JP6722401B2 - Ink, ink container, inkjet recording method, inkjet recording apparatus - Google Patents

Description

The present invention relates to an ink, an ink container using the ink, an inkjet recording method, and an inkjet recording device.

The ink jet recording method is a method of recording a character or image by ejecting a small amount of ink droplets from fine nozzles and adhering it to a recording medium such as paper, which has low noise, a simple process, and easy colorization. Widely used as a household printer.
In recent years, the inkjet recording method has been expanded to commercial printing because of advantages such as variable printing and compatibility with a wide range of media. In commercial printing, printing is performed on a wide variety of papers. The papers are roughly classified into plain papers and coated papers to secure the optical density (OD) of the plain papers and the glossiness of the coated papers. In securing, the required ink functions were different.

On the other hand, various methods have been proposed.
For example, it is known that the pigment particle size is increased to a certain extent to cover the printed surface in order to increase the image density on plain paper, and to produce gloss on glossy paper, the pigment particle size Is required to be small and surface uniformity is required. It is already known that the fixing property is improved by adding a urethane resin.
Patent Document 1 discloses an ink composed of a specific polyurethane resin, a surfactant and an organic solvent for the purpose of satisfying both the image fixing property and the image saturation.
In addition, in Patent Document 2, two types of hydrophilic resin and hydrophobic resin having an average particle diameter of 100 nm or less (preferably 30 nm to 90 nm) are added for the purpose of improving the color developability, glossiness, and fixability of printed matter, An ink formulation is disclosed in which the average particle diameter of the coloring material is specified to be 50 nm or less (preferably 10 nm to 40 nm) to improve these.
Further, Patent Document 3 discloses a prescription for solving the problem by controlling the amount of urethane and styrene acrylic resin to be 10:1 or more on a mass basis for the purpose of suppressing stickiness on the image surface and enhancing whiteness and scratch resistance. It is disclosed.

In ink-jet printing, due to the characteristics of plain paper and coated paper, the gloss of coated paper decreases and the gloss of coated paper decreases when the image density is increased compared to plain paper. However, the image density of plain paper was low.
In order to solve the problem, two kinds of ink sets for plain paper and coated paper are used by using an ink with a large pigment particle diameter for plain paper and an ink with a small pigment particle diameter for coated paper, or a dye ink. Or, we have dealt with this by mounting two types of ink.
However, with the conventional methods, the storage space of the ink tank is increased due to the increase in the ink type, the printer main body is enlarged, and the ink is changed depending on the paper type, so the hue differs between plain paper and coated paper. was there.
The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide an ink that can improve both gloss and fixability of coated paper and image density and fixability of plain paper. To do.

The above problem is solved by the invention of the following 1).
1) An ink comprising pigment particles, an organic solvent, styrene acrylic resin particles, urethane resin particles, and water, wherein the pigment particles have an average particle diameter (D ₅₀ ) of 90 nm or more and 120 nm or less, An ink characterized in that the particles, the styrene acrylic resin particles, and the urethane resin particles have an average particle diameter (D ₅₀ ) satisfying the following relationship.
Pigment particles (D _50)> Styrene acrylic resin particles (D _50)> urethane resin particles (D ₅₀₎

According to the present invention, an ink is provided which, while ensuring the image density of plain paper, can obtain high gloss for coated paper and good fixing properties for plain paper and coated paper. can do.

It is a diagram showing an example of a recording apparatus using the ink of the present invention. FIG. 3 is a perspective view of a main tank that stores the ink of the present invention.

