JP2002172847A - Liquid composition, ink-jet recording method, ink-set for ink-jet recording, recording unit, ink cartridge, ink-jet recording device, and ink for ink-jet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid composition, an ink set having black ink and color ink, a method and device for ink-jet recording using the same wherein an image of good printing quality is given and a long life of an ink-jet recording head can be achieved. SOLUTION: There are provided a liquid composition containing a polyvalent metal salt, an acid having an amino group, and a substance selected from the salt of the acid, and a liquid medium, an ink-jet recording method which gives the liquid composition and a coloring ink onto a recording medium so that the composition is brought into contact with the ink, a color ink containing a coloring material, the liquid medium, the polyvalent metal salt, the acid having an amino group and a substance selected from the salt of the acid, an ink set for ink-jet recording which contains the coloring material and a liquid medium in which the color ink is combined with a black ink, which reacts with the color ink by being brought into contact with the color ink, and an ink-jet recording method and device using the ink set.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid composition, an ink-jet ink, an ink-jet recording ink set, an ink-jet recording method, a recording unit, an ink cartridge, and an ink-jet recording apparatus. More specifically, a liquid composition, ink-jet ink, and ink-jet recording ink that have good print quality, reduce color bleed generated in the formation of a color image, and can further extend the life of the ink-jet recording head using thermal energy The present invention relates to a set, an ink jet recording method, a recording unit, an ink cartridge and an ink jet recording apparatus using any one of these sets.

[0002]

2. Description of the Related Art Ink-jet recording methods are easy to reduce the size of the apparatus, reduce running costs, facilitate colorization, etc., and are advantageous in forming color images. There are challenges. For example, when two different inks are applied to a recording medium adjacent to each other,
The inks mix at their borders,
There is a problem that a phenomenon (bleeding) in which the quality of a color image is deteriorated occurs. Since mixed color (bleed) at the boundary between black ink and color ink has a particularly large effect on image quality deterioration, various solutions have been developed.

[0003] For example, Japanese Patent Application Laid-Open No. Hei 5-202328,
U.S. Pat. No. 5,198,023 and Japanese Unexamined Patent Publication No.
As described in Japanese Patent No. 106841, a color is obtained by using a first liquid containing a precipitant and a second liquid containing a coloring material (coloring material) capable of forming a precipitate with the precipitant. Techniques for controlling bleed have been disclosed. And
A polyvalent metal salt is disclosed as the precipitant, and a dye having at least one carboxyl group is disclosed as a colorant that can be precipitated by the polyvalent metal salt. It is further stated that the first liquid may contain a coloring material, in which case the first liquid can also be used as ink.

[0004]

However, according to the study of the present inventors, in order to prevent the above-mentioned bleeding, a solution containing a polyvalent metal salt as described in JP-A-5-202328 has been disclosed. Was repeatedly ejected by a bubble jet (registered trademark) method, and it was found that kogation derived from the polyvalent metal salt might be formed on a heater in contact with the solution containing the polyvalent metal salt. As a result, the amount of ejected droplets and the speed of ejected droplets may be reduced as compared with the initial stage, and this may affect the image quality. Further, the inventors have found that the heater may be disconnected, which may cause a problem that the discharge of the polyvalent metal salt solution is disabled. This is because, when the ink or the liquid composition containing the polyvalent metal salt is overheated by the heater, the anion ions constituting the polyvalent metal salt are volatilized or broken,
This is considered to be because the concentration of cation ions (polyvalent metal ions) in the vicinity of the heater increases and the alkalinity increases, so that the outermost protective film made of a metal such as tantalum and / or a metal oxide is dissolved. .

The inventors of the present invention have conducted intensive studies on a liquid composition or ink which has an effect of preventing bleeding, suppresses disconnection and burning of the heater, and can extend the life of the head. Reached. Accordingly, an object of the present invention is to provide an image of good print quality in an ink jet recording method in which a liquid composition and a coloring ink are attached to perform recording on a recording medium, and furthermore, the life of the ink jet recording head is extended. It is an object of the present invention to provide a liquid composition that can achieve the following. Another object of the present invention is to provide an ink set for ink jets having a black ink and a color ink, which provides an image of good print quality and can achieve a longer life of the ink jet recording head. It is in. Further, another object of the present invention is to provide an ink set for ink jet recording, an ink jet recording method, a recording unit, an ink cartridge, and an ink jet recording apparatus which can provide an image of good print quality and can further extend the life of the ink jet recording head. Is to provide.

[0006]

The above object is achieved by the present invention described below. That is, the liquid composition according to an embodiment of the present invention is a liquid composition for inkjet recording that is used together with a colored ink and generates a reaction when contacted with the colored ink, and (a) a polyvalent metal salt; b) a substance selected from acids having an amino group and salts thereof, and (c)
And a liquid medium.

The ink jet recording method according to one embodiment of the present invention comprises: (i) applying energy to the liquid composition and discharging the liquid composition toward a recording medium to apply the liquid composition onto the recording medium. (Ii) applying energy to the colored ink that contains a colorant and a liquid medium, and reacts with the liquid composition by contact with the liquid composition, and discharges the colored ink toward a recording medium to form the colored ink; Applying on a recording medium, and performing the above steps (i) and (ii) such that a contact state between the liquid composition and the colored ink is formed on the recording medium. It is characterized by the following.

[0008] An ink set for ink jet recording according to one embodiment of the present invention comprises: (1) the liquid composition described above;
(2) It is characterized by comprising a coloring material and a liquid medium, and being combined with a colored ink that reacts with the liquid composition by contact with the liquid composition.

According to an embodiment of the present invention, there is provided a recording unit, comprising: a liquid composition containing section containing the above liquid composition; An ink storage unit containing 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. Is what you do.

[0010] An ink cartridge according to one embodiment of the present invention includes a liquid composition accommodating section accommodating the liquid composition, a coloring material and a liquid medium, and is provided by contact with the liquid composition. An ink container for containing a colored ink that reacts with the liquid composition.

An ink jet recording apparatus according to one embodiment of the present invention contains a liquid composition containing section containing a liquid composition, and contains a colored ink that reacts with the liquid composition by contact with the liquid composition. An ink jet recording apparatus equipped with a colored ink storage section, 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.

An ink set for ink jet recording according to another embodiment of the present invention comprises: (1) a colorant, a liquid medium,
A color ink comprising a polyvalent metal salt, a substance selected from an acid having an amino group and a salt thereof, and (2) a color material comprising a colorant and a liquid medium, and contacting the color ink with the color ink It is characterized by being combined with a reactive black ink.

According to another embodiment of the present invention, there is provided an ink jet recording method comprising: (i) applying energy for discharging ink to the black ink included in the ink set, and directing the black ink toward a recording medium. And (ii) applying energy for discharging the ink to the color ink included in the ink set, and discharging the color ink toward the recording medium. Having a step of applying on a recording medium, and performing the steps (i) and (ii) such that a contact state between the black ink and the color ink is formed on the recording medium. It is characterized by the following.

According to another embodiment of the present invention, there is provided a recording unit, wherein an ink is stored in each of the inks constituting the ink set, and energy is supplied to the ink supplied from the ink storing unit. And an ink jet recording head for ejecting ink.

[0015] An ink cartridge according to another embodiment of the present invention is characterized in that the ink cartridge is provided with an ink storage section for storing each of the inks constituting the ink set.

According to another embodiment of the present invention, there is provided an ink jet recording apparatus comprising: an ink container for accommodating an ink set comprising at least a black ink and a color ink; and an ink supplied from the ink container. And an ink jet recording apparatus equipped with an ink jet recording head for applying energy to the ink and ejecting the ink respectively, wherein the ink set is the ink set.

The ink-jet ink according to one embodiment of the present invention comprises (a) a polyvalent metal salt, (b) a substance selected from an acid having an amino group and a salt thereof, (c) a liquid medium, (D) a coloring material.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. [First Embodiment] As a specific embodiment of the present invention,
An ink jet recording liquid composition that reacts when contacted with a colored ink, and (a) a polyvalent metal salt;
A liquid composition comprising (b) a substance selected from an acid having an amino group and a salt thereof, and (c) a liquid medium is used. The recording may be performed by applying the liquid composition and the colored ink on a recording medium so that a contact state is formed with the colored ink used for recording. Hereinafter, the first embodiment will be described. The liquid composition used above preferably does not affect the color tone of the colored ink in the recorded image.

First, the polyvalent metal salt (a) constituting the liquid composition used in the above embodiment will be described. Examples of the polyvalent metal salt include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, organic acids such as acetic acid and hydroxycarboxylic acid, and polyol phosphate esters and the like, magnesium salts, calcium salts,
Barium salts, iron (II) salts, copper (II) salts, zinc salts, aluminum salts and the like. Among these, preferred are high solubility in a liquid medium, magnesium nitrate and calcium salts, magnesium acetate and calcium salts, magnesium and calcium hydroxycarboxylates, and magnesium and calcium salts of polyol phosphates. It is.

Specific examples of the above-mentioned hydroxycarboxylic acids include lactic acid, aldonic acids (polyoxydicarboxylic acids) such as malic acid, citric acid and tartaric acid, and aldonic acids such as gluconic acid. It is not limited to these. Among these hydroxycarboxylic acids, it is particularly preferable to use a polyvalent metal salt of aldonic acid having excellent solubility and safety.

Hereinafter, the polyvalent metal salt of aldonic acid will be described in detail. Aldonic acid is a polyoxycarboxylic acid corresponding to one obtained by oxidizing an aldehyde group of aldose to a carboxyl group, and is represented by the following general formula. Aldonic acid combines with polyvalent metal ions such as magnesium and calcium to form a soluble polyvalent metal salt, and thus can be suitably used as a constituent material of the liquid composition of the present invention.

As described above, since aldonic acid has an asymmetric carbon atom, there are many optical isomers. Aldonic acids having 5 or more carbon atoms (n = 3 or more in the above general formula) are rarely present alone in an aqueous solution. To γ-aldonolactone and δ-aldonolactone, respectively, and are said to exist as an equilibrium mixture of aldonic acid, γ-aldonolactone and δ-aldonolactone. And 4 carbon atoms (n = 2 in the above general formula)
It is rare that aldonic acid alone also exists in an aqueous solution, and usually, a part of aldonic acid forms a lactone with a hydroxyl group at the γ-position to become γ-aldonolactone, respectively, and aldonic acid and γ -It is said to exist as an equilibrium mixture of the two aldonolactones.

Aldonic acid is classified by the number of carbon atoms, and has 4 carbon atoms.
(N = 2 in the above general formula) is tetronic acid; those having 5 carbons (n = 3 in the above general formula) are pentonic acid; those having 6 carbons (n = 4 in the above general formula) Is collectively referred to as hexonic acid. Specific examples of the aldonic acid include, for example, glycolic acid having 2 carbon atoms (n = 0 in the above general formula) (alias: hydroxyacetic acid);
Glyceric acid of 1); 4 carbon atoms (n =
2) erythronic acid and threonic acid; 5 carbon atoms (n = 3 in the general formula), ribonic acid, arabonic acid, xylonic acid and lyxonic acid; 6 carbon atoms (n = 4 in the general formula) Acid, allonic acid, altronic acid, mannonic acid, gulonic acid, idonic acid, galactonic acid, and talonic acid; glucoheptonic acid having 7 carbon atoms (n = 5 in the above general formula) and the like; Some L-forms and DL-forms exist.

