JP2001310545A - Composition of liquid, ink set of ink-jet for recording, method of ink-jet recording recording unit and ink-jet recording device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid composition, an ink set, a method of ink-jet recording, a record device for which bleeding is controlled, water resistance is high and a formation of high quality image is made possible by using ink jet recording method combining coloring ink. SOLUTION: The ink jet recording liquid composition is used with coloring ink, and then a reaction is caused when it touches coloring ink. The liquid composition contains a multiple value metallic slat of polyol-phosphoric acid ester and a liquid medium, (1) the color ink that contains a color material, the multiple value metallic salt of the liquid medium and polyol-phosphoric acid ester, (2) it is an ink set containing a color material and a liquid medium for ink jet recording made by combining black ink which react with the above described color ink contacting with the color ink, ink jet recording method, recording unit and ink jet recording device.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid composition, an ink set for ink jet recording, an ink jet recording method, a recording unit, and an ink jet recording apparatus. More specifically, the present invention relates to a liquid composition capable of forming an image with reduced bleed, an image having excellent water resistance, an ink set for inkjet recording, an inkjet recording method using any of these, a recording unit, and an inkjet recording apparatus. .

[0002]

2. Description of the Related Art An ink jet recording method is a low-noise, non-impact recording method for recording an image by directly discharging ink onto a recording medium. In addition, since this method does not require a complicated device for implementation, low running costs, miniaturization of the device, colorization, and the like are easy. Accordingly, recording apparatuses such as a printer, a copying machine, a facsimile, a word processor, and the like to which the ink jet recording method is applied have been conventionally used. Further, using such an ink jet recording technique, a black ink and a color ink (for example, at least one color ink selected from a yellow ink, a cyan ink, a magenta ink, a red ink, a green ink, and a blue ink) are used. A color ink jet recording apparatus for forming a color image has also been put to practical use.

On the other hand, in the image formation by the ink jet recording method, when two different types of inks are applied to a recording medium adjacent to each other, the inks are mixed at the boundary between them, and a color image is formed. However, there is a problem that a phenomenon (bleeding) occurs in which the quality of the image is deteriorated. In particular, since the color mixture at the boundary between the black ink and the color ink greatly affects the image quality, various solutions have been developed.

A typical solution is that when two types of inks are applied to a recording medium adjacent to each other, at least one of the thickenings or aggregation or precipitation of at least one of the coloring materials occurs. And a recording method having a mechanism for preventing bleeding.

[0005] For example, Japanese Patent Application Laid-Open No. 5-202328,
U.S. Pat. No. 5,198,023 and Japanese Unexamined Patent Publication No.
As described in Japanese Patent No. 106841, the color bleed is controlled by using a first liquid containing a precipitant and a second liquid containing a colorant capable of forming a precipitate with the precipitant. Techniques are disclosed. A polyvalent metal salt is disclosed as the precipitant, and a dye or the like having at least one carboxyl group is disclosed as a colorant that can be precipitated by the polyvalent metal salt. Further, the first liquid may further contain a coloring agent, in which case the first liquid can also be used as ink.

However, as anions also polyvalent metal salt either in the above _{^{case, Cl -, NO 3 -,}} I -, Br
_{^{-, ClO 3 -, CH 3}} COO - using ion. JP-A-2000-136337 discloses, as a precipitant, a metal coordination compound in which a polyvalent metal ion is coordinated to a compound having a ligand such as lactic acid, in addition to the above polyvalent metal salt. It is disclosed.

[0007]

The inventors of the present invention have conducted intensive studies to improve bleeding. As a result, a first solution containing a polyvalent metal salt of a polyol phosphate ester and a polyhydric polyol phosphate polyol were used. When a second liquid containing a colorant that reacts with a metal salt is used in combination and applied on a recording medium so that they form a contact state, the colorant reacts with the polyvalent metal ion to cause bleeding. Found to be relaxed. The term “reaction” in the present invention means the formation of aggregation or precipitation or the increase in the viscosity of the second liquid, and includes the case where the liquids react after penetrating the recording medium. Furthermore,
It has also been found that a polyvalent metal salt of a polyol phosphate ester is excellent in solubility in ink, can be effectively used as a component of the ink, and is also excellent in safety to a human body. Further, when the first liquid and the second liquid are applied in an overlapping manner,
It was also confirmed that the formed image had improved water resistance.

Accordingly, an object of the present invention is to provide a liquid capable of forming a high-quality image in which bleed is suppressed and the water resistance of a recorded image is further improved by using the ink together with the colored ink in an ink jet recording method. It is to provide a composition. Another object of the present invention is to provide an ink set capable of forming a high-quality image with less bleed and excellent water resistance. It is another object of the present invention to provide an ink jet recording method capable of forming an image having good water resistance.

It is another object of the present invention to provide an ink jet recording method capable of forming a color image in which bleed is suppressed in a boundary area between images of different colors adjacent to each other. Still another object of the present invention is to provide an ink jet recording apparatus which can be suitably used for forming a color image in which bleed is suppressed or an image having good water resistance. Still another object of the present invention is to provide a recording unit that can be suitably used in the above-described ink jet recording apparatus.

[0010]

The above objects are achieved by the present invention described below. That is, the liquid composition according to one embodiment of the present invention is used together with a colored ink, is a liquid composition for inkjet recording that produces a reaction when contacted with the colored ink, and a polyol phosphate polyvalent metal salt and And a liquid medium.

The ink jet recording method according to one embodiment of the present invention comprises: (i) a step of ejecting each of the liquid composition and the colored ink toward a recording medium by an ink jet method; Forming a contact state between the liquid composition and the colored ink on a recording medium.

Further, an ink set for ink jet recording according to one embodiment of the present invention comprises (1) the above liquid composition, (2) a colorant and a liquid medium, and is in contact with the liquid composition. A colored ink that reacts with the liquid composition by
And a combination thereof.

[0013] A recording unit according to one embodiment of the present invention contains a liquid composition storage section that stores the liquid composition and a colored ink that reacts with the liquid composition by contact with the liquid composition. And an ink jet recording head for applying energy to the liquid composition and the colored ink to eject the liquid composition and the colored ink, respectively. Is what you do.

According to one embodiment of the present invention, there is provided an ink jet recording apparatus, comprising: a liquid composition containing section containing the liquid composition; and a colored ink which reacts with the liquid composition by contact with the liquid composition. In an ink jet recording apparatus equipped with an ink container that contains the ink composition and an ink jet recording head for applying energy to the liquid composition and the colored ink to eject the liquid composition and the colored ink, respectively. , Wherein the liquid composition is the liquid composition described above.

[0015] An ink jet recording apparatus according to another embodiment of the present invention is provided with the recording unit described above.

An ink set for ink jet recording according to another embodiment of the present invention comprises (1) a color ink containing a color material, a liquid medium and a polyvalent metal salt of a polyol phosphate, and (2) a color material and a liquid. And a black ink that includes a medium and reacts with the color ink by contact with the color ink.

An ink jet recording method according to another embodiment of the present invention includes: (i) a step of discharging each of the black ink and the color ink included in the ink set toward a recording medium by an ink jet method; A) forming a contact state between the black ink and the color ink on a recording medium.

According to another embodiment of the present invention, there is provided a recording unit which supplies ink to the ink container containing the ink set and discharges the ink by applying energy to the ink supplied from the ink container. And an ink jet recording head.

An ink jet recording apparatus according to another embodiment of the present invention is an ink jet recording apparatus which includes at least an ink container containing an ink set composed of a combination of black ink and color ink, and an ink supplied from the ink container. In an ink jet recording apparatus equipped with an ink jet recording head for applying energy and discharging ink, the ink set is the ink set described above.

An ink jet recording apparatus according to still another embodiment of the present invention includes the above recording unit.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. [First Embodiment] First, as a specific embodiment of the present invention, an embodiment in which a liquid composition containing a polyvalent metal salt of a polyol phosphate ester and a coloring ink containing a coloring material are used in combination will be described.

In the present embodiment, when the color ink in the color ink comes into contact with the color material, a reaction takes place, and the liquid composition containing the polyvalent metal that causes the aggregation or precipitation or the viscosity of the color ink is mixed with the color ink. It is applied on a recording medium so as to be in contact with it, and recording is performed. The liquid composition preferably does not affect the color tone of the colored ink in the recorded image.