The present invention 1) will be described in detail below. Since the embodiment 1) of the present invention includes the following 2) to 11), these will also be described together.
2) The ratio of the average particle diameter (D ₅₀ ) of the pigment, the styrene acrylic resin particles, and the urethane resin particles in the ink is 1.0:0.8:0.5 to 1.0:0. 4:0.1, and the ratio of the average particle diameter (D ₅₀ ) of the styrene acrylic resin and the urethane resin is 1.0:0.9 to 1.0:0.3. The ink according to 1) above.
3) The ink according to 1) or 2) above, wherein the styrene-acrylic resin particles have an average particle diameter (D ₅₀ ) of 40 nm or more and 60 nm or less.
4) The ink according to any one of 1) to 3) above, wherein the urethane resin particles have an average particle diameter (D ₅₀ ) of 10 nm or more and 30 nm or less.
5) The ink according to any one of 1) to 4) above, wherein the content of the styrene acrylic resin particles in the ink is 2.0% by mass or more and 10.0% by mass or less.
6) The ink according to any one of 1) to 5) above, wherein the content of the urethane resin particles in the ink is 1.0% by mass or more and 5.0% by mass or less.
7) The ratio (A/B) of the mass-based content A of the styrene acrylic resin particles in the ink to the mass-based content B of the urethane resin particles in the ink is 2 or more and 5 or less. 7. The ink according to any one of 1) to 6) above.
8) The ink according to any one of 1) to 7) above, wherein the urethane resin particles have a Tg of 45° C. or lower.
9) An ink container containing the ink according to any one of 1) to 8) in a container.
10) An ink jet recording method including an ink ejection step of ejecting the ink according to any one of 1) to 8) above to a recording medium to perform recording.
11) An ink jet recording apparatus comprising an ink ejecting device that ejects the ink according to any one of 1) to 8) above to a recording medium to perform recording.

For conventional inks, if the pigment particle size is increased and the image density of plain paper is secured, the gloss will decrease compared to glossy paper, and if the pigment particle size is reduced to ensure gloss on plain paper, it will be plain paper. The image density has decreased. When a urethane-based resin is added to secure the fixing property, glossiness is reduced on glossy paper, and it is not possible to satisfy all requirements, and there is a problem that some of the properties are deteriorated.
For example, the ink described in Patent Document 1 uses a polyurethane resin to ensure the fixability. However, although it has a certain effect on plain paper, glossiness cannot be ensured on coated paper and the image quality is insufficient, and image quality on coated paper cannot be secured.
Further, the ink described in Patent Document 2 has improved color developability/gloss/fixability by controlling the particle diameters of the pigment and the resin, but has a configuration in which the pigment is made smaller and the resin particles are made larger. The configuration is completely opposite to that of the present invention, and the ability to improve the image density of plain paper is extremely inferior, and the three are not compatible.
The ink described in Patent Document 3 uses a urethane resin and a styrene acrylic resin in combination. However, the particle size of the urethane resin is larger than the particle size of the styrene acrylic resin, the glossiness cannot be ensured for coated paper, and the image quality is insufficient, and the printing surface is not glossy. The image becomes low and the image becomes strange.

The present inventors have confirmed the effects of the difference in pigment particle size between plain paper and coated paper on the image density of plain paper and the glossiness and image density of coated paper.
As a result, the larger the pigment particle size, the higher the image density of plain paper, but the image is dull on coated paper and the gloss is lost. However, it was confirmed that the image density on plain paper tended to decrease. When the particle size of the styrene acrylic resin particles to be added was also checked in the same manner, it was confirmed that the same effect could be obtained with the styrene acrylic resin particles. However, for urethane resin particles, this tendency was not observed, and no improvement in glossiness was observed regardless of the particle size, but for fixability, a smaller particle size tended to be better. ..
Therefore, the particle size of each of the pigment particles, the styrene acrylic resin particles, and the urethane resin particles is controlled, and the average particle diameter (D ₅₀ ) of the pigment is 90 nm or more and 120 nm or less, and the pigment particles, the styrene acrylic resin particles, And that the average particle diameter (D ₅₀ ) of the urethane resin particles satisfies the relations described below, it is possible to obtain high image density, gloss, and good fixability on plain paper and coated paper. It was
Pigment particles (D _50)> Styrene acrylic resin particles (D _50)> urethane resin particles (D ₅₀₎

<Ink>
Hereinafter, the organic solvent, water, pigments, resins, additives and the like which compose the ink of the present invention will be described.

<Resin>
The resin used in the present invention needs to have glossiness with respect to coated paper, and therefore it is necessary to add two types of styrene-acrylic resin particles and urethane resin particles to secure fixability.
However, it is not limited to the two types, and may be added according to the purpose. For example, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, styrene-butadiene resin. , Vinyl chloride resin, acrylic silicone resin, and the like. You may use the resin particle which consists of these resins. It is possible to obtain an ink by mixing resin particles in the state of a resin emulsion in which water is used as a dispersion medium, with a material such as a coloring material or an organic solvent. As the resin particles, those synthesized appropriately may be used, or commercially available products may be used.

