following conditions.

Dispersing machine Sand grinder (Igarashi Kikai) Grinding media Zirconium beads 1 mm
Diameter Filling ratio of grinding media 50% (volume) Grinding time 3 hours Further centrifugal separation processing (12000 RPM, 20 minutes) was performed to remove coarse particles to obtain a dispersion liquid.

(Preparation of Ink) Dispersion 30 parts Glycerin 2 parts Diethylene glycol 15 parts N-methylpyrrolidone 5 parts Isopropyl alcohol 3 parts Emulbon T-83 0.5 parts Ion-exchanged water 44.5 parts The above components are mixed, pH 8 with monoethanolamine
It was adjusted to 10.

The ink prepared as described above was applied to the nozzle surface (face surface) with a water repellent CYTOP (trade name of Asahi Glass Co., Ltd.).
Was processed. The test was conducted using an inkjet recording apparatus having an on-demand type multi-recording head that ejects ink by applying thermal energy according to a recording signal.

Example 14 A head surface treatment agent (water repellent) was KP-801.
The test was conducted in the same manner as in Example 1 except that the product name was (Shin-Etsu Silicon Co., Ltd.).

Example 15 Example 1 except that the head surface treatment agent (water repellent) was a defender (trade name of Dainippon Ink and Chemicals, Inc.)
The test was conducted in the same manner as in.

Example 16 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 17 (Preparation of pigment dispersion liquid) Styrene-maleic acid-maleic acid half ester copolymer 4 parts (acid value 200, weight average molecular weight 12000) aminomethyl propanol 2 parts ion-exchanged water 74 parts diethylene glycol 5 parts Mix the above ingredients and heat to 70 ° C in a water bath,
Dissolve the resin completely. To this solution, 15 parts of carbon black (MCF88, manufactured by Mitsubishi Kasei Co., Ltd.) was added, and after premixing for 30 minutes, dispersion treatment was carried out 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) Dispersion 25 parts Glycerin 8 parts Ethylene glycol 5 parts Ethanol 5 parts Emulbon T-60 1 part Ion-exchanged water 56 parts The above components are mixed to adjust the pH to 8-10. Adjusted with aminomethyl propanol.

The ink prepared as described above was applied to the nozzle surface (face surface) with a water repellent CYTOP (trade name of Asahi Glass Co., Ltd.).
The test was conducted using an inkjet recording apparatus having an on-demand type multi-recording head that ejects ink by applying thermal energy according to the recording signal.

Example 18 (Preparation of recording liquid) (Preparation of pigment dispersion liquid) Roman D (manufactured by San Nopco, sodium salt of naphthalene sulfonic acid) 1.5 parts Ion-exchanged water 81.5 parts Ethylene glycol 5 parts Mixing the above components And heat to 70 ° C in a water bath,
Dissolve the resin completely. To this solution, 11 parts of a newly produced carbon black (S170, manufactured by Degussa) was added, 1 part of isopropyl alcohol was added, and after premixing for 60 minutes, a dispersion treatment was performed under the following conditions.

Disperser Sand grinder (Igarashi Kikai) Grinding media Zirconium beads 0.5
mm diameter Filling ratio of grinding media 70% (volume) Grinding time 10 hours Further centrifugal separation processing (12000 RPM, 20 minutes) was performed to remove coarse particles to obtain a dispersion liquid.

(Preparation of Ink) Dispersion 30 parts Glycerin 12 parts Diethylene glycol 15 parts 2-Pyrrolidone 5 parts Isopropyl alcohol 3 parts Emulbon T-83 0.3 parts Ion-exchanged water 34.7 parts The above components are mixed and pH is added. 8 with monoethanolamine
It was adjusted to 10.

The ink thus prepared is treated on the nozzle surface (face surface) with a water repellent defencer (trade name of Dainippon Ink and Chemicals, Inc.), and thermal energy is applied according to a recording signal to eject the ink. The test was conducted using an inkjet recording apparatus having an on-demand type multi-recording head.

Comparative Examples Comparative Examples 13 to 18 In this Comparative Example, the inks of Examples 13 to 18 were prepared by adding the ion-exchanged water instead of adding the organic boron compound according to the present invention. Other tests were performed in the same manner as in Examples 13 to 18.

The evaluation methods are as follows: Examples 1 to 6 and Comparative Examples 1 to 1.
The same evaluation method as in No. 6 is used.

Table 3 shows the results of these evaluations 1 to 4.