Among the aldonic acids suitable as constituent materials of the liquid composition according to the present invention, particularly preferred gluconic acid (n = 4 in the above formula) will be described. Gluconic acid is widely used as a food additive and is safe for the human body. Gluconic acid is rarely present alone in an aqueous solution, and usually, a part of gluconic acid forms a lactone with a hydroxyl group at the γ-position or δ-position, respectively.
-Gluconolactone and δ-gluconolactone, and are said to exist as an equilibrium mixture of gluconic acid, γ-gluconolactone and δ-gluconolactone. As gluconic acid, there are D-form, L-form and DL-form, and any of them may be used. In general, D-gluconic acid in D-form is easily available. In addition, as optical isomers of gluconic acid, for example, allonic acid, altronic acid, mannonic acid, gulonic acid, idonic acid, galactonic acid, taronic acid and the like are present, and they exhibit properties similar to gluconic acid. May be.

The above-mentioned polyvalent metal salts of gluconic acid include magnesium gluconate, calcium gluconate,
Examples thereof include barium gluconate, iron (II) gluconate, and copper (II) gluconate. In the present invention, it is particularly preferable to use magnesium gluconate or calcium gluconate. These compounds can be used alone or in combination of two or more.

Next, the polyvalent metal salt of the polyol phosphate ester will be described. Examples of the polyol phosphate ester include polyol, monosaccharide, oligosaccharide and polysaccharide phosphate esters. 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,
Ascorbic acid phosphate, sucrose phosphate, sorbitol phosphate, phosphorylated polyglycerin, phosphorylated polyethylene glycol, and the like.

Among these, glycerophosphoric acid, which is particularly preferred in the present embodiment, will be described. Glycerophosphate includes isomers of α-glycerophosphate and β-glycerophosphate. In the present invention, either isomer may be used or a mixture of isomers may be used. Examples of these polyvalent metal salts of glycerophosphate include magnesium glycerophosphate, calcium glycerophosphate, barium glycerophosphate, iron (II) glycerophosphate, copper (II) glycerophosphate, and the like.
In particular, it is preferable to use magnesium glycerophosphate or calcium glycerophosphate.

In the liquid composition according to the present invention, the total content of at least one compound selected from the above-mentioned polyvalent metal salts may provide more excellent bleed reduction effect and head durability. To achieve this, the content is preferably 0.005 to 20% by mass relative to the total amount of the liquid composition, and more preferably 0.05 to 12% by mass based on the total amount of the liquid composition.

Next, the substance (b) constituting the liquid composition according to the present invention, which is selected from acids having an amino group and salts thereof will be described. As the acid having an amino group,
For example, amidosulfuric acid (alias: sulfamic acid), aminomethanesulfonic acid, taurine (alias: 2-aminoethanesulfonic acid), carbamic acid, glycine, alanine, β
-Alanine, aspartic acid, glutamic acid, sulfanilic acid, phenylalanine, leucine, isoleucine,
Threonine, tryptophan, valine, methionine, lysine and arginine. Among these,
From the viewpoint of solubility in a liquid medium to be used in combination and availability, amidosulfuric acid (sulfamic acid), aminomethanesulfonic acid, taurine (also known as 2-aminoethanesulfonic acid), carbamic acid, glycine, alanine, β- It is preferred to use alanine, aspartic acid and glutamic acid.

In the case of using the above-mentioned acid salt having an amino group, a compound which is commercially available in a salt form or a salt form of an organic acid prepared by adding an alkali is used. May be used. As the alkaline agent used at this time, for example, lithium hydroxide, sodium hydroxide,
Potassium hydroxide, aqueous ammonia (or ammonium hydroxide), magnesium hydroxide, calcium hydroxide, organic amines (eg, triethanolamine, diethanolamine, monoethanolamine, diisopropanolamine, triisopropanolamine, tetramethylammonium hydroxide, Tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, and the like). These compounds can be used alone or in combination of two or more.

The total content of a substance selected from the above-mentioned acids having an amino group and salts thereof in the liquid composition is preferably set to a higher value in order to achieve a better kogation reduction effect and a longer head life. It is preferable to contain 0.005 to 20% by mass with respect to the total amount, and more preferably 0.05 to 12% by mass with respect to the total amount of the liquid composition.

The ink jet recording method used in the first embodiment of the present invention is an ink jet recording method for recording an image on a recording medium by applying an energy for discharging the ink and discharging the ink. The liquid composition having the above-described configuration is used in combination with a coloring ink as described below, and the recording is performed by applying these to a recording medium. Hereinafter, the coloring material used for the coloring ink will be described.

Next, in the first embodiment of the present invention (hereinafter referred to as the first embodiment), a colored ink used together with the above-described liquid composition will be described. The colored ink contains at least a coloring material and a liquid medium, but when the ink is brought into contact with the specific liquid composition described above,
It reacts with polyvalent metal ions derived from the polyvalent metal salt in the liquid composition to cause the coloring material in the colored ink to aggregate or precipitate or to increase the viscosity of the colored ink. Pigments and dyes can be used as coloring materials in the coloring ink. As the pigment, any pigment such as an inorganic pigment and an organic pigment can be used, and specific examples include the following.

Carbon black, C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 7
3, 74, 75, 83, 93, 95, 97, 98, 11
4, 128, 129, 151, 154 and 195, C.I.
I. Pigment Red 5, 7, 12, 48 (Ca), 4
8 (Mn), 57 (Ca), 57: 1, 57 (Sr),
112, 122, 123, 168, 184 and 202,
C. I. Pigment Blue 1, 2, 3, 15: 3, 1
5:34, 16, 22, and 60, C.I. I. Vat Blue 4 and 6 and the like.

When the pigments listed above are used as a coloring material, it is preferable to use a dispersant in order to stably disperse the pigment in the coloring ink. Examples of the dispersant include a polymer dispersant and a surfactant dispersant. 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-naphthalenesulfonic acid formalin condensate salt, polyvinylpyrrolidone , Polyethylene glycol and polyvinyl alcohol.

Among these, it is particularly preferable to use those having a weight average molecular weight of 1,000 to 30,000 and an acid value of 100 to 430. Examples of the surfactant-based dispersant include laurylbenzenesulfonate, laurylsulfonate, laurylbenzenecarboxylate, laurylnaphthalenesulfonate, an aliphatic amine salt, and a polyethylene oxide condensate.
It is preferable to use these dispersants in an amount of pigment: weight of dispersant = 10: 5 to 10: 0.5.

JP-A-5-18 is used as a coloring material of a colored ink.
Use of a self-dispersion type carbon black capable of self-dispersion by introducing a water-soluble group into the surface of carbon black as described in JP-A-6704 and JP-A-8-3498 as a coloring material. You can also. When the self-dispersion type carbon black as described above is used as the coloring material, since the use of the above-described dispersant is not necessarily required, the amount of the dispersant can be reduced, or depending on the case. Does not require the use of dispersants.

When the pigment ink as described above comes into contact with the liquid composition according to the first embodiment described above, the pigment ink is subjected to salting-out action of the polyvalent metal ions in the liquid composition and the like. Is rapidly aggregated and precipitated, and the fixing of the coloring material in the pigment ink to the recording medium is accelerated. As a result, even when two or more types of ink of different colors are applied adjacent to each other, it is considered that bleeding hardly occurs. In the first embodiment, a liquid composition for ink jet recording that causes a reaction when contacted with a colored ink is used. The “reaction” between the colored ink and the liquid composition includes a pigment based on the above-described action. The instability of the dispersion state of is also included in the “reaction”.

In the case where a dye is used as a coloring material constituting the colored ink used in the first embodiment, a water-soluble dye is preferably used. For example, dyes such as direct dyes, acid dyes, basic dyes and disperse dyes can be used. Preferable colored inks containing a dye include, by contact with the liquid composition according to the present embodiment having the above-described configuration, precipitation of the dye due to a salting-out effect, and poor water solubility due to the reaction between the polyvalent metal ion and the dye. Alternatively, a dye in which the dye in the colored ink is fixed to the recording medium at a high speed by the formation of a water-insoluble salt or compound or a combination of these actions is suitably used. As a dye that can be used in such a colored ink, when it comes into contact with the liquid composition according to the present embodiment, it reacts with a polyvalent metal salt in the liquid composition to form an insoluble salt or compound. For ease of use, it is preferable to use a dye having at least one carboxyl group in the molecule. Specifically, it is preferable to use a dye having a structure as exemplified in the following exemplified compounds 1 to 30, but the present invention is not limited thereto. or,
M in the exemplified compounds 1 to 5 is any of an alkali metal, ammonium and organic ammonium.

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

As the coloring material to be contained in the coloring ink used in the first embodiment, one of these dyes or the above-mentioned pigments may be used, or two or more of them may be used in combination. . The concentration of these dyes and pigments is usually appropriately selected from the range of 0.1 to 20% by mass based on the total amount of the ink.

Next, the liquid composition according to the first embodiment and the liquid medium used in the color ink used together will be described. As the liquid medium, it is preferable to use water and a water-soluble organic solvent in combination. In this case, 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 adjusts the viscosity of the ink to an appropriate viscosity that is preferable for use, thereby delaying the drying speed of the ink, or increasing the solubility of the coloring material to prevent clogging of the nozzles of the recording head. It is used for various purposes, for example. Specific aqueous organic solvents include, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
C1-C5 alkyl alcohols such as sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol and n-pentanol; amides such as dimethylformamide and dimethylacetamide; ketone or keto alcohol such as acetone and diacetone alcohol Ethers such as tetrahydrofuran and dioxane; diethylene glycol, triethylene glycol,
Tetraethylene glycol, dipropylene glycol,
Oxyethylene or oxypropylene copolymers such as tripropylene glycol, polyethylene glycol and polypropylene glycol; 2 to 6 alkylene groups such as ethylene glycol, propylene glycol, trimethylene glycol, triethylene glycol and 1,2,6-hexanetriol; Glycerin; trimethylolethane and trimethylolpropane; lower alkyls such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether and triethylene glycol monomethyl (or ethyl) ether Ethers: triethylene glycol dimethyl (or ethyl) ether and tetraethylene glycol dimethyl (or ethyl) ether Polyvalent lower dialkyl ethers of an alcohol, such as ether; alkanolamines monoethanolamine, diethanolamine and triethanolamine; sulfolane, N- methyl-2-pyrrolidone, 2
-Pyrrolidone and 1,3-dimethyl-2-imidazolidinone. The water-soluble organic solvents as described above may be used alone or as a mixture.

In order to stabilize the solubility of the dye in the ink and the dispersibility of the pigment in the ink by keeping the pH value of the colored ink constant, a pH adjusting agent may be contained in the colored ink. As the pH adjuster, specifically, for example, 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 carbonic acid Lithium, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, carbonates such as ammonium carbonate and ammonium bicarbonate, lithium phosphate, monosodium phosphate, disodium phosphate, trisodium phosphate, monopotassium phosphate , Dipotassium phosphate,
Phosphates such as tripotassium phosphate, monoammonium phosphate, diammonium phosphate and triammonium phosphate; acetates and hydrochlorides such as lithium acetate, sodium acetate, potassium acetate and ammonium acetate;

These pH adjusters may be added to the liquid composition described above. These may be used alone by adding them to the liquid composition and the colored ink, but more preferably, two or more pH adjusters are selected and used in combination. In particular, in order to keep the pH stable, enhance the dissolution stability of the water-soluble dye contained in the coloring ink, and prevent problems such as nozzle clogging, these pH adjusters are preferably used. It is added in the range of 0.1 to 10% by mass, more preferably 1 to 8% by mass.