Hereinafter, the polyvalent metal salt of the polyol phosphate ester contained in the liquid composition according to the present embodiment will be described. Examples of the polyol phosphate used in the polyvalent metal salt of the polyol phosphate include polyols, monosaccharides, oligosaccharides, and phosphates of polysaccharides. Specifically, for example, glycerophosphate, glucose-1-phosphate, glucose-6-phosphate, mannose-6-phosphate, galactose-6-phosphate, fructose-6-phosphate, glucose-1,6 -Diphosphate, fructose-1,6-diphosphate, ascorbate phosphate,
Sucrose phosphate, sorbitol phosphate, phosphorylated polyglycerin, phosphorylated polyethylene glycol, and the like.

Glycerophosphoric acid is particularly preferable among those used in the present embodiment. Glycerophosphate has α-glycerophosphate and β-glycerophosphate isomers, and either isomer may be used.
It may be used in a mixture of isomers. Examples of the polyvalent metal salts of glycerophosphate include magnesium glycerophosphate, calcium glycerophosphate, barium glycerophosphate, iron (II) glycerophosphate, copper (II) glycerophosphate, and the like. It is particularly preferable to use magnesium glycerophosphate or calcium glycerophosphate.

The above-mentioned polyvalent metal salts of polyol phosphates may be used alone or in combination of two or more. In addition, the total content of the polyol phosphate polyvalent metal salt as described above is 0.005 to 20 mass% based on the total amount of the liquid composition in order to obtain a higher bleed reduction effect and ejection stability. %, More preferably 0.05 to 12% by mass based on the total amount of the liquid composition.

Next, the colored ink used together with the liquid composition according to the present embodiment will be described. The colored ink contains at least a coloring material and a liquid medium, and when the ink comes into contact with the liquid composition containing the polyol phosphate ester polyvalent metal salt according to the present embodiment, the polyvalent metal It reacts with the salt to cause aggregation or precipitation of the coloring material in the colored ink, or to cause thickening of the colored ink. Examples of the colorant include dyes and pigments. Almost all pigments such as inorganic pigments and organic pigments can be used as the pigment.

Specifically, carbon black; I.
Pigment Yellow 1, 2, 3, 12, 13, 14, 1
6, 17, 73, 74, 75, 83, 93, 95, 9
7, 98, 114, 128, 129, 151, 154,
195; I. Pigment Red 5, 7, 12, 48
(Ca), 48 (Mn), 57 (Ca), 57: 1,5
7 (Sr), 112, 122, 123, 168, 18
4, 202; I. Pigment Blue 1, 2, 3, 1
5: 3, 15:34, 16, 22, 60; C.I. I. Vat Blue 4, 6 and the like.

When the above-mentioned pigments are used as the coloring material of the ink, it is preferable to use a dispersant in combination to stably disperse the pigment in the ink. As the dispersant, a polymer dispersant, a surfactant dispersant, or the like can be used. Specific examples of the polymer dispersant include, for example, polyacrylate, styrene-acrylic acid copolymer salt, styrene-methacrylic acid copolymer salt, styrene-acrylic acid-acrylic acid ester copolymer salt, styrene-
Maleic acid copolymer salt, acrylic acid ester-maleic acid copolymer salt, styrene-methacrylsulfonic acid copolymer salt, vinylnaphthalene-maleic acid copolymer salt, β-
Naphthalene sulfonic acid formalin polycondensate, polyvinyl pyrrolidone, polyethylene glycol, polyvinyl alcohol and the like. Among them, the weight average molecular weight is 1,000 to 30,000 and the acid value is 100 to
430 is preferred.

As the surfactant dispersant, for example, laurylbenzenesulfonate, laurylsulfonate,
Lauryl benzene carboxylate, lauryl naphthalene sulfonate, aliphatic amine salt, polyethylene oxide condensate and the like can be used, and all of them can be used. The use amount of these dispersants is preferably in the range of pigment mass: dispersant mass = 10: 5 to 10: 0.5.

In the present embodiment, for example,
Use of a carbon black pigment capable of self-dispersion by introducing a water-soluble group into the surface of carbon black as described in JP-A-186704 and JP-A-8-3498 as a coloring material. Can also. If such a self-dispersible carbon black is used, the use of the above-described dispersant is not necessarily required, and therefore, at least the amount of the dispersant used can be significantly reduced.

When the pigment ink as described above comes into contact with the liquid composition according to the present embodiment, the dispersion stability of the pigment in the pigment ink is destroyed due to salting out action of polyvalent metal ions in the liquid composition. As a result, the dispersion state of the pigment becomes unstable. As a result, the pigment in the pigment ink quickly aggregates,
It is considered that the color material in the pigment ink precipitates, and the fixing speed of the coloring material on the recording medium is increased, and bleeding is less likely to occur even when two or more different color inks are applied adjacently.
In the present embodiment, the instability of the dispersed state of the pigment based on the above-described action is also regarded as a “reaction” between the colored ink and the liquid composition.

Next, when a dye is used as a coloring material in the colored ink according to the present embodiment, a water-soluble dye is preferably used. Water-soluble dyes include direct dyes, acid dyes,
Any dye such as a basic dye and a disperse dye can be used. The colored ink containing a dye as a coloring material is contacted with the liquid composition according to the present embodiment to precipitate the dye due to a salting-out effect, or hardly water-soluble or water-insoluble salt or compound due to a reaction between the divalent metal ion and the dye. It is preferable to use a dye in which the dye in the colored ink is fixed to the recording medium at a high speed due to the formation of the dye or the combination of these actions.
And as a dye that can be used in such a colored ink, when contacted with a liquid composition containing a polyvalent metal salt of a polyol phosphate ester according to the present embodiment,
Dyes having at least one carboxyl group are preferred because they readily react with the polyvalent metal to form insoluble salts or compounds. Specifically, the following exemplified compounds 1 to 3
It is preferable to use a dye having a structure such as those described in No. 0, but it is not limited thereto.

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

As the coloring material contained in the colored ink according to the present embodiment, one of the above-described dyes and pigments may be used, or two or more of them may be used in combination. The concentration of these dyes and pigments is 0.1% with respect to the total amount of the ink.
It is preferably in the range of ２０20% by mass. Next, the liquid composition according to the present embodiment and the liquid medium used in the coloring ink used therewith will be described. As a liquid medium, it is preferable to use a mixed solvent of water and a water-soluble organic solvent.

As the water used in the present embodiment, it is desirable to use deionized water instead of general water containing various ions. Further, the content of water is preferably in the range of 35 to 96% by mass based on the total amount of the ink. The water-soluble organic solvent used by mixing with water may be appropriately selected and used from the following water-soluble organic solvents according to the purpose. The water-soluble organic solvent is
Since the viscosity of the ink can be adjusted to an appropriate suitable viscosity for use, it is used for various purposes such as slowing down the drying speed of the ink, increasing the solubility of the coloring material, and preventing clogging of the nozzles of the recording head.

Examples of the water-soluble organic solvent include, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, and n-butyl alcohol. Alkyl alcohols having 1 to 5 carbon atoms such as pentanol; amides such as dimethylformamide and dimethylacetamide;
Ketone or keto alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; oxyethylene or oxy such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol and polypropylene glycol Propylene copolymer; ethylene glycol,
Alkylene glycols having an alkylene group containing 2 to 6 carbon atoms, such as propylene glycol, trimethylene glycol, triethylene glycol, 1,2,6-hexanetriol; glycerin; trimethylolethane;
Trimethylolpropane; lower alkyl ethers such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, and triethylene glycol monomethyl (or ethyl) ether; triethylene glycol dimethyl (or ethyl) ether, tetraethylene glycol Lower dialkyl ethers of polyhydric alcohols such as dimethyl (or ethyl) ether; monoethanolamine,
Alkanolamines such as diethanolamine and triethanolamine; and sulfolane, N-methyl-2-pyrrolidone, 2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone. The water-soluble organic solvents as described above can be used alone or as a mixture.

The p of the colored ink according to the present embodiment is
In order to stabilize the solubility of the dye and the dispersibility of the pigment in the ink by keeping the H value constant,
An adjusting agent may be contained. Specific examples of the pH adjuster include hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and ammonium hydroxide, sulfates such as lithium sulfate, sodium sulfate, potassium sulfate and ammonium sulfate, and lithium carbonate. , Sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, carbonates such as ammonium carbonate and ammonium hydrogen carbonate, lithium phosphate, monosodium phosphate, disodium phosphate, trisodium phosphate, monopotassium phosphate, Phosphates such as dipotassium phosphate, tripotassium phosphate, monoammonium phosphate, diammonium phosphate and triammonium phosphate, and acetates such as lithium acetate, sodium acetate, potassium acetate and ammonium acetate are exemplified.