<Particle size of resin particles>
The resin used in the present invention has an average particle diameter (D ₅₀ ) of pigment particles of 90 nm or more and 120 nm or less, and the average particle diameter (D ₅₀ ) of the pigment particles, styrene acrylic resin particles, and urethane resin particles based on the value. It is important that the relationship of (1) is pigment particles>styrene acrylic resin particles>urethane resin particles.
Since the pigment particles are large compared to plain paper, they tend to stay on the paper surface, and high image density can be secured. With respect to coated paper, styrene acrylic resin particles enter the gaps between the pigment particles to make the printed surface uniform and to obtain high gloss. Further, by adding the urethane resin particles, the urethane resin particles enter the gaps between the pigment particles, the styrene acrylic resin particles, and the coat layer to enhance the adhesiveness.
For this reason, it is not necessary to separate the ink type into coated paper and plain paper as used in the conventional technology, the image density can be secured for plain paper, and high gloss is also available for coated paper. And the fixability can be obtained.
The pigment particles alone can secure the image density on plain paper, but on the coated paper, the gloss becomes lower than the surface texture of the paper, resulting in a matte tone.
When the average particle size of the styrene acrylic resin particles is larger than the average particle size of the pigment particles, no improvement in gloss is seen on the coated paper. Further, the fixing property cannot be secured only by the pigment particles and the styrene-acrylic resin particles, and image peeling may occur.
By adding urethane resin particles, the fixability to coated paper can be secured, but if the average particle size of the urethane resin particles is larger than the average particle size of the pigment particles and the styrene acrylic resin particles, the fixability is improved. Can be secured, but the image gloss is reduced. Therefore, by making the average particle size of the urethane resin particles smaller than the average particle size of the pigment particles and the styrene-acrylic resin particles, it becomes possible to achieve both the fixability and the image gloss on coated paper and the image density on plain paper.

A preferable ratio of the average particle diameter (D ₅₀ ) of the pigment particles, the styrene acrylic resin particles, and the urethane resin particles is 1.0:0.8:0.5 to 1.0:0.4:0. 0.1, and more preferably 1.0:0.8:0.5 to 1.0:0.4:0.3. Further, the ratio of the average particle diameter (D ₅₀ ) of the styrene acrylic resin and the urethane resin is preferably 1.0:0.9 to 1.0:0.3, more preferably 1.0:0.9 to 1. It is 0:0.5.
By containing the pigment particles and the styrene acrylic resin particles within the above range, the styrene acrylic resin particles can fill the gaps between the pigments and perform leveling.
Further, the urethane resin particles improve the fixability. When the average particle diameter of the urethane resin particles is within the range of the above ratio, the urethane resin particles enter the gap between the pigment and the styrene-acrylic resin particles, whereby the adhesion between each particle and the paper can be increased, Fixability is improved.

The average particle diameter (D ₅₀ ) of the styrene acrylic resin particles is preferably 40 nm or more and 60 nm or less, and the average particle diameter of the urethane resin particles is preferably 10 nm or more and 30 nm or less. When the average particle diameter (D ₅₀ ) of the styrene acrylic resin particles is 40 nm or more and 60 nm or less, the relatively hard styrene acrylic resin fills the gaps between the pigments to increase the fixing strength and at the same time the surface smoothness can be secured. The gloss increases. Further, when the average particle diameter of the urethane resin particles is 10 nm or more and 30 nm or less, the urethane resin having a smaller particle diameter enters the gap, whereby the adhesiveness is improved and the fixability is further improved.
The average particle diameter (D ₅₀ ) is a cumulative 50% by volume particle diameter, and can be measured using, for example, a particle size distribution device (Nanotrack Wave-UT151, Microtrac Bell Co., Ltd.),

<Content of resin in ink>
The content of styrene acrylic resin particles and urethane resin particles contained in the ink is not particularly limited and can be selected according to the purpose, but the styrene acrylic resin particles are 2.0% by mass or more based on the total amount of the ink. It is desirable that the content of the urethane resin particles is 1.0% by mass or more and 5.0% by mass or less.
By containing styrene-acrylic resin particles in an amount of 1.0% by mass or more, the printing surface is leveled and at the same time a transparent film is formed to improve the gloss. When the content is 10.0% by mass or less, the ejection reliability and the reliability of maintenance can be secured, and the storage stability of the ink can be secured.
By adding the urethane resin particles in an amount of 1.0% by mass or more, the adhesion between the pigment, the resin, and the paper surface can be improved, and the fixing property can be improved. Pressing and ink storage stability can be secured.