Further, in the liquid composition according to the first embodiment and the coloring ink used in combination therewith, in addition to the above-mentioned components, if necessary, various conventionally known general additives,
For example, viscosity modifiers, fungicides, preservatives, antioxidants,
An antifoaming agent and a nozzle drying inhibitor such as urea can be appropriately used in combination.

The suitable range of the physical properties of the liquid composition according to the first embodiment and the color ink used in combination is that the pH value at about 25 ° C. is preferably 3 to 12, more preferably 4 to 10, The surface tension is preferably 10 to 60 mN / m
(Dyn / cm), more preferably 15 to 50 mN / m
(Dyn / cm) and the viscosity is preferably 1 to 30 cp.
s, more preferably in the range of 1 to 10 cps.

In the ink jet recording method according to the first embodiment, a liquid composition having the above-described structure and a colored ink are used in combination, and the liquid composition is applied onto a recording medium so that they come into contact with and react with each other. Recording. The recording medium used at this time is not particularly limited. However, the ink jet recording method according to the first embodiment has a remarkable bleed reduction effect particularly when an image is formed on a so-called plain paper such as copy paper or bond paper which is conventionally used. It is preferable to use these.

The ink jet recording method according to the first embodiment may be any method that applies an energy necessary for ejection to the ink to eject the ink and records an image on a recording medium. And it is not particularly limited. However, in particular, when an image is formed using the recording method according to the present embodiment when an ink jet recording method using thermal energy is used for discharging ink, the occurrence of so-called “kogation” is effectively suppressed. An excellent effect of being able to obtain. As an ink jet recording method using thermal energy, for example, there is a so-called on-demand type bubble jet method in which droplets are ejected using bubbles generated by thermal energy.

In the ink jet recording method according to the first embodiment, a liquid composition having the above-described structure and a colored ink are used in combination, and these are applied so that they come into contact with and react on the recording medium. If the recording is performed, the order of applying the liquid composition and the coloring ink onto the recording medium when forming an image is such that the coloring composition is applied first even if the liquid composition is applied first. It may be either. That is, in the first embodiment, regardless of the order or method of application, the liquid composition and the colored ink are applied on the recording medium such that a contact state between the liquid composition and the colored ink is formed. Good character quality, fixability, water resistance and bleeding suppression effects of the formed image are achieved. This is because, when the liquid composition and the colored ink come into contact on the recording medium, the polyvalent metal ions resulting from the polyvalent metal salt constituting the liquid composition are mixed with the pigment and dye in the ink. This is considered to cause aggregation, precipitation, or thickening of the colored ink.

In particular, from the viewpoint of further improving the image density and the fixability, it is more preferable, for example, to apply the liquid composition after the application of the colored ink, and to subsequently apply the colored ink again. . The application of the colored ink on the recording medium may be performed after the application of the liquid composition on the recording medium, and the liquid composition may be applied on the recording medium.

When the application of the liquid composition is performed prior to the application of the coloring ink, the time from the application of the liquid composition to the recording medium to the application of the coloring ink is also particularly limited. is not. However, in order to make the present invention more effective, for example, within a few seconds,
It is particularly preferable to set the time within one second. This means
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 another embodiment for applying the liquid composition and the coloring ink to the recording medium, a method shown in FIG. 16 can be used. In such a form, the liquid composition 804 and the colored ink 8
05 is ejected from each of the recording heads 801 and 802 of the ink jet recording apparatus, the two are mixed immediately after the ejection, and the mixture 806 is applied onto the recording medium 803.

According to the ink jet recording method according to the first embodiment, as described above, regardless of the order or method of applying the liquid composition and the coloring ink, the liquid according to the present embodiment comprising specific components is used. By applying the composition onto a recording medium in such a manner that a contact state with the colored ink is formed, it is possible to achieve good character quality of an image formed by the colored ink, and to improve fixability and water resistance. In addition, the occurrence of bleeding when a color image is formed is effectively suppressed. This is because an agglomerate is formed by mixing the polyvalent metal ion contained in the liquid composition and the pigment and / or dye in the colored ink on the recording medium. It is considered that an effect can be obtained.

In the ink jet recording method according to the first embodiment, when the recording is performed by applying the liquid composition and the coloring ink on the recording medium by the method described above, the coloring ink in the image forming area is removed. The ratio of the applied amount per unit area of the recording medium to the liquid composition may be 1: 1. However, colored ink: liquid composition = 10: 1 to 1
It may be 10:10. Here, the adjustment of the ratio of the application amounts of the coloring ink and the liquid composition per unit area on the recording medium in the image forming region is specifically performed by, for example, placing the liquid composition and the coloring ink on the recording medium. Is controlled so that the number of pixels of the liquid composition adhered on the recording medium is in the range of 10 to 100% of the number of pixels of the colored ink adhered on the recording medium when the ink is applied by the inkjet recording method. Method, when the application of the liquid composition and the coloring ink is performed by an inkjet recording method, by controlling the ejection amount of the liquid composition to be smaller than the ejection amount of the coloring ink,
10 to 1 of the number of pixels of the colored ink adhering on the recording medium
The method can be carried out by a method of setting the range to 00%, a method of combining these methods, or the like.

Hereinafter, the ink jet recording method according to the first embodiment and the ink jet recording apparatus to which the method is applied will be described in more detail. In the ink jet recording method according to the first embodiment, as a method for attaching the liquid composition of the present embodiment and the coloring ink onto a recording medium, energy is applied to the ink, thereby discharging the ink, thereby An ink-jet recording method for forming an image on a recording medium is used. As the recording method, various conventionally known ink-jet methods (for example, an ink-jet recording method using mechanical energy due to deformation of a piezoelectric element) are used. Can be. However, it is particularly preferable to use an inkjet recording method in which ink is ejected by utilizing the action of thermal energy.

That is, as described above, a liquid composition containing a polyvalent metal salt is used in combination with a colored ink for the purpose of suppressing bleeding of mixed colors between different colors and improving the water resistance of a recorded material. The occurrence of kogation that occurs when an image is formed using an inkjet recording method that utilizes thermal energy to discharge an object, and the reduction in image quality caused by the kogation, are caused by using the liquid composition according to the first embodiment. It is effectively suppressed by the characteristic inkjet recording method. Further, in the conventional method, a solution used together with the coloring ink for the purpose of suppressing bleeding and improving the water resistance of the recorded matter is repeatedly ejected from the recording head, so that a solution (heat generating element substrate) for applying thermal energy is provided. The outermost surface protective layer made of a metal and / or metal oxide, for example, tantalum or a tantalum oxide, etc., is melted, thereby causing disconnection of the heater,
In some cases, such as a situation where ejection becomes impossible, or kogation occurs on the heater, which affects the quality of a formed image. Such a problem is effectively prevented.

An ink jet recording apparatus using the liquid composition according to the first embodiment described above includes a liquid composition containing section containing the above liquid composition, and a color ink containing a liquid ink. And an ink jet recording head for discharging the liquid composition and the colored ink, respectively. Still another preferred embodiment is an apparatus for discharging a liquid composition and a coloring ink by the action of thermal energy, wherein the liquid composition and the coloring composition in a flow path led from the liquid composition receiving section and the coloring ink receiving section are provided. An ink jet recording head having a heater for applying thermal energy to ink, and an ink jet recording apparatus having means for applying a pulse-like electric signal to the heater in accordance with recording information are exemplified. Furthermore, the above-mentioned heater is provided with an outermost surface protective layer containing a metal and / or a metal oxide, and in particular, the metal and / or the metal oxide is made of tantalum and / or an oxidation of tantalum. In the case of the ink jet recording apparatus of the aspect that is a product, the remarkable effects of the present invention are exhibited.

Further, as an embodiment in which the remarkable effects of the present invention are exhibited, there is an apparatus in which the energy applied to the heater is controlled as follows. That is, when the amount of energy input to the heater for discharging the liquid composition from the recording head is E _op and the minimum amount of energy required for discharging the ink from the recording head is E _th , E _op / E _th In particular, according to the inkjet recording apparatus in which the value (= γ value) is controlled so as to satisfy the following relationship, the remarkable effect of the present invention is exhibited. 1.10 ≦ E _op / E _th ≦ 1.90

Hereinafter, an ink jet recording apparatus to which an ink jet recording method for discharging ink by using thermal energy will be described 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. 1 is a cross-sectional view of the recording head 13 along the ink flow path, and FIG. 2 is a cross-sectional view taken along line AB in FIG. The recording head 13 is obtained by bonding a heating element substrate 15 to glass, ceramic, silicon, polysulfone, a plastic plate or the like having a flow path (nozzle) 14 through which ink passes. The heating element substrate 15 includes a protective layer 16-1 formed of silicon oxide, silicon nitride, silicon carbide, or the like, a metal such as platinum, or a metal oxide such as a platinum oxide, particularly,
Top surface protective layer 16-2 formed of tantalum or a tantalum oxide, electrodes 17-1 and 17-2 formed of aluminum, gold, an aluminum-copper alloy, etc., hafnium boride, tantalum nitride, tantalum aluminum, etc. A heating resistor layer 18 made of a high melting point material;
The heat storage layer 19 is formed of silicon oxide, aluminum oxide, or the like, and the substrate 20 is formed of a material having good heat dissipation properties, such as silicon, aluminum, or aluminum nitride.

In the ink jet recording apparatus utilizing thermal energy, the electrodes 17-1 and 17-
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, and the ink 21 is discharged through the nozzle 14 of the recording head 13, and the discharge orifice 2 is discharged.
The ink droplets 24 become ink droplets 24 and fly toward the recording medium 25. 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 includes a glass plate 27 having a multi-nozzle 26,
Is formed by bonding a heating head 28 similar to that described in the above.

(Amount of Energy Applied to Heater) Next, γ
The values will be described. The γ value is a factor representing the ratio of the energy actually input by the bubble jet head to the critical energy at which the ink or liquid composition can be ejected. That is, when the width of the pulse applied to the bubble jet head is P (the total width when a plurality of pulses are divided and applied), the applied voltage is V, and the resistance of the heater is R, the input energy E is It is represented by the following formula (A). E = P × V ² / R (A) At this time, the minimum energy required for the heater to be able to discharge the ink or liquid composition by the bubble jet head is defined as _Eth, and the input energy when actually driving is performed. Is E _op , the γ value is given by the following equation (B). γ = E _op / E _th (B)

From the driving conditions of the bubble jet head, for example, γ suitable for discharging a liquid composition
As a method of obtaining the value, the following two methods (1) and (2) are practically used. (1) When the pulse width is fixed First, an appropriate voltage at which the bubble jet head discharges the liquid composition is found and driven with the given pulse width.
Next, the voltage is gradually lowered to find a voltage at which the discharge of the liquid composition stops, and the minimum dischargeable voltage immediately before this voltage is set to _Vth . The voltage actually used for driving is V
Assuming _op , the γ value is obtained by the following equation (C). γ = (V _op / V _th ) ² (C)

(2) When the Voltage is Fixed First, at a given voltage, the bubble jet head finds and drives an appropriate pulse width for discharging the liquid composition.
Next, the pulse width is gradually reduced to find a pulse width at which the discharge of the liquid composition stops. The minimum pulse width that can be ejected immediately before this pulse width is _Pth . Assuming that the pulse width actually used in the driving is _Pop , the γ value is obtained by the following equation (D). γ = P _op / P _th (D)

Here, the voltage value is a voltage actually applied to the heater section for causing the bubble jet heater to generate heat. Since a voltage applied from outside the head may drop at a contact point, a wiring resistance, or the like, it cannot be used for calculating the γ value in a strict sense. However, when V _th and V _op are measured from outside the head, these voltage fluctuations are included and measured in both values. Therefore, unless the voltage fluctuations are large, γ is directly used by these values. Even if the value is calculated, the error is small, and thus the value obtained by this is conveniently referred to as γ
Can be used as a value.