These salts may be used alone by being added to the colored ink, but it is more preferable to use two or more of these salts in combination. Further, in order to keep the pH stable, enhance the dissolution stability of the water-soluble dye contained in the colored ink, and prevent problems such as nozzle clogging, these salts are preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass is added. Further, in addition to the components described above, the liquid composition according to the present embodiment and the coloring ink used therewith may optionally contain various conventionally known general additives such as a viscosity modifier, a fungicide, and a preservative. Agents, antioxidants, defoamers, urea and other nozzle drying inhibitors can be used in combination as appropriate.

The preferred ranges of the physical properties of the liquid composition of the present embodiment and the coloring ink used therewith include:
The pH value around 25 ° C., which is particularly suitable for inkjet recording, is preferably 3 to 12, more preferably 4 to 1.
0, the surface tension is preferably 10 to 60 mN / m (dy
n / cm), more preferably 15 to 50 mN / m (dy)
n / cm), and the viscosity is preferably in the range of 1 to 30 cps, more preferably 1 to 10 cps.

In the ink jet recording method according to this embodiment, the liquid composition having the above-described structure and the coloring ink are used in combination, and the liquid composition is applied onto the recording medium so that the two come into contact with and react with each other. This is an inkjet recording method for performing recording. The recording medium used at this time is not particularly limited. However, the ink jet recording method according to the present embodiment is particularly preferable when an image is formed on so-called plain paper such as copy paper or bond paper which has been conventionally used, since the bleed reduction effect is remarkably exhibited. .

The order of applying the liquid composition and the coloring ink onto the recording medium when forming an image may be either the liquid composition first or the coloring ink first. . Alternatively, a method may be used in which the liquid composition is applied after the colored ink is applied, and then the colored ink is applied. That is, in the present embodiment, regardless of the order or method of applying the liquid composition, the liquid composition is applied on the recording medium so as to be brought into contact with the colored ink, so that an image formed by the colored ink can be improved. The improved character quality, fixability, water resistance and bleeding suppression effect are achieved.
This is because, on the recording medium, for example, the polyvalent metal ion in the liquid composition is mixed with the pigment and the dye in the coloring ink, thereby causing aggregation or precipitation, or thickening of the coloring ink. it is conceivable that.

In particular, from the viewpoint of further improving the image density and the fixing property, it is more preferable to, for example, apply the liquid composition after applying the colored ink, and then apply the colored ink again subsequently. Also, for example,
When the application of the liquid composition is performed prior to the application of the colored ink, the time from when the liquid composition is applied to the recording medium to when the colored ink is applied is not particularly limited. In order to make the invention more effective, it is within a few seconds, particularly preferably within 1 second.
The same applies to the case where the liquid composition and the colored ink are applied on the recording medium in the reverse order. Further, as shown in FIG. 17, the liquid composition (804) and the coloring ink (805) are discharged from the respective recording heads (801, 802) of the ink jet recording apparatus, and mixed immediately after the discharging (806) to record. It may be applied on the medium (803).

The ratio of the applied amount of the colored ink to the liquid composition per unit area of the recording medium in the image forming area may be 1: 1, but the colored ink: liquid composition = 10: 1. 10 to 10:10. Incidentally, the adjustment of the application amount of the colored ink and the liquid composition per unit area on the recording medium in the image forming area, specifically, for example,
Both the application of the liquid composition and the application of the colored ink are performed by an ink jet recording method, and the number of pixels of the liquid composition to be deposited on the recording medium is in the range of 10 to 100% of the number of pixels of the colored ink to be deposited on the recording medium. How to control so that
Both the application of the liquid composition and the coloring ink are performed by the ink jet recording method, and the ejection amount of the liquid composition is controlled so as to be smaller than the ejection amount of the coloring ink at that time, so that the coloring ink adheres to the recording medium. 10 to 100% of the discharge amount
, Or a combination thereof.

As a method for adhering the liquid composition and the colored ink according to the present embodiment on a recording medium, it is preferable to use an ink jet recording method as described above. Various inkjet recording methods can be used.
In the present invention, it is preferable to use an ink jet recording method using thermal energy and an ink jet recording method using mechanical energy due to deformation of a piezoelectric element.

First, an ink jet recording apparatus using thermal energy will be described below with reference to the drawings. FIGS. 1 and 2 show an example of a head configuration which is a main part of an ink jet recording apparatus using thermal energy. FIG.
FIG. 2 is a sectional view of the head 13 along the ink flow path,
FIG. 2 is a sectional view taken along line AB in FIG. 1. Head 13
Is a glass having a flow path (nozzle) 14 through which ink passes,
It is obtained by bonding a heating element substrate 15 to a ceramic, silicon, polysulfone or plastic plate or the like. The heating element substrate 15 is made of a protective layer 16-1 formed of silicon oxide, silicon nitride, silicon carbide, or the like, a metal oxide such as a metal such as platinum or an oxide of platinum, preferably an oxide of tantalum or an oxide of tantalum. The outermost surface protective layer 16-2 formed of, for example, electrodes 17-1 and 17-2 formed of aluminum, gold, aluminum-copper alloy, etc., and formed of a high melting point material such as hafnium boride, tantalum nitride, and tantalum aluminum. And a heat storage layer 19 formed of silicon oxide, aluminum oxide, or the like, and a substrate 20 formed of a material having good heat dissipation properties, such as silicon, aluminum, or aluminum nitride.

The electrodes 17-1 and 17- of the head 13
When a pulse-like electric signal is applied to the area 2, the area (heater) indicated by n on the heating element substrate 15 rapidly generates heat,
Bubbles are generated in the ink 21 in contact with the surface, and the meniscus 23 protrudes by the pressure, the ink 21 is discharged through the nozzle 14 of the head, and becomes a small ink droplet 24 from the discharge orifice 22 toward the recording medium 25. To fly. FIG. 3 shows an external view of an example of a multi-head in which many heads shown in FIG. 1 are arranged. This multi-head is formed by bonding a glass plate 27 having a multi-nozzle 26 and a heating head 28 similar to that described in FIG.

FIG. 4 shows an example of an ink jet recording apparatus incorporating this head. In FIG. 4, reference numeral 61 denotes a blade as a wiping member, one end of which is held and fixed by a blade holding member, and forms a cantilever. The blade 61 is arranged at a position adjacent to the recording area of the recording head 65, and in the present example, is held in a form protruding into the movement path of the recording head 65.

Reference numeral 62 denotes a cap on the protruding opening surface of the recording head 65, which is disposed at a home position adjacent to the blade 61, moves in a direction perpendicular to the moving direction of the recording head 65, and contacts the ink discharge port surface. It is provided with a configuration for contacting and capping. Reference numeral 63 denotes an ink absorber provided adjacent to the blade 61, which is held in a form protruding into the movement path of the recording head 65, similarly to the blade 61. The blade 61, the cap 62 and the ink absorber 63 constitute an ejection recovery section 64, and the blade 61
In addition, the ink absorber 63 removes moisture, dust, and the like from the ejection port surface.

Reference numeral 65 denotes a discharge energy generating means,
A recording head 66 for performing recording by discharging ink onto a recording medium facing a discharge port surface having discharge ports is a carriage for mounting the recording head 65 and moving the recording head 65. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected to a belt 69 driven by a motor 68 (not shown). 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 adjacent area.

Reference numeral 51 denotes a paper feed unit for inserting a recording medium, and reference numeral 52 denotes a paper feed roller driven by a motor (not shown). With these configurations, the recording head 65
The recording medium is fed to a position facing the ejection port surface of the recording medium, and is discharged to a discharge section provided with a discharge roller 53 as the recording proceeds. In the above configuration, the recording head 65
When the recording is completed and returns to the home position, the cap 62 of the ejection recovery unit 64 is retracted from the moving path of the recording head 65, but the blade 61 protrudes into the moving path. As a result, the ejection openings of the recording head 65 are wiped.

When capping is performed with the cap 62 in contact with the ejection surface of the recording head 65, the cap 62 moves so as to protrude into the moving path of the recording head. When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are at the same position as the position at the time of the wiping described above. As a result, the ejection port surface of the recording head 65 is also wiped during this movement. The above-described movement of the print head to the home position is performed not only at the end of printing or at the time of ejection recovery, but also at a predetermined interval while the print head moves through the printing area for printing to the home position adjacent to the printing area. And
The wiping is performed along with this movement.