Further, the ratio (A/B) of the mass-based content A of the styrene-acrylic resin particles in the ink to the mass-based content B of the urethane resin particles in the ink is 2 or more and 5 or less. It is preferable.
By increasing the amount of urethane resin, tackiness is created on the printed surface and blocking easily occurs. When the ratio (A/B) of the content of the styrene acrylic resin particles to the content of the urethane resin particles is 2 or more and 5 or less and the styrene acrylic resin is more than the urethane resin, blocking is less likely to occur.

The glass transition temperature (Tg) of the urethane resin particles is preferably 45°C or lower. By setting the Tg to 45° C. or lower, the adhesion between the pigment, the styrene acrylic resin, and the paper is increased, and the fixability is improved.

<Pigment>
The average particle diameter (D ₅₀ ) of the pigment is 90 nm or more and 120 nm or less. When the thickness is 90 nm or more, the image density on plain paper can be secured, and when the thickness is 120 nm or less, nozzle clogging can be suppressed.
The pigment content in the ink is preferably 1.0% by mass or more and 10.0% by mass or less. A desired image density on plain paper can be obtained with 1.0% by mass or more, and ejection reliability can be ensured and maintenance-related reliability can be ensured with 10.0% by mass or less. it can.

An inorganic pigment or an organic pigment can be used as the pigment. These may be used alone or in combination of two or more. Also, a mixed crystal may be used.
Examples of pigments that can be used include black pigments, yellow pigments, magenta pigments, cyan pigments, white pigments, green pigments, orange pigments, luster color pigments such as gold and silver, and metallic pigments.
As an inorganic pigment, in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, carbon black produced by a known method such as a contact method, a furnace method, or a thermal method. Can be used.
Further, as the organic pigment, an azo pigment, a polycyclic pigment (for example, a phthalocyanine pigment, a perylene pigment, a perinone pigment, an anthraquinone pigment, a quinacridone pigment, a dioxazine pigment, an indigo pigment, a thioindigo pigment, an isoindolinone pigment, a quinofuraron pigment, etc.) , Dye chelates (for example, basic dye chelates, acid dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, etc. can be used. Among these pigments, those having a good affinity with the solvent are preferably used. In addition, hollow resin particles and hollow inorganic particles can also be used.
Specific examples of pigments include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black and channel black, or copper and iron (CI pigment black 11) for black. , Metal oxides such as titanium oxide, and organic pigments such as aniline black (CI Pigment Black 1).
Further, for color, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104. , 108, 109, 110, 117, 120, 128, 138, 150, 153, 155, 180, 185, 213, C.I. I. Pigment Orange 5, 13, 16, 17, 36, 43, 51, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48:2, 48:2 (Permanent Red 2B(Ca)), 48:3, 48:4, 49:1, 52: 2,53:1, 57:1 (Brilliant Carmine 6B), 60:1, 63:1, 63:2, 64:1, 81, 83, 88, 101 (Bengara), 104, 105, 106, 108 ( Cadmium red), 112, 114, 122 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 184, 185, 190, 193, 202, 207, 208, 209, 213, 219, 224, 254, 264, C.I. I. Pigment Violet 1 (Rhodamine Lake), 3, 5:1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15:1, 15:2, 15:3, 15:4 (phthalocyanine blue), 16, 17:1, 56, 60, 63, C.I. I. Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, and the like.