[0100]

[Table 3] Example 19 (Preparation of recording liquid) (Preparation of pigment dispersion liquid) Styrene-acrylic acid-butyl acrylate copolymer 1.5 parts (Acid value 116, weight average molecular weight 3700) Monoethanolamine 1 part Ion-exchanged water 81 0.5 parts Diethylene glycol 5 parts The above ingredients are mixed and heated to 70 ° C. in a water bath,
Dissolve the resin completely. 10 parts of carbon black (MCF88 manufactured by Mitsubishi Kasei) newly prototyped in this solution,
After adding 1 part of isopropyl alcohol and performing premixing for 30 minutes, dispersion treatment was performed under the following conditions.

Dispersing machine Sand grinder (Igarashi Kikai) Grinding media Zirconium beads 1 mm
Diameter Filling ratio of grinding media 50% (volume) Grinding time 3 hours Further centrifugal separation processing (12000 RPM, 20 minutes) was performed to remove coarse particles to obtain a dispersion liquid.

(Preparation of Ink) Dispersion 30 parts Glycerin 2 parts Diethylene glycol 15 parts N-Methylpyrrolidone 5 parts Isopropyl alcohol 3 parts Neugen ET-150E (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 0.1 parts Ion-exchanged water 44.9 Parts The above ingredients were mixed and the pH was adjusted to 8 with monoethanolamine.
It was adjusted to 10.

The ink thus prepared was treated with a water repellent CYTOP (trade name of Asahi Glass Co., Ltd.) on the nozzle surface (face surface).
Was processed. The test was conducted using an inkjet recording apparatus having an on-demand type multi-recording head that ejects ink by applying thermal energy according to a recording signal.

Example 20 A head surface treating agent (water repellent) was KP-801.
The test was conducted in the same manner as in Example 1 except that the product name was (Shin-Etsu Silicon Co., Ltd.).

Example 21 Example 1 was repeated except that the head surface treatment agent (water repellent) was a defender (trade name of Dainippon Ink and Chemicals, Inc.).
The test was conducted in the same manner as in.

Example 22 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 23 (Preparation of Pigment Dispersion) Styrene-maleic acid-maleic acid half ester copolymer 4 parts (acid value 200, weight average molecular weight 12000) aminomethyl propanol 2 parts ion-exchanged water 74 parts diethylene glycol 5 parts Mix the above ingredients and heat to 70 ° C in a water bath,
Dissolve the resin completely. To this solution, 15 parts of carbon black (MCF88, manufactured by Mitsubishi Kasei Co., Ltd.) was added, and after premixing for 30 minutes, dispersion treatment was carried out under the following conditions.

Disperser Pearl mill (manufactured by Ashizawa) Grinding media Zirconium beads 1 mm
Diameter Filling ratio of grinding media 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) Dispersion 25 parts Glycerin 8 parts Ethylene glycol 5 parts Ethanol 5 parts Neugen ET-120E (Daiichi Kogyo Seiyaku) 0.08 parts Ion-exchanged water 56.92 parts Mix the above components Then, the pH was adjusted to 8 to 10 with aminomethyl propanol.

The ink prepared in this way was applied to the nozzle surface (face surface) with a water repellent CYTOP (trade name of Asahi Glass Co., Ltd.).
Was processed. The test was conducted using an inkjet recording apparatus having an on-demand type multi-recording head that ejects ink by applying thermal energy according to a recording signal.

Example 24 (Preparation of recording liquid) (Preparation of pigment dispersion liquid) Roma D (manufactured by San Nopco, sodium salt of naphthalene sulfonic acid) 1.5 parts Deionized water 81.5 parts Ethylene glycol 5 parts The above components are mixed. And heat to 70 ° C in a water bath,
Dissolve the resin completely. To this solution, 11 parts of a newly produced carbon black (S170, manufactured by Degussa) was added, 1 part of isopropyl alcohol was added, and after premixing for 60 minutes, a dispersion treatment was performed under the following conditions.

Dispersing machine Sand grinder (Igarashi Kikai) Grinding media Zirconium beads 0.5
mm diameter Filling ratio of grinding media 70% (volume) Grinding time 10 hours Further centrifugal separation processing (12000 RPM, 20 minutes) was performed to remove coarse particles to obtain a dispersion liquid.

(Preparation of Ink) Dispersion 30 parts Glycerin 12 parts Diethylene glycol 15 parts 2-Pyrrolidone 5 parts Isopropyl alcohol 3 parts Emulgen 430 (manufactured by Kao) 0.2 parts Ion-exchanged water 34.8 parts The above components are mixed. , PH 8 with monoethanolamine
It was adjusted to 10.