FIG. 5 is a diagram showing an example of an ink cartridge 45 containing ink supplied to the recording head via an ink supply member, for example, a tube. Where 4
Reference numeral 0 denotes an ink storage unit that stores the supply ink, for example, an ink bag, and a rubber stopper 42 is provided at the tip of the ink storage unit. By inserting a needle (not shown) into the 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 container preferably has a liquid contact surface with ink formed of polyolefin, particularly polyethylene.

The ink jet recording apparatus according to the present embodiment is not limited to the one in which the head and the ink cartridge are separated as described above, but may be the one shown in FIG.
They may be integrated. In FIG. 6, 7
Numeral 0 denotes a recording unit, in which an ink storage section containing ink, for example, an ink absorber is stored, and the ink in the ink absorber is ejected as ink droplets from a head section 71 having a plurality of orifices. It is configured to be. It is preferable to use polyurethane as the material of the ink absorber. Further, a structure in which the ink container is an ink bag in which a spring or the like is charged inside without using an ink absorber may be used. Reference numeral 72 denotes an atmosphere communication port for communicating the inside of the cartridge with the atmosphere. The recording unit 70 includes a recording head 65 as shown in FIG.
And is detachable from the carriage 66.

As an ink jet recording apparatus of another embodiment, a nozzle forming substrate having a plurality of nozzles, a pressure generating element made of a piezoelectric material and a conductive material disposed opposite to the nozzles, and a pressure generating element An on-demand ink jet recording head that includes ink filling the surroundings, displaces a pressure generating element by an applied voltage, and discharges small droplets of ink from a nozzle can be given. FIG. 7 shows a configuration example of a recording head which is a main part of the recording apparatus.

The head includes an ink flow path 80 communicating with an ink chamber (not shown), an orifice plate 81 for discharging ink droplets of a desired volume, a vibration plate 82 for directly applying pressure to ink, and a A piezoelectric element 83 joined to the vibration plate 82 and displaced by an electric signal; and a base 84 for supporting and fixing the orifice plate 81, the vibration plate 82 and the like.
It is composed of

In FIG. 7, an ink flow path 80 is formed of a photosensitive resin or the like, and a discharge port 85 is formed in an orifice plate 81 by drilling a metal such as stainless steel or nickel by electroforming or pressing. I have. The vibration plate 82 is formed of a metal film such as stainless steel, nickel, titanium or the like, a high elastic resin film, or the like.
Reference numeral 3 is formed of a dielectric material such as barium titanate or PZT.

The recording head having the above configuration is
By applying a pulsed voltage to the piezoelectric element 83, a strain stress is generated, and the energy deforms the vibration plate 82 bonded to the piezoelectric element 83, and vertically pressurizes the ink in the ink flow path 80. An operation is performed such that a droplet (not shown) is ejected from the ejection port 85 of the orifice plate to perform recording. Such a recording head is used by being incorporated in a recording apparatus similar to that shown in FIG. The detailed operation of the recording apparatus may be performed in the same manner as described above.

When a color image is formed by the ink jet recording method according to the present embodiment, for example, five recording heads as shown in FIG.
Use the recording device listed above. FIG. 8 shows an example. Reference numerals 91, 92, 93, and 94 denote recording heads for ejecting inks of yellow, magenta, cyan, and black, respectively. Reference numeral 95 denotes a head for discharging a liquid composition. The head is arranged in the above-described printing apparatus, and discharges ink of each color according to a print signal. Further, the liquid composition is, for example, moved in a direction of an arrow of a carriage, and is previously attached to at least an image forming portion where the landing ink adheres to the recording medium.

FIG. 8 shows an example in which five recording heads are used. However, the present invention is not limited to this. As shown in FIG. 9, a single recording head can be used for yellow 101, magenta 102, cyan 103 and cyan 103. It is also preferable that the colored ink of black 104 and the liquid composition 105 be separated from each other in a liquid flow path. Of course, the heads may be arranged such that the recording order of each ink and the liquid composition is opposite to the above-described order.

FIG. 1 shows a specific configuration example of the arrangement of the ink jet recording head suitably used in this embodiment.
There are three types as shown in 0 to 12. Figures 10-1
2, 111-114, 121-124 and 13
Reference numerals 1-134 denote recording heads for ejecting inks of yellow (Y), magenta (M), cyan (C), and black (Bk), respectively. Also, 11
5, 125 and 135 are recording heads for discharging the liquid composition (S). Each recording head is arranged on a carriage as shown in FIG. 8 (depending on the configuration example). Each recording head is disposed in the above-described recording apparatus, and discharges ink of each color according to a recording signal. Further, the liquid composition is attached to an image area where at least ink of each color is attached to a recording medium before or after that. Each recording head is moved by a carriage in the direction of arrow (1), and the recording medium is moved by a paper feed roller or the like in the direction of arrow (2).

First, in the first configuration example shown in FIG. 10, S (1
15), Bk (114), Y (113), M (11
2) The recording heads for C (111) are arranged in parallel on the carriage. In the second configuration example shown in FIG. 11, the recording heads for the liquid composition (125) and the black ink (124) are arranged in parallel, and Y is arranged in parallel with each other and in series with each other. (123), M
(122) and a recording head for C (121).
Here, the ejection volume per dot of each recording head is:
The recording heads need not necessarily be the same, and one of the recording heads may be adjusted so that the recording suitability is optimized depending on the composition of the liquid composition and the like.
The ejection volume per dot (Vd) may be adjusted. Preferably, Vd of S, Y, M, and C is set to be the same, and Bk is set to be twice that of Sd, but is not limited thereto. FIG.
In the third configuration example shown in FIG.
(134), S (135), Bk (134), Y (13
3) The recording heads for M (132) and C (131) are arranged in parallel on the carriage, and the ejection amount of the black ink is set to be twice the ejection amount of the other liquid composition and the color ink. be able to.

[Second Embodiment] Next, as a specific second embodiment of the present invention, a color ink containing a polyvalent metal salt of a polyol phosphate ester and a coloring material; The case of using an ink jet recording ink set composed of a black ink containing a reactive coloring material will be described.

In this embodiment, printing is performed by applying the color ink and the black ink so as to form a contact state on the recording medium. In the ink set according to the present embodiment, the purpose is to prevent bleeding between the black ink and the color ink, and special measures are taken to prevent bleeding between color inks such as yellow ink, magenta ink, and cyan ink. Although it is not done, if ink design such as adding a surfactant to the color ink is made so as to have a quick penetration into plain paper sized for the color ink, Is also effective in preventing bleeding.

First, the color ink constituting the ink set according to the present embodiment will be described. The color ink used in the present embodiment includes a coloring material, a liquid medium, and a polyvalent metal salt of a polyol phosphate ester. The polyvalent metal salt of the polyol phosphate ester is as described in detail in the first embodiment.

Next, the color materials contained in the color inks constituting the ink set according to the present embodiment will be described. Coloring materials include direct dyes, acid dyes, basic dyes,
Examples thereof include disperse dyes and pigments, and it is preferable that the coloring material does not react with the polyvalent metal salt of a polyol phosphate and maintains its solubility even when it is prepared. As such a coloring material, specifically,

C. I. Acid yellow 23; I.
Acid Red 52, 289; I. Acid Blue 9; I. Reactive Red 180; C.I. I. Direct blue 189, 199; I. Basic Yellow 1, 2, 11, 13, 14, 19, 21, 2
5, 32, 33, 36, 51; I. Basic orange 2, 15, 21, 22; C.I. I. Basic Red 1,2,9,12,13,37,38,39,9
2; I. Basic Violet 1, 3, 7, 1
0, 14; I. Basic Blue 1, 3, 5,
7, 9, 19, 24, 25, 26, 28, 29, 45,
C. 54, 65; I. Basic green 1,4;
C. I. Basic Brown 1, 12; C.I. I. Basic Black 2, 8 and the like, but are not limited thereto. These water-soluble dyes may be used alone or in combination of two or more. The concentration of these water-soluble dyes is preferably in the range of 0.1 to 20% by mass based on the total amount of the ink.

It is preferable that the color inks constituting the ink set according to the present embodiment contain at least one surfactant in each of the color inks in addition to the components described above. By including a surfactant, desired permeability and viscosity can be imparted to the color ink, and the performance required for the ink for inkjet recording can be further satisfied. That is, as described above, by adding a surfactant to the color ink, it has a high permeability to plain paper, which is effective in preventing bleeding between color inks.