To disperse the pigment in the ink, a method of introducing a hydrophilic functional group into the pigment to obtain a self-dispersing pigment, a method of coating the surface of the pigment with a resin to disperse, a method of dispersing using a dispersant, And so on.
Examples of a method for introducing a hydrophilic functional group into a pigment to give a self-dispersing pigment include, for example, a self-dispersing pigment that is dispersible in water by adding a functional group such as a sulfone group or a carboxyl group to a pigment (for example, carbon) Can be used.
As a method of coating the surface of the pigment with a resin to disperse the pigment, a method in which the pigment is contained in microcapsules and can be dispersed in water can be used. This can be rephrased as a resin-coated pigment. In this case, it is not necessary for all the pigments mixed in the ink to be coated with the resin, and as long as the effect of the present invention is not impaired, uncoated pigments or partially coated pigments are dispersed in the ink. May be.
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low molecular type dispersant or polymer type dispersant represented by a surfactant.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant or the like can be used depending on the pigment.
Takemoto Yushi Co., Ltd. RT-100 (nonionic surfactant) and naphthalenesulfonic acid Na formalin condensate can also be suitably used as the dispersant.
The dispersants may be used alone or in combination of two or more.

<Pigment dispersion>
It is possible to obtain an ink by mixing a material such as water or an organic solvent with the pigment. Further, it is also possible to manufacture an ink by mixing a pigment and other materials such as water and a dispersant to form a pigment dispersion, and mixing materials such as water and an organic solvent.
The pigment dispersion is obtained by dispersing water, a pigment, a pigment dispersant, and other components as necessary, and adjusting the particle size. A dispersion machine may be used for dispersion.
Regarding the particle size of the pigment in the pigment dispersion, the maximum frequency is preferably 90 nm or more and 120 nm or less in terms of the maximum number in order to ensure the image density of plain paper.
The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).
The content of the pigment in the pigment dispersion is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good ejection stability and increasing the image density, it is 0.1% by mass. % Or more and 50 mass% or less is preferable, and 0.1 mass% or more and 30 mass% or less is more preferable.
The pigment dispersion is preferably degassed by filtering coarse particles with a filter, a centrifugal separator or the like, if necessary.

<Organic solvent>
The organic solvent used in the present invention is not particularly limited, and a water-soluble organic solvent can be used. Examples thereof include polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds.
Specific examples of the water-soluble organic solvent include, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butane. Diol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol , 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, Glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl- Polyhydric alcohols such as 1,3-pentanediol and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether Polyhydric alcohol alkyl ethers such as ethers, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone , Nitrogen-containing heterocyclic compounds such as 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone, formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N- Amides such as dimethylpropionamide and 3-butoxy-N,N-dimethylpropionamide, amines such as monoethanolamine, diethanolamine and triethylamine, sulfur-containing compounds such as dimethylsulfoxide, sulfolane and thiodiethanol, propylene carbonate and ethylene carbonate. Etc.
It is preferable to use an organic solvent having a boiling point of 250° C. or less because it not only functions as a wetting agent but also obtains good drying properties.

A polyol compound having 8 or more carbon atoms and a glycol ether compound are also preferably used. Specific examples of the polyol compound having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.
Specific examples of glycol ether compounds include polyhydric alcohol alkyls such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether. Ethers; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether and the like.

The polyol compound having 8 or more carbon atoms and the glycol ether compound can improve the ink permeability when paper is used as the recording medium.

The content of the organic solvent in the ink is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of ink drying properties and ejection reliability, 10% by mass or more and 60% by mass or less is preferable, 20 mass% or more and 60 mass% or less are more preferable.

<water>
The content of water in the ink is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of ink drying properties and ejection reliability, 10% by mass to 90% by mass is preferable, and 20% by mass is preferable. % To 60% by mass is more preferable.

The particle size of the solid content in the ink is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of enhancing the image quality such as ejection stability and image density, the maximum number of times converted to the maximum number Is preferably 20 nm or more and 1000 nm or less, more preferably 20 nm or more and 150 nm or less. The solid content includes resin particles and pigment particles. The particle size can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell KK).

<Additive>
If necessary, a surfactant, a defoaming agent, an antiseptic/antifungal agent, a rust preventive, a pH adjuster and the like may be added to the ink.