Also, when recording is performed by an actual printer, it is necessary to pay attention to the fact that a plurality of heaters are driven, so that the voltage for one heater may be affected by the influence and may fluctuate. is there. Further, from the above equations (A) and (B), at the same γ value, it seems that the square of V and P are inversely proportional, but in fact, the electrical characteristics such that the pulse waveform does not become rectangular, etc. If the pulse waveform is different, there is a thermal problem such as different heat diffusion around the heater, and if the voltage is different, there is a problem specific to bubble jet such as a different heat flux from the heater to the ink and a change in the foaming state. V2
The power and P are not in a simple relationship. Therefore, the methods described in the above (1) and (2) must be handled independently, and it is noted that converting from one value to another by calculation may cause an error. Must.
In the present invention, unless otherwise specified, the value obtained by the above method (1) was used as the γ value.

For stable ejection of the ink or liquid composition, the γ value obtained as described above should be 1.12 to 1.γ.
It is general that the ink jet recording apparatus is driven under a condition of about 96. However, in the first embodiment in which thermal energy is applied to the liquid composition having the above-described configuration and the liquid composition is ejected from the recording head, the γ value is in a predetermined range, specifically, the γ value is 1.10 to 1.10. If the ink jet recording apparatus is driven within the range of 1.90, sticking of kogation to the heater due to ejection of the liquid composition having the above configuration is further prevented, and the life of the recording head is further extended. Therefore, it is preferable.

When the γ value in applying the thermal energy to the liquid composition according to the first embodiment and ejecting the liquid composition from the recording head is within the above range, the adhesion of kogation to the heater can be particularly effectively prevented. As a result, the reason why the life of the recording head can be extended is not clear, but the present inventors think as follows. That is, first, if the inkjet recording apparatus is driven so that the γ value is in the above range, the acid having an amino group and / or the acid contained in the liquid composition according to the present embodiment are contained. Salt (a)
However, it is considered that as a result of protecting the outermost surface protective layer of the heater, the erosion of the metal constituting the outermost surface protective layer and / or the oxide of the metal is effectively prevented. Secondly,
If the inkjet recording apparatus is driven so that the γ value is in the above-described range, the energy is not excessively supplied to the heater, and the surface temperature of the heater does not become excessively high. Polyvalent metal ions resulting from the polyvalent metal salt (a) added to the liquid composition for the purpose of improving the water resistance of the recorded matter increase the alkalinity, resulting in excessive metal erosion (dissolution). It is thought that it is because there is no thing.

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

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 comes into contact with the ink discharge port surface. And a configuration for performing capping. Further, 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 unit 64, and the blade 61
In addition, moisture, dust, and the like are removed from the ejection port surface by the ink absorber 63.

Reference numeral 65 denotes a discharge energy generating means.
A recording head 66 for performing recording by ejecting ink to a recording medium facing an ejection port surface provided with ejection 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 65
The recording medium is fed to a position facing the discharge port surface, and is discharged to a discharge section provided with a discharge roller 53 as recording proceeds. In the above configuration, when the recording head 65 finishes recording 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 by contacting the cap 62 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 positions as the positions at the time of the wiping described above. As a result,
Also in this movement, the ejection port surface of the recording head 65 is wiped. 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 to the home position adjacent to the printing area while the printing head moves through the printing area for printing. Then, the wiping is performed along with this movement.

FIG. 5 is a view showing an example of an ink cartridge 45 containing ink supplied to a 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 first embodiment is not limited to the apparatus in which the recording head and the ink cartridge are separated as described above, but may be an apparatus in which they are integrated as shown in FIG. . In FIG. 6, reference numeral 70 denotes a recording unit, in which an ink storage unit storing ink, for example, an ink absorber is stored, and a head unit 71 having a plurality of orifices in the ink in the ink absorber. Are ejected as ink droplets from the ink. It is preferable to use polyurethane as the material of the ink absorber. Further, a structure may be used in which the ink storage unit is an ink bag in which a spring or the like is provided inside without using the ink absorber. Reference numeral 72 denotes an atmosphere communication port for communicating the inside of the cartridge with the atmosphere. This recording unit 70 is used in place of the recording head 65 shown in FIG. 4, and is detachable from the carriage 66.

When a color image is formed by the ink jet recording method according to the first embodiment, for example,
A printing apparatus in which five print heads shown in FIG. 3 are arranged on a carriage 96 is used. FIG. 7 shows an example. 91,
Reference numerals 92, 93, and 94 denote recording heads for ejecting yellow, magenta, cyan, and black inks, respectively. Reference numeral 95 denotes a head for discharging a liquid composition. The head is disposed in the above-described printing apparatus, and discharges each color ink according to a print signal. In addition, for example, prior to the ejection of each color ink, the liquid composition is allowed to adhere to at least the image forming portion where the ink adheres to the recording medium.

FIG. 7 shows an example in which five recording heads are used. However, the present invention is not limited to this. As shown in FIG. 8, one recording head uses yellow 101 and magenta 1
02, cyan 103 and black 104, liquid composition 1
It is also preferable to perform the step 05 and step 05 separately from each other. Of course, the heads may be arranged such that the recording order of each ink and liquid composition is reversed from the above-described order.

As specific examples of the arrangement of the ink jet recording head suitably used in the first embodiment, there are three types as shown in FIGS. 9 to 11
, 111-114, 121-124 and 131
To 134 are yellow (Y), magenta (M),
This is a recording head for discharging inks of cyan (C) and black (Bk). Reference numerals 115, 125, and 135 denote recording heads for discharging the liquid composition (S). Each recording head is arranged on the carriage in the same manner as shown in FIG. 7 (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. Before or after the liquid composition, the liquid composition is applied to an image area where at least each color ink adheres to the recording medium. 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.
(115), Bk (114), C (113), M (11
The recording heads for 2) and Y (111) are arranged on the carriage in parallel. The second configuration example shown in FIG. 10 includes recording heads for the liquid composition and the black ink arranged in parallel, and Y (121) arranged in parallel with these recording heads and arranged in series with each other. M (122) and C (123) recording heads. Here, the ejection volume per dot of each recording head does not necessarily have to be the same, and the ejection volume per dot of each recording head may be adjusted according to the composition of the liquid composition and the like so that optimal recording is performed. (Vd) may be adjusted. Preferably,
A configuration in which Vd of S, Y, M, and C is the same and Bk is twice as large is preferable, but not limited to this. Further, in the third configuration example shown in FIG. 11, Bk (13
4), S (135), Bk (134), C (133),
The recording heads for M (132) and Y (131) are arranged in parallel on the carriage, and the ejection amount of the black ink can be twice the ejection amount of the other liquid composition and the color ink. . Note that also in the configuration example shown in FIG. 11, the ejection volumes (Vd) of S, Bk, Y, M, and C are:
They are not necessarily the same.

Further, as described above, in the first embodiment, the ratio of the applied amount per unit area of the recording medium between the liquid composition and the coloring ink, particularly the magenta ink, in the image forming area is as follows. The ratio may be 1: 1, but the ratio of the color ink to the liquid composition may be 10: 1 to 10:10. The adjustment of the ratio of the liquid composition per unit area on the recording medium and the applied amount of the colored ink in the image forming region is, specifically, for example, the number of pixels of the liquid composition to be deposited on the recording medium, A method of controlling the number of pixels of the colored ink adhering on the recording medium to be in a range of 10 to 100%, and a discharge amount of the liquid composition when applying the liquid composition and the colored ink. The number of pixels of the liquid composition deposited on the recording medium is in the range of 10 to 100% of the number of pixels of the colored ink deposited on the recording medium, by a method of controlling the number of pixels to be smaller than that of the colored ink. And the discharge amount of the liquid composition when applying the liquid composition and the colored ink onto the recording medium may be made smaller than the discharge amount of the colored ink.

[Second Embodiment] Next, a specific second embodiment of the present invention (referred to as a second embodiment) will be described. In the second embodiment, (1) a color ink containing a colorant, a liquid medium, a polyvalent metal salt, a substance selected from an acid having an amino group and a salt thereof, (2) a colorant and a liquid A black ink and a color ink comprising an ink set for inkjet recording, comprising a medium and a black ink that reacts with the color ink by contact with the color ink. Are applied to form a contact state on the recording medium, and recording is performed.

The purpose of the ink set according to the second embodiment of the present invention is to prevent bleeding between the black ink and the color ink. No special measures have been taken. However, if the color ink is subjected to a process of giving quick penetration to sized plain paper, specifically, for example,
If an ink design such as adding a surfactant to the color ink is performed, it is effective to prevent bleeding between color inks of different colors.

First, the color ink constituting the ink set according to the second embodiment will be described. The color ink includes a coloring material, a liquid medium, a polyvalent metal salt, and a substance selected from an acid having an amino group and a salt thereof. The polyvalent metal salt, the acid having an amino group or a salt thereof 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 second embodiment will be described. Examples of the coloring material include direct dyes, acid dyes, basic dyes, disperse dyes and pigments. preferable. As such coloring materials, those listed below can be used.

For example, C.I. I. Acid yellow 23;
C. 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,
25, 32, 33, 36, 51; I. Basic orange 2, 15, 21, 22; C.I. I. Basic Red 1, 2, 9, 12, 13, 37, 38, 39, 92;
C. I. Basic violet 1, 3, 7, 10, 1
4; I. Basic Blue 1, 3, 5, 7, 9, 1
9, 24, 25, 26, 28, 29, 45, 54, 6
5; I. Basic green 1, 4; C.I. 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 0.1 to 20% by mass based on the total amount of the ink.
It is preferable to be within the range.

It is preferable that the color ink constituting the ink set for ink jet recording according to the second embodiment contains at least one surfactant in addition to the components described above. By including a surfactant, it becomes possible to impart desired permeability and viscosity to the color ink. That is, as described above, in the second embodiment, no special measures are taken to prevent bleeding between color inks such as yellow ink, magenta ink, and cyan ink. By adding a surfactant to the ink, an ink having a high permeability to sized plain paper can be obtained. As a result, it is possible to prevent bleeding between the color inks, and it is possible to prevent a large reduction in print quality in practical use.

As the above-mentioned surfactant, a conventionally known surfactant such as an anionic surfactant, a cationic surfactant and a nonionic surfactant may be used. Among them, it is preferable to use a nonionic surfactant. The amount of these surfactants to be added to the color ink is not particularly limited. However, in order to obtain a desired permeability and obtain an appropriate ink viscosity, 0.01 to 10% by mass of the total amount of the ink is used.
It is preferable to be within the range. More preferably, 0.1
To 10% by mass.