The amount of the surfactant to be added to the color ink is not particularly limited, but a desired permeability can be obtained.
In order to obtain an appropriate ink viscosity, 0.0% of the total mass of the ink is required.
It is preferably in the range of 1 to 10%, more preferably in the range of 0.1 to 5.0%.

Next, the black ink constituting the ink set according to the present embodiment will be described. The black ink used in the present embodiment includes a colorant that reacts with the polyvalent metal salt of the polyol phosphate ester and a liquid medium. As the color material of the black ink, a black color material that can be used for the colored ink of the first embodiment can be used. These coloring materials may be used alone or in combination of two or more. Further, the amount of these coloring materials added is preferably in the range of 0.1 to 20% by mass based on the total amount of the ink.

It is more preferable to add a nonionic surfactant to the black ink. By adding a nonionic surfactant, bleeding between black ink and color ink is further suppressed,
As described below, there is also obtained an effect that a decrease in the density of the black ink at the boundary between the black ink and the color ink, that is, generation of so-called “white haze” can be suppressed.

As described above, the color ink used in the ink set according to the present embodiment preferably contains a surfactant, and has high permeability to a recording medium such as plain paper. In many cases, the surface tension is low. When the color ink having a low surface tension and the black ink having a high surface tension are adjacent to each other, an area where the color material is small at an adjacent interface between the black ink and the color ink is generated, and a phenomenon called “white haze” occurs. May occur. Therefore, if a nonionic surfactant is added to the black ink to lower the surface tension, the above “white haze”
The phenomenon can be effectively suppressed.

In the present embodiment, the content of the nonionic surfactant to be contained in the black ink is not particularly limited, but it is possible to improve the suppression of bleeding between the black ink and the color ink and to reduce the occurrence of white haze. In order to effectively suppress the ink and maintain good ink dischargeability and print quality, the content is preferably in the range of 0.1 to 0.5% of the total mass of the ink, particularly preferably 0.2 to 0.4%. % Range.

Examples of the nonionic surfactant contained in the black ink according to this embodiment include higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, aliphatic ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide, and the like. Adduct, aliphatic amide ethylene oxide adduct,
Nonionic surfactants such as higher alkylamine ethylene oxide adducts, polypropylene glycol ethylene oxide adducts, fatty acid esters of polyhydric alcohols, and fatty acid amides of alkanolamines.
All of these are preferably used, and more preferably, an ethylene oxide adduct of a higher alcohol, an ethylene oxide adduct of an alkylphenol,
Ethylene oxide-propylene oxide copolymer,
It is preferable to use a nonionic surfactant such as an ethylene oxide adduct of acetylene glycol. More preferably, the addition mole number of the ethylene oxide adduct is from 4 to
20.

The liquid medium used for the black ink and the color ink constituting the ink set according to the present embodiment is described in detail as the liquid composition used in the first embodiment and the liquid medium used for the colored ink used therewith. The water-soluble organic solvents, additives, amounts added, and physical properties described above can be used.

Next, an ink jet recording method according to the present embodiment and a recording apparatus according to the present embodiment capable of realizing the ink jet recording method will be described. The ink jet recording method according to the present embodiment is directed to an ink jet recording method according to the present embodiment, wherein the ink is ejected by applying energy for ejecting the ink, and the color image is recorded on a recording medium. It is characterized in that a recording ink set is used. The recording medium used at this time is not particularly limited. But,
The ink jet recording method according to the present embodiment is, in particular,
When an image is formed on so-called plain paper such as copy paper or bond paper which has been conventionally used, the effect of reducing the bleed between the black ink and the color ink appears remarkably. Of course, the inkjet recording method according to the present embodiment can suitably use, for example, a coated paper or a transparent film for OHP specially created for inkjet recording. Further, it can be suitably used for general high-quality paper and glossy paper.

In the ink jet recording method according to the present embodiment, as a method of applying the black ink and the color ink on the recording medium, a method of applying the black ink and the color ink such that the black ink and the color ink are in contact with each other at the boundary can be mentioned. Can be As another mode, black ink and color ink are applied so as to overlap on the recording medium,
In addition, there is a method of applying the color ink to the recording medium prior to the black ink (hereinafter, referred to as an undercoating method). By performing such an undercoating method, the bleeding between the black ink and the color ink is further improved, and the “white haze” described above is reduced and the water resistance is improved. In the underlaying method described above, the time from when the color ink is applied to the recording medium to when the black ink is applied is not particularly limited, but in order to make the present invention more effective, , Within several seconds, particularly preferably within one second.
There is also a mode in which the color ink is applied (overstrike) after the black ink is applied, or the color ink and the black ink are mixed immediately after the ejection as shown in FIG.

In the underlaying method, the ratio of the amount of black ink and color ink applied per unit area on the recording medium in the image forming area may be 1: 1. Ink = 10: 1 to 1
It may be 0:10. By doing so, the white haze of the obtained image is reduced, and solid uniformity is achieved.
Incidentally, the adjustment of the application amounts of the black ink and the color ink per unit area on the recording medium in the image forming area,
Specifically, for example, it can be performed by the following various methods. That is, a method of controlling the number of pixels of the color ink deposited on the recording medium to be in the range of 10 to 100% of the number of pixels of the black ink deposited on the recording medium, the application of the black ink and the color ink Are both performed by an ink jet recording method, and in that case, a method of controlling the discharge amount of the color ink to be smaller than the discharge amount of the black ink, or a combination of these methods, the number of pixels of the color ink to be deposited on the recording medium Is controlled so as to be in the range of 10 to 100% of the number of pixels of the color ink and the black ink adhering on the recording medium,
In addition, there is a method in which both the color ink and the black ink are applied to the recording medium by an ink jet recording method, and the ejection amount of the color ink is smaller than the ejection amount of the black ink.

In the present invention, an ink jet recording method is used as a method for attaching the black ink and the color ink on the recording medium, and various conventionally known ink jet methods can be used as the ink jet recording method. Particularly preferred in the present invention are an ink jet recording method using thermal energy and an ink jet recording method using mechanical energy due to deformation of a piezoelectric element. The ink jet recording apparatus using thermal energy is as described in detail in the first embodiment.

When a color image is formed by the ink jet recording method according to the present embodiment, for example, a recording apparatus in which four recording heads shown in FIG. 3 are arranged on a carriage (145) is used. FIG. 13 shows an example.
Reference numerals 141, 142, 143, and 144 denote recording heads for ejecting black ink (Bk), yellow ink (Y), magenta ink (M), and cyan ink (C), respectively. The head is disposed in the above-described printing apparatus, and ejects ink of each color according to a print signal while moving a carriage in the direction of an arrow, for example.

FIG. 13 shows an example in which four recording heads are used. However, the present invention is not limited to this. As shown in FIG.
It is also preferred that the liquid flow paths of the yellow ink 151, the magenta ink 152, and the cyan ink 153 be performed separately.

FIG. 1 shows a specific example of the arrangement of an ink jet recording head suitably used in this embodiment.
5 and FIG. 16. FIG.
And in FIG. 16, 161 to 164 and 171 to 17
Reference numeral 4 denotes a recording head for ejecting various kinds of inks of yellow, magenta, cyan, and black, respectively. Each recording head is arranged on the carriage in the same manner as shown in FIG. 13 (depending on the configuration example). Each recording head is
The ink jet recording apparatus is arranged in the above-described ink jet recording apparatus and ejects various kinds of ink in accordance with a recording signal. Each recording head is moved by a carriage in the direction of arrow (1), and the recording medium is moved by a paper feed roller or the like in the direction of arrow (2).

First, in the configuration example shown in FIG.
(164), Y (163), M (162), C (16
The recording heads for 1) are arranged on the carriage in parallel. In another configuration example shown in FIG. 16, the recording head for black ink (174) and the recording heads Y (173) and M (1) are arranged in parallel with each other and in series with each other.
72), and a recording head for C (171). still,
In FIG. 15, the invention may be applied to a so-called line printer in which the carriage is fixed and the recording medium is moved in the direction of arrow (2) by a paper feed roller or the like.