<Surfactant>
As the surfactant, any of silicone-based surfactants, fluorine-based surfactants, amphoteric surfactants, nonionic surfactants, and anionic surfactants can be used.
The silicone-based surfactant is not particularly limited and can be appropriately selected according to the purpose. Among them, those that do not decompose even at high pH are preferable, and examples thereof include side-chain modified polydimethylsiloxane, both-end modified polydimethylsiloxane, one-end modified polydimethylsiloxane, and side-chain both-end modified polydimethylsiloxane. Those having an oxyethylene group or a polyoxyethylene polyoxypropylene group are particularly preferable because they exhibit good properties as an aqueous surfactant. In addition, as the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include a compound having a polyalkylene oxide structure introduced into the side chain of the Si moiety of dimethylsiloxane.
Examples of the fluorinated surfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphoric acid ester compound, a perfluoroalkyl ethylene oxide adduct and a perfluoroalkyl ether group in the side chain. A polyoxyalkylene ether polymer compound is particularly preferable because it has a low foaming property. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid and perfluoroalkyl sulfonate. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylic acid salts. Examples of the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in its side chain include a sulfuric acid ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in its side chain and a perfluoroalkyl ether group in its side chain. Examples thereof include salts of polyoxyalkylene ether polymers. The counterions of the salts in these fluorine-based surfactants include Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ and NH(CH ₂ CH ₂ OH). ₃ etc.
Examples of the amphoteric surfactant include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.
Examples of nonionic surfactants include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, polyoxyethylene sorbitan. Examples thereof include fatty acid esters and ethylene oxide adducts of acetylene alcohol.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl salt, and salt of polyoxyethylene alkyl ether sulfate.
These may be used alone or in combination of two or more.

（但し、一般式（Ｓ−１）式中、ｍ、ｎ、ａ、及びｂは整数を表わす。Ｒ及びＲ’はアルキル基、アルキレン基を表わす。）
上記のポリエーテル変性シリコーン系界面活性剤としては、市販品を用いることができ、例えば、ＫＦ−６１８、ＫＦ−６４２、ＫＦ−６４３（信越化学工業株式会社）、ＥＭＡＬＥＸ−ＳＳ−５６０２、ＳＳ−１９０６ＥＸ（日本エマルジョン株式会社）、ＦＺ−２１０５、ＦＺ−２１１８、ＦＺ−２１５４、ＦＺ−２１６１、ＦＺ−２１６２、ＦＺ−２１６３、ＦＺ−２１６４（東レ・ダウコーニング・シリコーン株式会社）、ＢＹＫ−３３、ＢＹＫ−３８７（ビックケミー株式会社）、ＴＳＦ４４４０、ＴＳＦ４４５２、ＴＳＦ４４５３（東芝シリコン株式会社）などが挙げられる。 The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include side-chain modified polydimethylsiloxane, both-end modified polydimethylsiloxane, one-end modified polydimethylsiloxane, and side-modified. Examples include polydimethylsiloxane modified at both chain ends, and a polyether-modified silicone surfactant having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group shows good properties as an aqueous surfactant, preferable.
As such a surfactant, an appropriately synthesized product may be used, or a commercially available product may be used. Commercially available products can be obtained from, for example, Big Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., Kyoeisha Kagaku, etc.
The polyether-modified silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the polyalkylene oxide structure represented by the general formula (S-1) may be represented by dimethylpolyethylene. Examples thereof include those introduced into the side chain of the Si portion of siloxane.

(However, in the formula (S-1), m, n, a, and b represent an integer. R and R'represent an alkyl group or an alkylene group.)
As the above polyether-modified silicone-based surfactant, commercially available products can be used, and for example, KF-618, KF-642, KF-643 (Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5602, SS-. 1906EX (Nippon Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (Toray Dow Corning Silicone Co., Ltd.), BYK-33, BYK-387 (Big Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.), etc. are mentioned.