Next, the black ink constituting the ink set for ink jet recording according to the second embodiment will be described. The black ink used in the second embodiment includes a color material and a liquid medium, and reacts with the color ink by contact with the color ink having the above configuration. Specifically, it is preferable to use a coloring material that reacts with a polyvalent metal ion resulting from the polyvalent metal salt in the color ink. Here, the “reaction” has the same meaning as in the above-described first embodiment. Examples of the color material used for the black ink include a black color material that can be used for the color ink of the first embodiment. These coloring materials may be used alone or in combination of two or more. Further, the amount of these coloring materials to be added is preferably in the range of 0.1 to 20% by mass based on the total amount of the ink.

In the second embodiment, it is more preferable to add a nonionic surfactant to the black ink. That is, by doing so, it is possible to further suppress bleeding between the black ink and the color ink, and by adding a nonionic surfactant, as described below, the black ink In addition, it is possible to obtain an effect that the reduction of the density of the black ink at the boundary between the ink and the color ink, that is, the occurrence of the so-called “white haze” can be more effectively suppressed.

As described above, the color ink used in the ink set for ink jet recording according to the second embodiment contains a surfactant for the purpose of improving the characteristics of the ink for ink jet recording. Therefore, many of them have high permeability to a recording medium such as plain paper and low surface tension. When a color ink having a low surface tension and a black ink having a high surface tension as used in the second embodiment are adjacent to each other, an area where the color material is small at an adjacent interface of the black ink is generated, and “white” A phenomenon called "haze" may occur.
Therefore, if a nonionic surfactant is added to the black ink to lower the surface tension, the above-mentioned “white haze” phenomenon can be suppressed.

In the second embodiment, the content of the nonionic surfactant contained in the black ink is not particularly limited as long as bleeding and white haze can be suppressed. In order to improve the suppression, to effectively suppress the occurrence of white haze, and to maintain good ink dischargeability and print quality, the content should be in the range of 0.1 to 0.5% by mass of the total amount of the ink. It is preferably, particularly preferably, in the range of 0.2 to 0.4% by mass.

The nonionic surfactant used in this case includes, for example, higher alcohol ethylene oxide adduct, alkylphenol ethylene oxide adduct, aliphatic ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, fatty acid Group amide ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polypropylene glycol ethylene oxide adducts, fatty acid esters of polyhydric alcohols, and nonionic surfactants of fatty acid amides of alkanolamines. All of these are preferably used, and more preferably, nonionics such as ethylene oxide adducts of higher alcohols, ethylene oxide adducts of alkylphenols, ethylene oxide-propylene oxide copolymers, and ethylene oxide adducts of acetylene glycol. Use a surfactant. Further, those having an addition mole number of the ethylene oxide adduct in the range of 4 to 20 are particularly preferable.

Next, as the liquid medium used for the black ink and the color ink constituting the ink set for ink jet recording according to the second embodiment, the liquid composition according to the first embodiment and the coloring used together therewith are used. As the liquid medium used for the ink, the water-soluble organic solvents, additives, amounts added, physical properties and the like described in detail can be used.

Next, an ink jet recording method according to the second embodiment and an ink jet recording apparatus according to the second embodiment which can realize the method will be described. The ink jet recording method according to the second embodiment includes the following steps.
Applying energy for ejecting the ink to the black ink included in the ink set according to the embodiment, ejecting the black ink toward the recording medium, and applying the black ink onto the recording medium; The method according to the second embodiment includes a step of applying energy for ejecting the ink to the color ink included in the ink set, ejecting the color ink toward the recording medium, and applying the energy to the recording medium. And In this case, as a suitable inkjet recording method, there is a method in which thermal energy is applied to the ink to eject the ink.

The recording medium used at this time is not particularly limited. However, in the present invention, particularly, when an image is formed on a so-called plain paper such as copy paper or bond paper which is conventionally used by using the ink set according to the second embodiment, the bleed reduction effect is obtained. Is remarkable, which is preferable. Of course, the ink set for ink jet recording according to the second embodiment can suitably use, for example, a coated paper or a transparent film for OHP specially prepared for ink jet recording. Can also be suitably used.

Further, in the ink jet recording method according to the second embodiment, the steps (i) and (ii) are performed such that a contact state between the black ink and the color ink is formed on a recording medium. It is characterized by performing. As a specific mode of applying the black ink and the color ink on the recording medium as described above, there is a method of applying the black ink and the color ink such that the black ink and the color ink are in contact at the boundary.

As another embodiment, a method of applying the black ink (1) and the color ink (2) so as to overlap on the recording medium and applying the color ink to the recording medium prior to the black ink. (Hereinafter, referred to as an underlay method). By performing the underlaying method, the bleed between the black ink and the color ink is further improved, and the above-mentioned “white haze” is further reduced. 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 the above-described second embodiment is more effective. In order to achieve this, it is preferable that the time be within several seconds, particularly preferably within one second.
There is also a mode in which the color ink is applied after the black ink is applied (overstrike), or the color ink and the black ink are mixed immediately after ejection as shown in FIG.

In the underlaying method, the ratio of the amounts of the black ink (1) and the color ink (2) applied per unit area of the recording medium in the image forming area may be 1: 1. Black ink (1): color ink (2) = 10: 1 to 10:10. By doing so, the white haze of the obtained image is reduced, and uniformity is achieved particularly in a solid image. Incidentally, the adjustment of the ratio of the application amounts of the black ink and the color ink per unit area on the recording medium in the image forming area is, specifically,
For example, when the black ink and the color ink are applied by the inkjet recording method, the number of pixels of the color ink adhered on the recording medium is 10 to 100% of the number of pixels of the black ink adhered on the recording medium. The control is performed so as to be within the range, or the discharge amount of the color ink is controlled to be smaller than the discharge amount of the black ink. The number is 10 to 100 of the number of pixels of the color ink and the black ink adhering on the recording medium.
%, And the color ink ejection amount at that time is made smaller than the black ink ejection amount.

In the second embodiment, an ink jet recording method is used as a method for depositing the black ink and the color ink constituting the ink set for ink jet recording according to the second embodiment on a recording medium. Conventionally, various known ink jet systems (for example, an ink jet recording method using mechanical energy due to deformation of a piezoelectric element) can be used. Is preferable because a remarkable effect of (1) is obtained.

That is, as described above, when a color ink containing a polyvalent metal salt is used for the purpose of improving the suppression of bleeding of color mixture between the black ink and the color ink, the discharge of the color ink is prevented. The occurrence of kogation that occurs when an image is formed by using an ink jet recording method that utilizes heat energy, and the reduction in image quality caused by the kogation, are caused by the specific black ink (1) and the color ink (2) according to the second embodiment. ) Is effectively suppressed by an ink jet recording method using an ink set composed of the combination of Furthermore, in the conventional method, when a color ink having a polyvalent metal salt for the purpose of suppressing bleeding is repeatedly ejected from a recording head, it is formed on a heater (heating element substrate) for applying thermal energy. The outermost protective layer made of a metal and / or a metal oxide, for example, tantalum or a tantalum oxide, is melted, thereby causing disconnection of the heater, making discharge impossible, or causing burnout on the heater. In some cases, sticking occurs and affects the quality of the formed image, but such a problem is effectively prevented. The ink jet recording apparatus using thermal energy is as described in detail in the description of the first embodiment.

In the case of forming a color image by the ink jet recording method according to the second embodiment, for example,
A recording apparatus in which four recording heads shown in FIG. 3 are arranged on a carriage is used. FIG. 12 shows an example. 141,
142, 143 and 144 are yellow ink (Y), magenta ink (M) and cyan ink (C), respectively.
And a recording head for discharging black ink (Bk). The head is disposed in the above-described recording apparatus, and discharges each color ink in accordance with a recording signal for discharging each color ink, for example, while moving a carriage in the direction of an arrow.

FIG. 12 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 preferable that the liquid channels of the cyan ink 153, the magenta ink 152, and the yellow ink 151 be separated. Two specific examples of the arrangement of the ink jet recording head suitably used in the second embodiment are shown in FIGS. 14 and 15. 14 and 15, 161 to 164 and 171 to 174
Are recording heads for discharging various yellow, magenta, cyan and black inks, respectively. Each recording head is arranged on the carriage in the same manner as shown in FIG. 12 (depending on the configuration example). Each recording head is arranged in the ink jet recording apparatus as described above, and discharges various inks according to a recording signal. still,
Each recording head is moved by a carriage in the direction of arrow (1), and the recording medium is moved in a direction of arrow (2) by a paper feed roller or the like.

First, in the configuration example shown in FIG.
(164), C (163), M (162) and Y (16
The recording heads for 1) are arranged on the carriage in parallel. In the second configuration example shown in FIG. 15, the recording head for black ink (174) and the recording heads C (173) and M (M) are arranged in parallel with each other and in series with each other.
(172) and a recording head for Y (171).
In FIG. 14, 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.

[0114]

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. In the following description, “parts” and “%” are based on mass unless otherwise specified.

[Examples and Comparative Examples of the First Embodiment] (Examples 1 to 36 and Comparative Examples 1 to 12) The following components were used for each liquid composition and colored ink. As the production method, for the liquid composition and the coloring ink using a dye as a coloring material, after dissolving the following components, a micro filter having a pore size of 0.2 μm (manufactured by Fuji Photo Film Co., Ltd.) is used. The mixture was filtered under pressure to prepare colored inks using the respective liquid compositions and dyes as coloring materials. 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 (Fuji Photo Film Co., Ltd.) (Manufactured by Co., Ltd.) to obtain a colored ink using each pigment as a coloring material.

Liquid compositions 1 to 4 were prepared with the following components.
The liquid composition 4 corresponds to a comparative example. <Liquid composition 1>-20 parts of diethylene glycol-2 parts of acetylenol EH (manufactured by Kawaken Fine Chemical)-2 parts of magnesium nitrate hexahydrate-2 parts of taurine-74 parts of water

<Liquid composition 2> Triethylene glycol monobutyl ether 10 parts Glycerin 10 parts Magnesium gluconate 4 parts Taurine 3 parts Water 73 parts

<Liquid composition 3> Triethylene glycol monobutyl ether 10 parts Glycerin 10 parts Calcium glycerophosphate 1 part Monosodium aspartate 2 parts Water 77 parts

<Liquid composition 4>-20 parts of diethylene glycol-2 parts of acetylenol EH (manufactured by Kawaken Fine Chemical)-78 parts of water

<Black Ink 1> (Preparation of Pigment Dispersion 1) 300 g of commercially available acidic carbon black “MA77” (pH 3; manufactured by Mitsubishi Chemical Corporation) was thoroughly mixed in 1000 ml of water, and then hypochlorous acid was added thereto. 450 g of soda (effective chlorine concentration 12%) was dropped and 10
The mixture was stirred at 0 to 105 ° C for 10 hours. The obtained slurry was applied to Toyo Filter Paper No. 2 (Advantis), and the pigment particles were sufficiently 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. Introducing -COONa group on the surface of carbon black by the above method,
Pigment dispersion liquid 1 having the self-dispersion type carbon black was obtained.