[0094]

Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In the following description, “parts” and “%” are based on mass unless otherwise specified. [Examples and Comparative Examples of First Embodiment] (Examples 1 to 22 and Comparative Examples 1 to 11) An example corresponding to the first embodiment described above. The components listed below were used for each liquid composition and colored ink. As a production method, for a liquid composition and a coloring ink using a dye as a coloring material, after dissolving the following components, a micro filter (manufactured by Fuji Photo Film Co., Ltd.) having a pore size of 0.2 μm is further used. Each liquid composition and colored ink were prepared by filtration under pressure. In the case of a colored ink using a pigment as a coloring material, first, a pigment dispersion is prepared by each method, and the obtained dispersion is mixed with a liquid medium or the like, and then a micro filter having a pore size of 3 μm (Sumitomo Electric ( And pressure-filtered to prepare respective pigment inks.

After dissolving the following components, the mixture was filtered under pressure using a micro filter having a pore size of 0.2 μm (manufactured by Fuji Photo Film Co., Ltd.) to prepare Liquid Compositions 1 to 3. Note that the liquid composition 3 corresponds to a comparative example.

[0096]

[0097]

<Preparation of Black Ink 1> (Preparation of Pigment Dispersion 1) 300 g of a commercially available acidic carbon black “MA77” (pH 3; manufactured by Mitsubishi Chemical Corporation) was thoroughly mixed in 1,000 ml of water, and then mixed with this. 450 g of sodium hypochlorite (effective chlorine concentration 12%) was dropped, and 1
The mixture was stirred at 00 to 105 ° C for 10 hours. The obtained slurry was applied to Toyo Filter Paper No. 2 (Advantis)
The pigment particles were thoroughly washed with water. This pigment wet cake was redispersed in 3,000 ml of water and desalted with a reverse osmosis membrane until the electric conductivity was 0.2 μs. Further, the pigment dispersion (pH = 8 to 1)
0) was concentrated to a pigment concentration of 10% by mass. By the above method, Pigment Dispersion Liquid 1 containing self-dispersible carbon black having -COONa groups introduced on the surface of carbon black was obtained.

(Preparation of Ink) The following composition containing the pigment dispersion liquid 1 obtained above was mixed, and the pore size was 3 μm.
The resultant was subjected to pressure filtration using a micro filter (manufactured by Sumitomo Electric Industries, Ltd.) to prepare Black Ink 1.・ 40 parts of pigment dispersion liquid ・ 8 parts of glycerin ・ 5 parts of trimethylolpropane ・ 4 parts of isopropyl alcohol ・ 43 parts of water

<Preparation of Black Ink 2> (Preparation of Pigment Dispersion Liquid 2) Styrene-acrylic acid-butyl acrylate copolymer (acid value 116, average molecular weight 3,700) 5 parts Triethanolamine 0.5 Parts ・ Diethylene glycol 5 parts ・ Water 69.5 parts

The above components were mixed and mixed in a water bath at 70
Heat to ° C. to completely dissolve the resin component. To this solution, 15 parts of carbon black “MA-100” (pH 3.5; manufactured by Mitsubishi Chemical Corporation) and 5 parts of 2-propanol were added.
After premixing for 30 minutes, dispersion treatment was performed under the following conditions. -Dispersing machine: Sand glider (made by Igarashi Kikai)-Grinding media: zirconium beads 1 mm diameter-Filling rate of grinding media: 50% (volume)-Grinding time: 3 hours Further, centrifugal dispersion treatment (12,000 rpm, 20 minutes)
Was performed to remove coarse particles to obtain a carbon black pigment dispersion liquid 2.

(Preparation of Ink) The following composition containing the pigment dispersion liquid 2 obtained above was mixed, and a pore size of 3 μm was further added.
The resultant was subjected to pressure filtration using a micro filter (manufactured by Sumitomo Electric Industries, Ltd.) to prepare Black Ink 2.

<Preparation of Black Ink 3> After the following components were dissolved, the mixture was filtered under pressure using a micro filter having a pore size of 0.2 μm (manufactured by Fuji Photo Film Co., Ltd.) to prepare Black Ink 3. Exemplified Compound 1 (M is NH ₄ ⁺⁾ 2 parts Diethylene glycol 10 parts 2-pyrrolidone 5 parts 2-propanol 0.1 parts 5 parts of sodium hydroxide, water 77.9 parts

<Yellow Ink 1> (Preparation of Pigment Dispersion Liquid 3) Styrene-acrylic acid copolymer (acid value 200, average molecular weight 7,000) 5.5 parts Monoethanolamine 1.0 part Ion exchange Water 67.5 parts ・ Diethylene glycol 5.0 parts The above components were mixed and heated to 70 ° C. in a water bath.
The resin was completely dissolved. To this solution was added C.I. I. Pigment Yellow 93 and 20 parts of isopropyl alcohol were added, and the mixture was premixed for 30 minutes and then dispersed under the following conditions. -Dispersing machine: sand grinder-Grinding media: glass beads 1 mm diameter-Filling rate of the grinding media: 50% (volume)-Grinding time: 3 hours Further centrifugation (12,000 rpm, 20 minutes) to remove coarse particles The pigment dispersion 3 was removed.

(Preparation of Ink) The following composition containing the pigment dispersion liquid 3 obtained above was mixed, and a pore size of 3 μm was further added.
The resultant was subjected to pressure filtration using a micro filter (manufactured by Sumitomo Electric Industries, Ltd.) to prepare Yellow Ink 1.

<Yellow Ink 2> After dissolving the following components, yellow ink 2 was prepared by filtration under pressure using a micro filter having a pore size of 0.2 μm (manufactured by Fuji Photo Film Co., Ltd.). Exemplified Compound 2 (M is NH ₄ ⁺⁾ 3 parts Glycerin 7 parts Diethylene glycol 5 parts Urea 5 parts Ethanol 2 parts Water 78 parts

[0107]

The above components were mixed and mixed in a water bath at 70
The mixture was heated to ° C. to completely dissolve the resin. To this solution was added C.I. I. Pigment Red 122 and 1.0 part of isopropyl alcohol were added, and the mixture was premixed for 30 minutes and then dispersed under the following conditions. -Dispersing machine: sand grinder-Grinding media: glass beads 1 mm diameter-Filling rate of the grinding media: 50% (volume)-Grinding time: 3 hours Further centrifugation (12,000 rpm, 20 minutes) to remove coarse particles The pigment dispersion 4 was removed.

(Preparation of Ink) The following composition containing the pigment dispersion liquid 4 obtained above was mixed, and a pore size of 3 μm was further added.
The resulting mixture was subjected to pressure filtration using a m. micro filter (manufactured by Sumitomo Electric Industries, Ltd.) to prepare magenta ink 1.

<Preparation of Magenta Ink 2> After dissolving the following components, magenta ink 2 was prepared by filtration under pressure using a micro filter having a pore size of 0.2 μm (manufactured by Fuji Photo Film Co., Ltd.). Exemplified Compound 3 (M is NH ₄ ⁺⁾ 3 parts Glycerin 7 parts Diethylene glycol 5 parts Urea 5 parts Ethanol 2 parts Water 78 parts

[0111]

The above components were mixed and mixed in a water bath at 70
The mixture was heated to ° C. to completely dissolve the resin. To this solution was added C.I. I. Pigment Blue 15: 3 (20 parts) and isopropyl alcohol (1.0 part) were added, followed by premixing for 30 minutes, followed by dispersion treatment under the following conditions. -Dispersing machine: sand grinder-Grinding media: glass beads 1 mm diameter-Filling rate of the grinding media: 50% (volume)-Grinding time: 3 hours Further centrifugation (12,000 rpm, 20 minutes) to remove coarse particles The pigment dispersion 5 was removed.

(Preparation of Ink) The following composition containing the pigment dispersion liquid 5 obtained above was mixed, and a pore size of 3 μm was further added.
The resulting mixture was filtered under pressure using a m. micro filter (manufactured by Sumitomo Electric Industries, Ltd.) to prepare Cyan Ink 1.