上記一般式（Ｆ−１）で表される化合物において、水溶性を付与するためにｍは０〜１０の整数が好ましく、ｎは０〜４０の整数が好ましい。
一般式（Ｆ−２）
Ｃ_nＦ_2n+1−ＣＨ₂ＣＨ(ＯＨ)ＣＨ₂−Ｏ−(ＣＨ₂ＣＨ₂Ｏ)_a−Ｙ
上記一般式（Ｆ−２）で表される化合物において、ＹはＨ、又はＣ_nＦ_2n+1でｎは１〜６の整数、又はＣＨ₂ＣＨ(ＯＨ)ＣＨ₂−Ｃ_nＦ_2n+1でｎは４〜６の整数、又はＣ_pＨ_2p+1でｐは１〜１９の整数である。ａは４〜１４の整数である。
上記のフッ素系界面活性剤としては市販品を使用してもよい。この市販品としては、例えば、サーフロンＳ−１１１、Ｓ−１１２、Ｓ−１１３、Ｓ−１２１、Ｓ−１３１、Ｓ−１３２、Ｓ−１４１、Ｓ−１４５（いずれも、旭硝子株式会社製）；フルラードＦＣ−９３、ＦＣ−９５、ＦＣ−９８、ＦＣ−１２９、ＦＣ−１３５、ＦＣ−１７０Ｃ、ＦＣ−４３０、ＦＣ−４３１（いずれも、住友スリーエム株式会社製）；メガファックＦ−４７０、Ｆ−１４０５、Ｆ−４７４（いずれも、大日本インキ化学工業株式会社製）；ゾニール（Ｚｏｎｙｌ）ＴＢＳ、ＦＳＰ、ＦＳＡ、ＦＳＮ−１００、ＦＳＮ、ＦＳＯ−１００、ＦＳＯ、ＦＳ−３００、ＵＲ（いずれも、ＤｕＰｏｎｔ社製）；ＦＴ−１１０、ＦＴ−２５０、ＦＴ−２５１、ＦＴ−４００Ｓ、ＦＴ−１５０、ＦＴ−４００ＳＷ（いずれも、株式会社ネオス社製）、ポリフォックスＰＦ−１３６Ａ，ＰＦ−１５６Ａ、ＰＦ−１５１Ｎ、ＰＦ−１５４、ＰＦ−１５９（オムノバ社製）、ユニダインＤＳＮ−４０３Ｎ（ダイキン工業株式会社製）などが挙げられ、これらの中でも、良好な印字品質、特に発色性、紙に対する浸透性、濡れ性、均染性が著しく向上する点から、Ｄｕ Ｐｏｎｔ社製のＦＳ−３００、株式会社ネオス製のＦＴ−１１０、ＦＴ−２５０、ＦＴ−２５１、ＦＴ−４００Ｓ、ＦＴ−１５０、ＦＴ−４００ＳＷ、オムノバ社製のポリフォックスＰＦ−１５１Ｎ及びダイキン工業株式会社製のユニダインＤＳＮ−４０３Ｎが特に好ましい。 The fluorine-based surfactant is preferably a fluorine-substituted compound having 2 to 16 carbon atoms, more preferably a fluorine-substituted compound having 4 to 16 carbon atoms.
Examples of the fluorine-based surfactant include a perfluoroalkyl phosphate ester compound, a perfluoroalkylethylene oxide adduct, and a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in its side chain.
Among these, polyoxyalkylene ether polymer compounds having a perfluoroalkyl ether group in the side chain are preferable because they have a low foaming property, and the fluorine-based compounds represented by the general formula (F-1) and the general formula (F-2) are particularly preferable. Surfactants are preferred.

In the compound represented by the general formula (F-1), m is preferably an integer of 0 to 10 and n is preferably an integer of 0 to 40 in order to impart water solubility.
General formula (F-2)
_{C n F 2n + 1 -CH 2} CH (OH) CH 2 -O- (CH 2 CH 2 O) a -Y
In the compound represented by the above general formula (F-2), Y is H, or C _n F _2n+1 and n is an integer of 1 to 6, or CH ₂ CH(OH)CH ₂ -C _n F _{2n+. 1,} n is 4-6 integer, or p in C _p H _{2p + 1} is an integer of 1 to 19. a is an integer of 4-14.
A commercial item may be used as the above-mentioned fluorine-based surfactant. Examples of this commercially available product include Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, S-145 (all manufactured by Asahi Glass Co., Ltd.); Fullrad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Limited); Megafac F-470, F -1405, F-474 (all manufactured by Dainippon Ink and Chemicals, Inc.); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR (all , DuPont); FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW (all are Neos Co., Ltd.), Polyfox PF-136A, PF-156A, PF-151N, PF-154, PF-159 (manufactured by OMNOVA), Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.) and the like can be mentioned. Among these, good print quality, especially color developability and penetrability to paper , WP-300 manufactured by Du Pont, FT-110, FT-250, FT-251, FT-400S, FT-150, FT- manufactured by Neos Co., Ltd. from the viewpoint of significantly improving wettability and leveling property. 400 SW, Polyfox PF-151N manufactured by Omnova Co., Ltd. and Unidyne DSN-403N manufactured by Daikin Industries, Ltd. are particularly preferable.