(Preparation of Ink) The following components including the pigment dispersion 1 obtained above were mixed, and a microfilter having a pore size of 3 μm (Fuji Photo Film Co., Ltd.)
) To obtain Black Ink 1. -40 parts of the above pigment dispersion liquid-8 parts of glycerin-5 parts of trimethylolpropane-4 parts of isopropyl alcohol-43 parts of water

<Black Ink 2> (Preparation of Pigment Dispersion 2) 5 parts of styrene-acrylic acid-butyl acrylate copolymer (acid value 116, average molecular weight 3,700) 5 parts of triethanolamine 0.5 part Diethylene glycol 5 parts ・ Water 69.5 parts The above components were mixed and heated to 70 ° C in a water bath.
Completely dissolve the resin component. Carbon black “MA-100” (pH 3.5; Mitsubishi Chemical Corporation)
15 parts) and 5 parts of 2-propanol were added, and premixing was performed for 30 minutes, followed by dispersion treatment under the following conditions. -Disperser: Sand grinder (Igarashi Kikai)-Grinding media: zirconium beads 1 mm diameter-Filling ratio of the grinding media: 50% (volume)-Grinding time: 3 hours Further, centrifugation (12,000 rpm, 20 minutes)
Was carried out to remove coarse particles to obtain a pigment dispersion liquid 2 containing carbon black.

(Preparation of Ink) The following components including the pigment dispersion 2 obtained above were mixed, and the
μm micro filter (Fuji Photo Film Co., Ltd.)
The mixture was subjected to pressure filtration using to prepare Black Ink 2. -20 parts of the above pigment dispersion 2-5 parts of trimethylolpropane-10 parts of diethylene glycol-5 parts of 2-pyrrolidone-Acetyleneol EH (manufactured by Kawaken Fine Chemicals)
2 parts ・ Water 59.8 parts

<Black Ink 3> The following components containing Exemplified Compound 1 as a coloring material were mixed, and 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.). A black ink 3 was prepared. 2 parts of the exemplified compound 1 (where M is NH ₄ ⁺ ) 10 parts of diethylene glycol 5 parts of 2-pyrrolidone 5 parts of 2-propanol 0.1 part of sodium hydroxide 77.9 parts of water

<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. Pi
gment Yellow 93 and 20 parts of isopropyl alcohol were added, and the mixture was premixed for 30 minutes, and then subjected to a dispersion treatment under the following conditions.

-Dispersing machine: sand grinder-Grinding media: glass beads 1 mm diameter-Filling rate of grinding media: 50% (volume)-Grinding time: 3 hours Further centrifugation treatment (12,000 rpm, 20 minutes) was performed. The coarse particles were removed to obtain a pigment dispersion 3.

(Preparation of Ink) The following components including the pigment dispersion 3 obtained above were mixed, and
μm micro filter (Fuji Photo Film Co., Ltd.)
The mixture was filtered under pressure to prepare Yellow Ink 1. -20 parts of the above pigment dispersion 3-15 parts of glycerin-10 parts of diethylene glycol-Acetyleneol EH (manufactured by Kawaken Fine Chemicals)
3 parts ・ Water 54.7 parts

<Yellow Ink 2> The following components containing Exemplified Compound 2 as a coloring material were used and dissolved. The mixture was filtered under pressure to prepare a yellow ink 2. - Compound Example 2 (M in the formula NH ₄ ⁺⁾ 3 parts Glycerin 7 parts Diethylene glycol 5 parts Urea 5 parts Ethanol 2 parts Water 78 parts

<Magenta Ink 1> (Preparation of Pigment Dispersion Liquid 4) 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 mixed in a water bath.
The mixture was heated to ° C. to completely dissolve the resin component. To this solution was added C.I. I. Pigment Red 122 (20 parts) and isopropyl alcohol (1.0 part) were added, and premixing was performed 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 grinding media: 50% (volume)-Grinding time: 3 hours Further centrifugation treatment (12,000 rpm, 20 minutes) was performed. The coarse particles were removed to obtain Pigment Dispersion Liquid 4.

(Preparation of Ink) The following components including the pigment dispersion liquid 4 obtained above were mixed, and the
μm micro filter (Fuji Photo Film Co., Ltd.)
, And magenta ink 1 was prepared. -20 parts of pigment dispersion 4-15 parts of glycerin-10 parts of diethylene glycol-Acetyleneol EH (manufactured by Kawaken Fine Chemicals)
3 parts ・ Water 54.7 parts

<Magenta Ink 2> The following components containing Exemplified Compound 3 as a coloring material were used, and after dissolving them, the mixture was applied using a micro filter having a pore size of 0.2 μm (manufactured by Fuji Photo Film Co., Ltd.). The mixture was filtered under pressure to prepare magenta ink 2. 3 parts of the above exemplified compound 3 (M is NH ₄ ⁺ ) 3 parts of glycerin 5 parts of diethylene glycol 5 parts of urea 2 parts of ethanol 78 parts of water

<Cyan Ink 1> (Preparation of Pigment Dispersion Liquid 5) 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. Further, C.I. I.
Pigment Blue 15: 3 (20 parts) and isopropyl alcohol (1.0 part) 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 grinding media: 50% (volume) Grinding time: 3 hours Further, centrifugation treatment (12,000 rpm, 20 minutes)
Was carried out to remove coarse particles to obtain a pigment dispersion liquid 5.

(Preparation of Ink) The following components including the pigment dispersion 5 obtained above were mixed, and the
μm micro filter (Fuji Photo Film Co., Ltd.)
The resultant was subjected to filtration under pressure to prepare Cyan Ink 1. -20 parts of pigment dispersion 5-15 parts of glycerin-10 parts of diethylene glycol-Acetyleneol EH (manufactured by Kawaken Fine Chemicals)
3 parts ・ Water 54.7 parts

<Cyan Ink 2> The following components containing Exemplified Compound 4 as a coloring material were used, and after dissolving them,
Pressure filtration was performed using a micro filter having a pore size of 0.2 μm (manufactured by Fuji Photo Film Co., Ltd.) to prepare a cyan ink 2. 3 parts of the exemplified compound 4 (M in the formula is NH ₄ ⁺ ) 7 parts of glycerin 5 parts of diethylene glycol 5 parts of urea 2 parts of ethanol 78 parts of water

(Evaluation and Evaluation Criteria) <Evaluation Test> The evaluation test is shown below. [Evaluation 1] The liquid compositions 1 to 3 having the constitution of the present invention obtained as described above, and the liquid composition 4 of the comparative example
The on-demand type multi-recording head (BC-02 (manufactured by Canon Inc.)) which applies a thermal energy corresponding to a recording signal to the ink to discharge the liquid composition: the outermost surface protective layer on the heater is tantalum and The liquid composition was evaluated by discharging the liquid composition under the following conditions using an inkjet recording apparatus having a tantalum oxide). The discharge conditions of the liquid composition of the above-mentioned inkjet recording apparatus are as follows: pulse width 1.1 μs (On) +3.0 μs (Off) +3.2.
At μs (On) and a driving frequency of 6,250 Hz, V _th (critical voltage just before discharging) is actually measured, and a liquid composition is discharged by applying V _op (driving voltage) corresponding to a γ value of 1.6. Was. Then, when ink jet recording was performed under these conditions, the ejection durability of the ink jet recording head and the state of occurrence of kogation on the heater were evaluated by the following methods and criteria. The results are shown in Table 1.

[0139] 1. Discharge durability Continuous discharge is performed under the same driving conditions as the device, and droplets discharged from the recording head are collected in a container every 1 × 10 ⁶ shots.
Weighed on an electronic balance. The average amount of ejected droplets at 1 × 10 ⁶ shots was calculated from the increased amount of the container. The continuous discharge is 1
The test was performed up to × 10 ⁸ and evaluated according to the following criteria. A: The average amount of ejected droplets between 9.9 × 10 ^{7 and} 1 × 10 ⁸ shots is 90 compared to the average amount of ejected droplets after 0-1 × 10 ⁶ shots.
%that's all. B: The average amount of ejected droplets between 9.9 × 10 ^{7 and} 1 × 10 ⁸ shots is 90 compared to the average amount of ejected droplets after 0-1 × 10 ⁶ shots.
% To 70%. C: The average amount of ejected droplets between 9.9 × 10 ^{7 and} 1 × 10 ⁸ shots is 70 compared to the average amount of ejected droplets after 0-1 × 10 ⁶ shots.
%Less than. D: Discharge failed on the way.

2. Deposition of kogation The recording head, which has been subjected to the discharge durability evaluation test of the head, is disassembled, and the heater surface of the nozzle after the endurance of discharge is observed with an optical microscope (400-fold magnification) to check the amount of kogation deposited. The adhered amount was evaluated according to the following criteria. A: Almost no kogation was observed. B: Slight adhesion of kogation is observed. C: Many kogation adheres. D: Very much kogation is observed.

[0141]

[Evaluation 2] Each of the coloring inks obtained above and each of the liquid compositions 1 to 3 were recorded on recording paper using the combinations shown in Table 2. As the inkjet 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 firstly applied and 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. The ejection volume per dot is 80 pl / dot for the colored ink and 40 pl / d for the liquid composition.
ot head was used. The recording paper used was PB paper (manufactured by Canon Inc .: common paper for copier and ink jet recording) and XEROX 4024 paper (manufactured by Xerox Corporation).

3. Image Water Resistance Each colored ink and liquid composition were printed using the combination shown in Table 2 by the above method, and after the printed matter was allowed to stand for 1 hour, the print density was adjusted to Macbeth RD915 (trade name: Macbeth) Measurement). 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 was determined, and the water resistance was evaluated. It is practically preferable that the residual ratio of the print density is 95% or more. Table 2 shows the evaluation results.

[0144] 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%.

4. Image print quality (bleeding) Print alphanumeric characters (12 points) in the same way and leave for 1 hour, then visually evaluate the sharpness of the characters and the degree of mustache-like bleeding that occurs at the edges of the characters did. Table 2 shows the evaluation results. 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.

[0146]

[0147]

[0148] 5. Bleed (mixed color bleeding between different colors) First, a solid portion was printed with the liquid composition on each of the two plain papers using an ink set including the combination of the liquid composition and the colored ink shown in Table 3. Immediately thereafter, a solid portion is printed with the black ink over the solid portion of the liquid composition, and immediately thereafter, the yellow portion over the solid portion of the liquid composition is adjacent to the solid portion of the black ink, or A solid portion of each color ink was printed with magenta or cyan ink. 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 were as follows. 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. Table 3 shows the evaluation results.

[0149]

[Examples and Comparative Examples of Second Embodiment] (Examples 37 to 39 and Comparative Example 13) Examples 37 to 39 and Comparative Example 13 by combining black ink and yellow, magenta, and cyan color inks. Was prepared. Each ink was prepared by the following method using the components listed below. For the black ink constituting each ink set, the same pigment dispersions 1 and 2 as described in the first embodiment were used, and after mixing with the following components, the pore size was 3 μm. It was prepared by pressure filtration using a micro filter (manufactured by Fuji Photo Film Co., Ltd.). Further, for the color inks constituting each ink set, as a preparation method, for a liquid composition, and for a colored ink using a dye as a coloring material, after mixing with each component listed below, the pore size is 0.2 μm.
Each of the color inks was subjected to pressure filtration using a micro filter (manufactured by Fuji Photo Film Co., Ltd.). Table 4 shows the main compositions of the ink sets of Examples 37 to 39 and Comparative Example 13.