The ink thus prepared was treated on the nozzle surface (face surface) with a water repellent defencer (trade name of Dainippon Ink and Chemicals, Inc.). The test was conducted using an inkjet recording apparatus having an on-demand type multi-recording head that ejects ink by applying thermal energy according to a recording signal.

Comparative Examples Comparative Examples 19 to 24 In this comparative example, the polyoxyethylene alkyl ether or the polyoxyethylene alkenyl ether compound according to the present invention was not added at the time of preparing the inks of Examples 19 to 24, and ion exchange was performed instead. The test was conducted in the same manner as in Examples 19 to 24 except that the ink to which water was added was used.

The evaluation methods are as follows: Examples 1 to 6 and Comparative Examples 1 to 1.
It is the same as the evaluation method of 6.

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

[0118]

[Table 4]

[0119]

As described above, when the water-based pigment ink according to the present invention is used, no liquid pool is formed around the ejection port of the recording head, and the ink does not move away from the predetermined flight direction. Problems such as non-ejection of ink are solved,
A stable recorded image can be obtained. Further, there is an effect that various problems such as ink ejection stability, solidification at the head tip, and deterioration of the quality of printed matter can be solved without deteriorating other characteristics.

[Brief description of drawings]

FIG. 1A is a vertical cross-sectional view of a head portion of an inkjet recording apparatus. (B) It is a cross-sectional view taken along the line AB of (a).

FIG. 2 is an external perspective view of a head unit of the inkjet recording apparatus.

FIG. 3 is a perspective view showing an example of an inkjet recording apparatus.

FIG. 4 is a vertical sectional view of an ink cartridge.

FIG. 5 is a perspective view of a recording unit.

[Explanation of reference numerals] 13 head 14 groove 15 heating head 16 protective film 17-1 aluminum electrode 17-2 same as 18 heating resistor layer 19 heat storage layer 20 substrate 21 ink 22 orifice 23 meniscus 24 recording droplet 25 recording material 26 multi-groove 27 Glass Plate 28 Heating Head 40 Ink Bag 42 Plug 44 Ink Absorber 45 Ink Cartridge 51 Recording Material 52 Paper Feed Roller 53 Paper Ejection Roller 61 Blade as Wiping Material 62 Cap 62 'Cap 63 Ink Absorber 64 Ejection Recovery Section 65 Recording Head 65 ′ Same as above 66 Carriage 67 Guide shaft 68 Motor 69 Belt 70 Inkjet cartridge 71 Head part 72 Atmosphere communication port

Claims (4)

[Claims] 1. In an inkjet recording method for recording by applying energy to a recording liquid to eject the recording liquid as droplets from fine pores, the recording liquid is a water-soluble solvent, a pigment,
Containing water-soluble resin, water and phosphoric acid ester-based surfactant, fluorine-containing surfactant, boron-containing surfactant, polyoxyethylene alkyl ether or polyoxyethylene alkenyl ether-based surfactant A recording liquid characterized by the following. 2. The phosphoric acid ester surfactant according to claim 1 is represented by the following general formula (1): M = hydrogen, ammonium, Na, Li, K m = 1 to 18, x = 8 to 18, y + z = 8 to 18 (m,
x, y, z are integers), or the fluorine-containing surfactant described in claim 1 is represented by the following general formula (2): M = Na, K, Li, ammonium, hydrogen, n = 1 to an integer of 1 to 15, or the boron-containing surfactant according to claim 1 is represented by the following general formula (3): [Chemical 3] R = C ₇ -C ₂₁ alkyl group, n, m = 1 to 20 integer, or the polyoxyethylene alkyl ether or polyoxyethylene alkenyl ether described in claim 1 is represented by the following general formula (4). Is represented by x = 12 to 18 y = ± 1 z = 10 to 20 Recording liquid. 3. An ink jet recording method in which energy is applied to a recording liquid to eject the recording liquid as droplets from fine pores for recording, and the recording liquid is a water-soluble solvent, a pigment,
An ink jet recording method comprising a water-soluble resin, water and a compound represented by the general formula (1) or (2) or (3) or (4). 4. An ink jet recording method, wherein energy is applied to a recording liquid to eject the recording liquid as droplets from fine pores for recording, and the recording liquid is a water-soluble solvent, a pigment,
An ink jet recording apparatus comprising a water-soluble resin, water and a compound represented by the general formula (1) or (2) or (3) or (4).