<Preparation of Cyan Ink 2> After dissolving the following components, the mixture was further filtered under pressure using a micro filter having a pore size of 0.2 μm (manufactured by Fuji Photo Film Co., Ltd.).
Cyan ink 2 was prepared. Exemplified Compound 4 (M is one or more of NH ₄ ⁺⁾ 3 parts Glycerin 7 parts Diethylene glycol 5 parts Urea 5 parts Ethanol 2 parts Water 78 parts

<Evaluation> (Evaluation Test for Ink) The evaluation test is shown below. Using the combinations shown in Table 1, each of the coloring inks and the respective liquid compositions obtained above was recorded on recording paper. As the ink jet recording apparatus used, a recording apparatus having the same configuration as that shown in FIG. 4 was used, and an image was formed using two of the five recording heads shown in FIG. At this time, the liquid composition was first struck, first adhered on the recording paper, and then the colored ink was adhered.
The position where the liquid composition was applied onto the recording paper was adjusted so as to exactly overlap the position where the colored ink was applied onto the recording paper. The recording head used here had a recording density of 360 dpi and a driving frequency of 5 kHz. Also,
The ejection volume per dot is 80 pl / d for colored ink.
ot, the liquid composition used a 40 pl / dot head. The recording paper is PB paper (manufactured by Canon Inc .: common paper for copier and ink jet recording), XEROX
4024 paper (Xerox Co., Ltd.) was used.

[0116] 1. Water resistance Each of the colored inks and the liquid composition was used in combination as shown in Table 1 for printing, and after the printed matter was left for 1 hour, the print density was measured with a Macbeth RD915 (trade name: manufactured by Macbeth). Perform Thereafter, the printed matter was immersed in a container filled with tap water for 3 minutes, left to stand, dried, and the print density was measured again. The residual ratio of the printed matter density was obtained from the following formula, and the water resistance of the image was determined as follows. Evaluation was based on criteria. Table 1 shows the evaluation results. It is practically preferable that the residual ratio of the print density is 95% or more.

[0117] A: Remaining rate of print density is 95% or more. B: The residual ratio of the print density is 85% or more and less than 95%. C: Residual rate of print density is less than 85%.

[0118] 2. Printing Quality (Bleeding) Alphanumeric characters (12 points) were printed in the same manner, left for 1 hour, and then visually evaluated for the sharpness of the characters and the degree of mustache-like bleeding generated from the characters. Table 1 shows the evaluation results.
It was shown to. A: The character is sharp and has no whisker-like bleeding. B: The character is not sharp and bleeding occurs a little. C: The character is not sharp and has much bleeding.

[0119]

[0120] 3. Bleed On the two plain papers used earlier, an ink set consisting of the liquid composition in the combination shown in Table 2 and each colored ink was used. First, a solid portion was printed with the black ink in the ink set, and immediately thereafter. , Yellow as adjacent to it,
Alternatively, a solid portion of each color ink was printed with magenta or cyan ink. Next, a solid portion was printed with yellow ink in the same manner as described above, and immediately thereafter, a solid portion of each color ink was printed with black, magenta, or cyan ink adjacent thereto. Next, a solid portion was printed with magenta ink in the same manner as described above, and immediately thereafter, a solid portion of each color ink was printed with black, yellow, or cyan ink adjacent thereto. Further, in the same manner as described above, a solid portion was printed with cyan ink, and immediately thereafter, a solid portion of each color ink was printed with black, magenta, or yellow ink adjacent thereto. The boundary portion of the solid printing obtained as described above was visually observed, and bleeding between each colored ink was evaluated. The evaluation criteria are as follows, and the evaluation results are shown in Table 2. A: No bleeding is observed at all boundaries. B: Slight bleeding is observed, but not so much concern. C: Bleeding is severe at almost all boundaries.

[0121]

[Examples and Comparative Examples of Second Embodiment] (Examples 23 to 25 and Comparative Examples 12 to 14) Examples 23 to 25 and Comparative Examples 12 to 14 were prepared by combining a black ink and each color ink of yellow, magenta and cyan. Comparative Examples 12 to 14
Was prepared. Each ink was prepared by the following method using the respective components listed below. As for the black ink constituting each ink set, after using the pigment dispersions 1 and 2 obtained above and mixing the following components, a microfilter having a pore size of 3 μm (manufactured by Sumitomo Electric Industries, Ltd.) ) And filtered under pressure. For the color inks constituting each ink set, the following components were mixed, sufficiently stirred and dissolved, and then a micro filter having a pore size of 0.2 μm (manufactured by Fuji Photo Film Co., Ltd.) was used. Each of the color inks was prepared by filtration under pressure. Table 3 shows Example 2
The main compositions of the ink sets of 3 to 25 and Comparative Examples 12 to 14 are shown.

<Ink set of Example 23> (Black ink) 40 parts of pigment dispersion 1 8 parts of glycerin 5 parts of trimethylolpropane 4 parts of isopropyl alcohol 43 parts of water

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

<Evaluation Method and Evaluation Criteria> Each ink of the ink sets of Examples 23 to 25 and Comparative Examples 12 to 14 obtained above was applied to the ink by applying heat energy to the ink in accordance with a recording signal. Color inkjet printer (BJC-700) which is an inkjet recording apparatus having an on-demand type multi-recording head for discharging
J: manufactured by Canon Inc.). And 2. Was evaluated. The paper for the evaluation test must be P
B paper (manufactured by Canon Inc .: common paper for copier and ink jet recording) and two plain papers of XEROX 4024 (manufactured by Xerox Corporation) were used. Table 4 shows the obtained results.

[0149] 1. Bleeding between black ink and color ink A solid portion is printed on the above two plain papers with the black ink in each ink set, and immediately after that, adjacent to it,
A solid portion of each color ink was printed with yellow, magenta, or cyan ink. The boundary portion of the obtained solid print was visually observed to evaluate bleeding between the black ink and the color ink. The evaluation criteria were as follows. A: No bleeding is observed at all boundaries. B: Slight bleeding is observed. C: Bleeding is severe at almost all boundaries.

2. Density of Black Ink at Adjacent Boundary Between Black Ink and Color Ink (White Haze Occurrence) Solid area is printed with black ink with each ink set on the above two plain papers, and immediately adjacent to it Then, a solid portion was printed with yellow, magenta, or cyan ink, and occurrence of white haze at an adjacent boundary portion with black ink was visually observed and evaluated. The evaluation criteria were as follows. A: No decrease in the density of the black ink portion at the boundary was observed, and no white haze was generated. B: It can be seen that the density of the black ink portion at the boundary portion has decreased and white haze has occurred, but this is a practically acceptable level. C: The density of the black ink portion at the boundary was significantly reduced.
The occurrence of white haze is remarkable.

(Examples 26 to 28 and Comparative Examples 15 to 1)
7) Using the ink sets of Examples 23 to 25 and Comparative Examples 12 to 14 to apply a color ink to a place where a black ink is applied on a recording medium prior to the application of the black ink (underprinting) The image was formed by a recording method further including The ink jet recording method according to the underlaying method using the ink sets of Examples 23 to 25 is referred to as Examples 26 to 28, and the ink jet recording method according to the underprinting method using the ink sets of Comparative Examples 12 to 14 is referred to as Comparative Examples 15 to 17 was set. Examples 26 to 28 and Comparative Example 1
The ratio of the applied amount per unit area of the recording medium between the black ink and the color ink in 5 to 17 was black ink: color ink = 10: 2.5. Table 4 shows the evaluation results.

[0152]

[0153]

As described above, according to the present invention, a liquid composition, an ink jet recording ink set, and an ink jet recording method for obtaining a high-quality image in which bleed is suppressed by using an ink jet recording method, A recording unit and an inkjet recording device are obtained. Further, a liquid composition, an ink set for ink jet recording, an ink jet recording method, a recording unit, and an ink jet recording apparatus for obtaining an image having excellent water resistance are also obtained.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view showing an example of a head of an ink jet recording apparatus.

FIG. 2 is a cross-sectional view illustrating an example of a head of the inkjet recording apparatus.

FIG. 3 is an external perspective view of a head obtained by multiplying the head shown in FIG. 1;

FIG. 4 is a schematic perspective view showing an example of an ink jet recording apparatus.

FIG. 5 is a longitudinal sectional view showing an example of an ink cartridge.

FIG. 6 is a perspective view illustrating an example of a recording unit.

FIG. 7 is a schematic cross-sectional view showing an example of a configuration of an ink jet recording head using energy of a piezoelectric element.

FIG. 8 is a perspective view showing a recording unit in which a plurality of recording heads are arranged.

FIG. 9 is a perspective view of another recording head used in the present invention.

FIG. 10 is a diagram showing a first configuration example of a recording head.

FIG. 11 is a diagram showing a second configuration example of the recording head.

FIG. 12 is a diagram illustrating a third configuration example of the recording head.

FIG. 13 is a perspective view showing a recording unit in which a plurality of recording heads are arranged.