<Ink set of Example 37> (Black ink composition)-40 parts of the above pigment dispersion liquid-8 parts of glycerin-5 parts of trimethylolpropane-4 parts of isopropyl alcohol-43 parts of water

(Yellow ink composition) C.I. I. Acid Yellow 23 2.5 parts ・ Glycerin 5 parts ・ Diethylene glycol 5 parts ・ Acetyleneol EH (manufactured by Kawaken Fine Chemicals) 1 part ・ Magnesium acetate tetrahydrate 2 parts ・ Taurine 1 part ・ Water 83.5 parts

(Magenta ink composition) I Acid Red 289 2 parts-Glycerin 8 parts-Diethylene glycol 5 parts-Acetylenol EH (manufactured by Kawaken Fine Chemical) 1 part-Magnesium nitrate hexahydrate 1 part-Aspartic acid-sodium 0.5 part-Water 82.5 Department

(Cyan ink composition) C.I. I Acid Blue 9 2 parts ・ Glycerin 8 parts ・ Diethylene glycol 5 parts ・ Acetyleneol EH (Kawaken Fine Chemical) 1 part ・ Magnesium nitrate hexahydrate 1 part ・ Taurine 1 part ・ Water 82 parts

<Ink set of Example 38> (Black ink composition)-40 parts of the above pigment dispersion liquid-5 parts of glycerin-5 parts of diethylene glycol-5 parts of 2-pyrrolidone-acetylenol EH (manufactured by Kawaken Fine Chemicals) 0.3 Part ・ Water 44.7 parts

(Yellow ink composition) C.I. I. Acid Yellow 23 2.5 parts ・ Glycerin 5 parts ・ Diethylene glycol 5 parts ・ Trimethylolpropane 5 parts ・ Acetylene EH (Kawaken Fine Chemical) 1 part ・ Magnesium gluconate 1 part ・ Taurine 1 part ・ Water 79.5 parts

(Magenta ink composition) I Acid Red 289 2 parts-Glycerin 8 parts-Diethylene glycol 5 parts-Thiodiglycol 5 parts-Acetyleneol EH (manufactured by Kawaken Fine Chemical) 1 part-Magnesium gluconate 1.5 parts-Taurine 1 part-Water 76.5 parts

(Cyan ink composition) C.I. I Acid Blue 9 2 parts ・ Ethylene glycol 8 parts ・ Diethylene glycol 5 parts ・ Trimethylolpropane 5 parts ・ Acetylenol EH (Kawaken Fine Chemical) 1 part ・ Calcium gluconate 1 part ・ Taurine 1 part ・ Water 77 parts

<Ink set of Example 39> (Black ink composition) 20 parts of the above pigment dispersion 2 5 parts of trimethylolpropane 10 parts of diethylene glycol 5 parts of 2-pyrrolidone acetylenol EH (manufactured by Kawaken Fine Chemicals) 0 .2 parts ・ Water 59.8 parts

(Yellow ink composition) C.I. I. Acid Yellow 23 2.5 parts ・ Glycerin 5 parts ・ Diethylene glycol 5 parts ・ Trimethylolpropane 5 parts ・ Acetyleneol EH (Kawaken Fine Chemical) 1 part ・ Calcium glycerophosphate 1 part ・ Taurine 1 part ・ Water 79.5 parts

(Magenta ink composition) C.I. I Acid Red 289 2 parts-Glycerin 8 parts-Diethylene glycol 5 parts-Thiodiglycol 5 parts-Acetyleneol EH (Kawaken Fine Chemical) 1 part-Calcium glycerophosphate 1 part-Taurine 1 part-Water 77 parts

(Cyan ink composition) C.I. I Acid Blue 9 2 parts ・ Ethylene glycol 8 parts ・ Diethylene glycol 5 parts ・ Trimethylolpropane 5 parts ・ Acetyleneol EH (Kawaken Fine Chemical) 1 part ・ Calcium glycerophosphate 1 part ・ Taurine 1 part ・ Water 77 parts

<Ink Set of Comparative Example 13> (Black ink composition) ・ 40 parts of the above pigment dispersion liquid ・ 8 parts of glycerin ・ 5 parts of trimethylolpropane ・ 4 parts of isopropyl alcohol ・ 43 parts of water

(Yellow ink composition) C.I. I. Acid Yellow 23 2.5 parts ・ Glycerin 5 parts ・ Diethylene glycol 5 parts ・ Acetyleneol EH (Kawaken Fine Chemical) 1 part ・ Water 86.5 parts

(Magenta ink composition) I Acid Red 289 2 parts ・ Glycerin 8 parts ・ Diethylene glycol 5 parts ・ Acetyleneol EH (Kawaken Fine Chemical) 1 part ・ Water 84 parts

(Cyan ink composition) C.I. I Acid Blue 9 2 parts ・ Glycerin 8 parts ・ Diethylene glycol 5 parts ・ Acetyleneol EH (Kawaken Fine Chemical) 1 part ・ Water 84 parts

[0167]

(Evaluation and Evaluation Criteria) <Evaluation Test> The evaluation test is shown below. [Evaluation 1] An on-demand type multi-recording head (BC-02) that ejects ink by applying thermal energy according to a recording signal to the inks of the ink sets of Examples 37 to 39 and Comparative Example 13 The evaluation was performed by ejecting ink under the following conditions using an ink jet recording apparatus having a (top surface protective layer on the heater made of tantalum and an oxide of tantalum) (manufactured by Canon Inc.). The ink ejection conditions of the ink jet recording apparatus are as follows: pulse width 1.1 μs (On) +3.0 μs (Of
f) +3.2 μs (On), drive frequency 6,250 Hz
Then, V _th (critical voltage just before discharging) is actually measured, and γ
The ink was ejected by applying V _op (drive voltage) corresponding to the value = 1.6. The ejection durability and the amount of kogation adhered to the heater in the ink jet recording head when ink jet recording was performed under these conditions were evaluated by the following methods and criteria. Table 5 shows the results.

(1) Ejection Durability Continuous ejection is performed under the above-described apparatus and driving conditions, and droplets ejected from the recording head every 1 × 10 ⁶ are collected in a container.
Weighed on an electronic balance. The average amount of ejected droplets at 1 × 10 ⁶ shots was calculated from the increased amount of the container. The continuous discharge is 1
The test was performed up to × 10 ⁸ and evaluated according to the following criteria. A: The average amount of ejected droplets between 9.9 × 10 ^{7 and} 1 × 10 ⁸ shots is 90 compared to the average amount of ejected droplets after 0-1 × 10 ⁶ shots.
%that's all. B: The average amount of ejected droplets between 9.9 × 10 ^{7 and} 1 × 10 ⁸ shots is 90 compared to the average amount of ejected droplets after 0-1 × 10 ⁶ shots.
% To 70%. C: The average amount of ejected droplets between 9.9 × 10 ^{7 and} 1 × 10 ⁸ shots is 70 compared to the average amount of ejected droplets after 0-1 × 10 ⁶ shots.
%Less than. D: Discharge failed on the way.

(2) Amount of kogation adhesion The recording head, which has been evaluated for the discharge durability of the head, is disassembled, and the heater surface of the nozzle used for evaluation of the discharge durability is visually observed with an optical microscope (400 times magnification). And the amount of kogation adhered were evaluated according to the following criteria. A: Almost no kogation is observed. B: Slight adhesion of kogation is observed. C: Many kogation adheres. D: Very much kogation is observed.

[0171]

[Evaluation 2] Examples 37 to 42 and Comparative Examples 13 and 14 A recording signal on which each ink of the ink sets of Examples 37 to 39 and Comparative Example 13 of the present invention obtained above was mounted. An image is formed using a color inkjet printer (BJC-700J: manufactured by Canon Inc.), which is an inkjet recording apparatus having an on-demand type multi-recording head that ejects ink by applying thermal energy to the ink in accordance with the temperature. The following (3) and (4) were evaluated.

Further, using the ink sets of Examples 37 to 39 of the present invention and Comparative Example 13, the black ink and the color ink were applied to the same position on the recording medium, and the recording of the color ink was performed. An image was created so that the application to the medium could be performed prior to the black ink (underprint). The ink jet recording method by the underlaying method using the ink sets of Examples 37 to 39 is described in Examples 40 to 4.
The same evaluation was performed by setting the ink jet recording method according to Comparative Example 14 to the ink jet recording method using the ink set of Comparative Example 13 as the under printing method. Note that the ratio of the applied amount per unit area of the recording medium between the black ink and the color ink in the underlay method is black ink: color ink = 10:
2.5, and the ratio of the applied amounts of the color inks was set to yellow ink: magenta ink: cyan ink = 1: 1: 1. Two sheets of plain paper, Canon copy paper (trade name: PB PAPER) and Xerox copy paper (trade name: 4024 PAPER), were used for the evaluation test. Table 6 shows the obtained results.

(3) 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 thereafter, yellow or magenta, Alternatively, a solid portion of each color ink was printed with 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.

(4) Density of Black Ink at Adjacent Boundary between Black Ink and Color Ink (Occurrence of White Haze) A solid portion is printed with black ink on each of the above two plain papers with each ink set. Immediately thereafter, a solid portion was printed with yellow, magenta, or cyan ink so as to be adjacent to the black ink, and the occurrence of white haze at an adjacent boundary portion with the 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 there is no practical problem. C: The density of the black ink portion at the boundary was significantly reduced.
The occurrence of white haze is remarkable.

[0176]

[0177]

As described above, according to the present invention, it is possible to form an image having water resistance, good printing quality, and reduced color bleed generated in the formation of a color image. Provided are a liquid composition, an ink-jet ink, an ink-jet recording ink set, an ink-jet recording method, a recording unit, an ink cartridge, and an ink-jet recording apparatus capable of achieving a long life.

[Brief description of the drawings]

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

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

FIG. 3 is an external perspective view of a multi-headed recording head shown in FIG. 1 of the present invention.

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

FIG. 5 is a perspective view of an internal configuration showing an example of an ink cartridge.

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

FIG. 7 is a perspective view showing a recording unit in which a plurality of recording heads are arranged.

FIG. 8 is a perspective view of another recording head used in the present invention.

FIG. 9 is a diagram illustrating a first configuration diagram of a recording head.

FIG. 10 is a diagram illustrating a second configuration diagram of the recording head.

FIG. 11 is a diagram illustrating a third configuration diagram of the recording head.

FIG. 12 is a perspective view showing a recording unit in which a plurality of recording heads are arranged.

FIG. 13 is a perspective view of another recording head used in the present invention.

FIG. 14 is a diagram illustrating a fourth configuration example of the recording head.

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

FIG. 16 is a schematic view of an inkjet recording method according to an embodiment of the present invention.

[Explanation of symbols]

 13: Recording Head 14: Ink Groove (Nozzle) 15: Heating Element Substrate 16-1: Protective Layer 16-2: Top Surface Protective Layer 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 (multi-nozzle) 27: glass plate 28: heating head 40: ink bag 42: stopper 44: ink absorber 45: ink cartridge 51: paper feed unit 52: paper feed roller 53: paper discharge roller 61: blade 62: cap 63: ink absorber 64: discharge recovery unit 65: recording head 66: carriage 67: guide shaft 68: motor 69 : Drive belt 70: recording unit 71: head section 72: atmosphere communication port 80: ink flow path 81: orifice plate 2: diaphragm 83: piezoelectric element 84: substrate 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 recording head 112: magenta ink recording head 113: cyan ink recording head 114: black Ink recording 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: A Low ink recording head 132: Magenta ink recording head 133: Cyan ink recording head 134: Black ink recording head 135: Liquid composition recording head 141: Yellow ink recording head 142: Magenta ink recording head 143: Cyan ink recording head 144: Black ink Recording head 145: Carriage 151: Yellow ink channel 152: Magenta ink channel 153: Cyan ink channel 154: Black ink channel 161: Yellow ink recording head 162: Magenta ink recording head 163: Cyan ink recording 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 Compositions 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

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hideto Yokoi 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term in Canon Inc. (reference) 2C056 EA05 EA21 FA03 FC01 FC02 2H086 BA01 BA02 BA53 BA55 BA56 BA59 BA62 4J039 BA04 BA17 BA30 BA31 BA37 BA39 BB00 BC06 BC07 BC19 BC32 BC34 BC56 BE01 BE06 BE12 CA03 CA06 EA15 EA16 EA17 EA19 EA44 EA48 GA24

Claims (46)

[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) a polyvalent metal salt; and (b) an acid having an amino group and a salt thereof. And (c) a liquid medium. 2. The total content of the polyvalent metal salt is 0.005 to 20% by mass based on the total amount of the liquid composition, and the total content of a substance selected from the above-mentioned amino group-containing acids and salts thereof The amount is 0.005 to 20% by mass based on the total amount of the liquid composition.
The liquid composition according to claim 1, which is: 3. The liquid composition according to claim 1, wherein the polyvalent metal salt is at least one selected from polyvalent metal salts of nitric acid, acetic acid, hydroxycarboxylic acid, and polyol phosphate ester. 4. The polyvalent metal salt of nitric acid, acetic acid, hydroxycarboxylic acid and polyol phosphate ester is selected from the group consisting of magnesium nitrate, calcium nitrate, barium nitrate, iron (II) nitrate, copper (II) nitrate, zinc nitrate and acetic acid. magnesium,
Calcium acetate, barium acetate, iron (II) acetate, copper (II) acetate, zinc acetate, magnesium gluconate, calcium gluconate, barium gluconate, iron gluconate (I
The liquid composition according to claim 3, comprising I), copper (II) gluconate, zinc gluconate, magnesium glycerophosphate and calcium glycerophosphate. 5. The method according to claim 1, wherein the acid having an amino group is amidosulfuric acid (also called sulfamic acid),
At least one selected from taurine (alias: 2-aminoethanesulfonic acid), carbamic acid, glycine, alanine, β-alanine, aspartic acid and glutamic acid
The liquid composition according to any one of claims 1 to 4, which is a seed. 6. The liquid composition according to claim 1, wherein energy is applied to the liquid composition and the liquid composition is ejected toward a recording medium to apply the liquid composition onto the recording medium. (Ii) applying energy to the colored ink that contains a coloring material and a liquid medium and reacts with the liquid composition by contact with the liquid composition, and discharges the colored ink toward a recording medium to form the colored ink; Applying on a recording medium, and performing the above steps (i) and (ii) such that a contact state between the liquid composition and the colored ink is formed on the recording medium. An ink jet recording method comprising: 7. The ink jet recording method according to claim 6, wherein the coloring material of the colored ink is a pigment. 8. The color material of the colored ink has at least one colorant.
The ink jet recording method according to claim 6, wherein the dye has two carboxyl groups. 9. The ink jet recording method according to claim 6, wherein the energy is heat energy. 10. The ink jet recording method according to claim 6, wherein the application of the liquid composition onto the recording medium is performed prior to the application of the colored ink onto the recording medium. 11. The ink jet recording method according to claim 6, wherein the application of the liquid composition onto the recording medium is performed after the application of the colored ink onto the recording medium. 12. The method according to claim 6, 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 thereafter, the coloring ink is further applied to the recording medium. The inkjet recording method according to any one of the above items. 13. The method according to claim 6, wherein the application of the colored ink onto the recording medium is performed after the application of the liquid composition onto the recording medium, and then the liquid composition is further applied onto the recording medium. 10. The inkjet recording method according to any one of items 9 to 9. 14. mixing the liquid composition and the coloring ink immediately after ejection from an ink jet recording apparatus;
Thereafter, the mixture is applied onto a recording medium.
The inkjet recording method according to any one of the above items. 15. A liquid composition comprising (1) the liquid composition according to any one of claims 1 to 5, and (2) a colorant and a liquid medium, wherein the liquid composition is brought into contact with the liquid composition. What is claimed is: 1. An ink set for inkjet recording, comprising a combination of a substance and a colored ink that reacts. 16. A liquid ink containing a liquid composition according to claim 1, and a colored ink which 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. And a recording unit. 17. The recording unit according to claim 16, wherein the ink jet recording head includes a heater having an outermost protective layer containing a material selected from a metal and a metal oxide. 18. The recording unit according to claim 17, wherein the outermost protective layer contains tantalum or a tantalum oxide as a substance selected from a metal and a metal oxide. 19. A liquid composition containing a liquid composition according to claim 1, comprising a coloring material and a liquid medium, and contacting the liquid composition. An ink container that contains a colored ink that reacts with the liquid composition. 20. A liquid composition accommodating section accommodating a liquid composition, a colored ink accommodating section accommodating a colored ink that reacts with the liquid composition by contact with the liquid composition, and the liquid 6. An ink jet recording apparatus equipped with an ink jet recording head for applying energy to the composition and the colored ink to discharge the liquid composition and the colored ink, respectively, wherein the liquid composition is used. An ink jet recording apparatus comprising the liquid composition according to any one of the above. 21. The ink jet recording head includes a heater having an outermost surface protection layer containing a substance selected from a metal and a metal oxide, and the ink jet recording apparatus causes the heater to pulse to the heater in accordance with recording information. 21. The ink jet recording apparatus according to claim 20, further comprising means for applying the electric signal of (1). 22. The substance selected from the group consisting of a metal and a metal oxide includes tantalum or a tantalum oxide.
2. The ink jet recording apparatus according to 1. 23. The ink jet recording apparatus according to claim 20, wherein the energy (E _op ) _supplied to discharge the liquid composition satisfies the following relationship: 1.10 ≦ E _op / E _th ≦ 1.90 (E _th is the minimum energy required to eject the liquid composition from the recording head). 24. A color ink containing (1) a colorant, a liquid medium, a polyvalent metal salt, an acid having an amino group and a substance selected from the salt, (2) a colorant and a liquid medium And a black ink that reacts with the color ink upon contact with the color ink. 25. The total content of the polyvalent metal salt contained in the color ink is 0.005 to the total amount of the color ink.
25. The ink jet recording apparatus according to claim 24, wherein the total content of a substance selected from an acid having an amino group and a salt thereof is 0.005 to 20% by mass relative to the total amount of the color ink. Ink set. 26. The polyvalent metal salt is at least one selected from polyvalent metal salts of nitric acid, acetic acid, hydroxycarboxylic acid and polyol phosphoric acid ester.
Or the ink set for inkjet recording according to 25. 27. The polyvalent metal salt of nitric acid, acetic acid, hydroxycarboxylic acid and polyol phosphate ester is selected from the group consisting of magnesium nitrate, calcium nitrate, barium nitrate, iron (II) nitrate, copper (II) nitrate, zinc nitrate and acetic acid. magnesium,
Calcium acetate, barium acetate, iron (II) acetate, copper (II) acetate, zinc acetate, magnesium gluconate, calcium gluconate, barium gluconate, iron gluconate (I
The ink set for inkjet recording according to claim 26, comprising I), copper (II) gluconate, zinc gluconate, magnesium glycerophosphate, and calcium glycerophosphate. 28. The acid having an amino group includes amidosulfuric acid (alias: sulfamic acid), aminomethanesulfonic acid, taurine (alias: 2-aminoethanesulfonic acid),
The ink set for inkjet recording according to any one of claims 24 to 27, wherein the ink set is at least one selected from carbamic acid, glycine, alanine, β-alanine, aspartic acid, and glutamic acid. 29. The ink set for inkjet recording according to claim 24, wherein the coloring material of the black ink is at least one selected from carbon black and pigment. 30. The black ink colorant is a dye having at least one carboxyl group.
The ink set for inkjet recording according to any one of items 4 to 28. 31. The water content in the black ink and the color ink is 35 to the total mass of the ink, respectively.
The ink set for inkjet recording according to any one of claims 24 to 30, wherein the content is from about 96% by mass to about 96% by mass. 32. The color ink according to claim 24, wherein the color ink is at least one ink selected from the group consisting of yellow ink, magenta ink and cyan ink.
2. The ink set for inkjet recording according to any one of 1. 33. The ink set includes a heater for applying thermal energy to the ink to eject the ink from an orifice, and a top surface protection including a material selected from a metal and a metal oxide for protecting the heater. The ink set for ink jet recording according to any one of claims 24 to 32, which is an ink set used for an ink jet printer having a recording head provided with a layer. 34. The ink jet recording ink set according to claim 33, wherein the outermost surface protective layer contains tantalum or a tantalum oxide as a substance selected from a metal and a metal oxide. 35. (i) any one of claims 24 to 34
(Ii) applying energy for discharging the ink to the black ink included in the ink set described in (1), discharging the black ink toward the recording medium, and applying the black ink onto the recording medium; Item 34. An energy is applied to the color ink included in the ink set according to any one of Items 24 to 34 for discharging the ink, and the color ink is discharged toward the recording medium and applied to the recording medium. Wherein the steps (i) and (ii) are performed such that a contact state between the black ink and the color ink is formed on a recording medium. Recording method. 36. The black ink and the color ink are applied so as to overlap on a recording medium, and
The ink jet recording method according to claim 35, wherein the application of the color ink to the recording medium is performed prior to the black ink. 37. The ink jet recording method according to claim 35, wherein the energy is heat energy. 38. An ink storage section containing the inks constituting the ink set according to claim 24, and energy supplied to the ink supplied from the ink storage section. A recording unit comprising an ink jet recording head for applying and discharging ink. 39. The ink jet recording head,
39. The recording unit according to claim 38, further comprising a heater having an outermost surface protective layer containing a substance selected from a metal and a metal oxide. 40. The substance selected from the metal and metal oxide includes tantalum or a tantalum oxide.
10. The recording unit according to 9. 41. An ink cartridge, comprising: an ink storage section for storing each of the inks constituting the ink set according to claim 24. 42. An ink containing section containing at least an ink set composed of a combination of black ink and color ink, and applying ink to the ink supplied from the ink containing section to eject the ink. 35. 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 24 to 34. 43. The ink jet recording head includes a heater having an outermost surface protective layer containing a substance selected from a metal and a metal oxide, and the ink jet recording apparatus supplies a pulse to the heater according to recording information. 43. The ink jet recording apparatus according to claim 42, further comprising means for applying an electric signal in a shape of a circle. 44. The substance selected from the group consisting of metal and metal oxide includes tantalum or an oxide of tantalum.
4. The inkjet recording apparatus according to 3. 45. Injection for discharging the ink
The energy (E _op) Is a claim that satisfies the following relationship:
The inkjet recording apparatus according to any one of Items 42 to 44, 1.10 ≦ E_op/ E_th≤ 1.90 (E_thIs necessary to eject ink from the printhead.
Is the minimum energy required). 46. A composition comprising (a) a polyvalent metal salt, (b) a substance selected from an acid having an amino group and a salt thereof, (c) a liquid medium, and (d) a coloring material. Inkjet ink.