FIG. 14 is a perspective view of another recording head used in the present invention.

FIG. 15 is a diagram illustrating a fourth configuration example of the recording head.

FIG. 16 is a diagram showing a fifth configuration example of the recording head.

FIG. 17 is a schematic view of an inkjet recording method according to an embodiment of the present invention.

[Explanation of symbols]

 13: Head 14: Ink groove 15: Heating element substrate 16-1: Protective film 16-2: Top surface protective film 17-1, 17-2: Electrode 18: Heating resistor layer 19: Heat storage layer 20: Substrate 21: Ink 22: ejection orifice 23: meniscus 24: ink droplet 25: recording medium 26: multi-groove 27: glass plate 28: heating head 40: ink bag 42: plug 43: carriage 44: ink absorber 45: ink cartridge 51 : Paper feed part 52: paper feed roller 53: paper discharge roller 61: blade 62: cap 63: ink absorber 64: discharge recovery part 65: recording head 66: carriage 67: guide shaft 68: motor 69: drive belt 70: Recording unit 71: Head part 71 72: Air communication port 80: Ink flow path 81: Orifice plate 82: Vibration 83: Piezoelectric element 84: Base 85: Discharge port 91: Yellow ink recording head 92: Magenta ink recording head 93: Cyan ink recording head 94: Black ink recording head 95: Liquid composition recording head 96: Carriage 101: Yellow ink flow Path 102: Magenta ink flow path 103: Cyan ink flow path 104: Black ink flow path 105: Liquid composition flow path 111: Yellow ink print head 112: Magenta ink print head 113: Cyan ink print head 114: Black ink print head 115 : Liquid composition recording head 121: yellow ink recording head 122: magenta ink recording head 123: cyan ink recording head 124: black ink recording head 125: liquid composition recording head 131: yellow in Recording head 132: Magenta ink recording head 133: Cyan ink recording head 134: Black ink recording head 135: Liquid composition recording head 141: Black ink recording head 142: Yellow ink recording head 143: Magenta ink recording head 144: Cyan ink recording Head 145: Carriage 151: Yellow ink flow path 152: Magenta ink flow path 153: Cyan ink flow path 154: Black ink flow path 161: Yellow ink print head 162: Magenta ink print head 163: Cyan ink print head 164: Black ink Recording head 171: Yellow ink recording head 172: Magenta ink recording head 173: Cyan ink recording head 174: Black ink recording head 801: Liquid composition recording Head 802: color ink recording head 803: the recording medium 804: Liquid composition 805: Colored Ink 806: mixture with a liquid composition colored inks

Claims (35)

[Claims] 1. A liquid composition for inkjet recording which is used together with a colored ink and which reacts when brought into contact with the colored ink, comprising a polyvalent metal salt of a polyol phosphate ester and a liquid medium. Liquid composition. 2. The liquid composition according to claim 1, wherein the polyvalent metal salt of the polyol phosphate is magnesium glycerophosphate or calcium glycerophosphate. 3. The total content of the polyol phosphate ester polyvalent metal salt is 0.005 to 2 with respect to the total amount of the liquid composition.
The liquid composition according to claim 1, which is 0% by mass. (I) a step of applying energy to the liquid composition and the colored ink according to any one of claims 1 to 3 to discharge each of the liquid composition and the colored ink toward a recording medium; Forming a contact state between the liquid composition and the colored ink on a recording medium. 5. The ink jet recording method according to claim 4, wherein the coloring material of the coloring ink is a pigment. 6. The ink jet recording method according to claim 4, wherein the coloring material of the coloring ink is a dye having at least one carboxyl group. 7. The ink jet recording method according to claim 4, wherein the energy is heat energy. 8. The ink jet recording method according to claim 4, wherein the energy is mechanical energy due to deformation of the piezoelectric element. 9. The method of applying a liquid composition on a recording medium,
The ink jet recording method according to any one of claims 4 to 8, wherein the method is performed prior to applying the colored ink to the recording medium. 10. The ink jet recording method according to claim 4, wherein the application of the liquid composition onto the recording medium is performed after the application of the colored ink onto the recording medium. 11. The method according to claim 4, wherein the application of the liquid composition to the recording medium is performed after the application of the coloring ink to the recording medium, and then the coloring ink is further applied to the recording medium.
9. The ink jet recording method according to any one of items 1 to 8. 12. The method according to claim 4, wherein the application of the colored ink on the recording medium is performed after the application of the liquid composition on the recording medium, and the liquid composition is further applied on the recording medium.
9. The ink jet recording method according to any one of items 1 to 8. 13. The ink jet recording method according to claim 4, wherein the liquid composition and the colored ink are mixed immediately after ejection from the ink jet recording apparatus and applied onto a recording medium. 14. A liquid composition comprising (1) the liquid composition according to any one of claims 1 to 3, and (2) a coloring material and a liquid medium, and the liquid composition being brought into contact with the liquid composition. An ink set for ink-jet recording, comprising a combination of a colored ink reacting with an object. 15. A colored ink that reacts with a liquid composition containing a liquid composition according to any one of claims 1 to 3 by contacting the liquid composition with the liquid composition. And an ink jet recording head for applying energy to the liquid composition and the colored ink to eject the liquid composition and the colored ink, respectively. And a recording unit. 16. The ink jet recording unit according to claim 15, wherein the energy is heat energy. 17. The ink jet recording unit according to claim 15, wherein the energy is mechanical energy due to deformation of the piezoelectric element. 18. A liquid composition storage section containing a liquid composition, an ink storage section containing a colored ink that reacts with the liquid composition upon contact with the liquid composition,
2. An ink jet recording apparatus equipped with an ink jet recording head for applying energy to the liquid composition and the colored ink to eject the liquid composition and the colored ink, respectively, wherein the liquid composition is used. ~
3. An ink jet recording apparatus, which is the liquid composition according to any one of 3. 19. An ink jet recording apparatus comprising the recording unit according to claim 15. Description: 20. A color ink containing (1) a colorant, a liquid medium and a polyvalent metal salt of a polyol phosphate, and (2)
An ink set for ink jet recording, comprising: a combination of a black ink that includes a color material and a liquid medium, and that reacts with the color ink by contact with the color ink. 21. The ink set for inkjet recording according to claim 20, wherein the polyvalent metal salt of the polyol phosphate ester is magnesium glycerophosphate or calcium glycerophosphate. 22. The total content of the polyol phosphate ester polyvalent metal salt is 0.005 to 20 with respect to the total amount of the ink.
22. The ink set for inkjet recording according to claim 20, wherein the content is% by mass. 23. The ink set for inkjet recording according to claim 20, wherein the coloring material of the black ink is a pigment. 24. The coloring material of the black ink is a dye having at least one carboxyl group.
23. The ink set for inkjet recording according to any one of 22. 25. The content of water in the black ink and the color ink is 35 to 9 with respect to the total mass of the ink, respectively.
The ink set for inkjet recording according to any one of claims 20 to 24, wherein the content is 6% by mass. 26. The ink set for inkjet recording according to claim 20, wherein the color ink is at least one ink selected from the group consisting of a yellow ink, a magenta ink, and a cyan ink. 27. (i) any one of claims 20 to 26
(C) applying energy to the black ink and the color ink included in the ink set described in (1) and discharging each of them toward a recording medium; and (ii) forming the black ink and the color ink on the recording medium. Forming a contact state of the ink jet recording method. 28. The method according to claim 27, wherein the black ink and the color ink are applied so as to overlap on the recording medium, and the application of the color ink to the recording medium is performed prior to the application of the black ink. Ink jet recording method. 29. The ink jet recording method according to claim 27, wherein the energy is heat energy. 30. The ink jet recording method according to claim 27, wherein the energy is mechanical energy due to deformation of the piezoelectric element. 31. An ink container containing the ink set according to any one of claims 20 to 26, and an ink ejected by applying energy to the ink supplied from the ink container. A recording unit comprising: 32. The ink jet recording unit according to claim 31, wherein the energy is heat energy. 33. The ink jet recording unit according to claim 31, wherein the energy is mechanical energy due to deformation of the piezoelectric element. 34. An ink containing section containing at least an ink set composed of a combination of black ink and color ink, and an ink supplied from the ink containing section for applying energy to eject the ink. An ink-jet recording apparatus comprising the above-mentioned ink-jet recording head, wherein the ink set is the ink set according to any one of claims 20 to 26. 35. An ink jet recording apparatus comprising the recording unit according to claim 31.