The content of the surfactant in the ink is appropriately selected depending on the intended purpose without any limitation, but it is 0.001 mass% from the viewpoint of excellent wettability and ejection stability and improving image quality. % Or more and 5 mass% or less is preferable, and 0.05 mass% or more and 5 mass% or less is more preferable.

<Antifoam>
The defoaming agent is not particularly limited, and examples thereof include a silicone defoaming agent, a polyether defoaming agent, and a fatty acid ester defoaming agent. These may be used alone or in combination of two or more. Among these, a silicone-based defoaming agent is preferable because of its excellent foam breaking effect.

<Antiseptic and fungicide>
The antiseptic/antifungal agent is not particularly limited, and examples thereof include 1,2-benzisothiazolin-3-one.

<Rust preventive>
The rust preventive agent is not particularly limited, and examples thereof include acid sulfite and sodium thiosulfate.

<pH adjuster>
The pH adjuster is not particularly limited as long as the pH can be adjusted to 7 or higher, and examples thereof include amines such as diethanolamine and triethanolamine.

The physical properties of the ink are not particularly limited and may be appropriately selected depending on the purpose. For example, the viscosity, surface tension, pH and the like are preferably in the following ranges.
The viscosity of the ink at 25° C. is preferably 5 mPa·s or more and 30 mPa·s or less, from the viewpoint that the printing density and character quality are improved and good ejection properties are obtained, and 5 mPa·s or more and 25 mPa·s or less are preferable. More preferable. Here, as the viscosity, for example, a rotary viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.) can be used. The measurement conditions are 25° C., standard cone rotor (1°34′×R24), sample liquid volume 1.2 mL, rotation speed 50 rpm, and 3 minutes.
The surface tension of the ink is preferably 35 mN/m or less, and more preferably 32 mN/m or less at 25° C., since the ink is preferably leveled on the recording medium and the drying time of the ink is shortened.
The pH of the ink is preferably 7 to 12, and more preferably 8 to 11 from the viewpoint of preventing the corrosion of the metal member with which the ink comes into contact.

<Recording medium>
The recording medium used for recording is not particularly limited, and examples thereof include plain paper, glossy paper, special paper, cloth, film, OHP sheet, and general-purpose printing paper.

<Recorded matter>
The ink recorded matter of the invention has an image formed by using the ink of the invention on a recording medium.
A recorded matter can be obtained by recording with an inkjet recording apparatus and an inkjet recording method.

(Ink container)
The ink storage container of the present invention has an ink storage portion that stores the ink of the present invention, and further has other members appropriately selected as necessary.
The ink container is not particularly limited, and its shape, structure, size, material and the like can be appropriately selected according to the purpose. For example, an ink container formed of an aluminum laminate film, a resin film or the like. And the like, for example, a main tank having an ink containing portion, an ink cartridge, and the like are preferable.

<Recording device, recording method>
The ink of the present invention can be suitably used for various recording apparatuses using an inkjet recording system, such as printers, facsimile machines, copying machines, printer/fax/copier multifunction machines, and three-dimensional modeling apparatuses.
In the present application, the recording device and the recording method are a device capable of ejecting ink, various treatment liquids, and the like onto a recording medium, and a method of performing recording using the device. The recording medium means a medium to which ink or various treatment liquids can be attached even temporarily.
This recording apparatus can include not only a head portion for ejecting ink, but also means for feeding, conveying, and discharging a recording medium, and other devices such as a pre-processing device and a post-processing device. ..
The recording device and the recording method may have a heating means used in the heating step and a drying means used in the drying step. The heating means and the drying means include, for example, means for heating and drying the printing surface or the back surface of the recording medium. The heating means and the drying means are not particularly limited, but, for example, a warm air heater or an infrared heater can be used. Heating and drying can be performed before printing, during printing, after printing, and the like.
Further, the recording device and the recording method are not limited to those in which a significant image such as a character or a figure is visualized by ink. For example, it also includes one that forms a pattern such as a geometric pattern and one that models a three-dimensional image.
Further, the recording apparatus includes both a serial type apparatus that moves the ejection head and a line type apparatus that does not move the ejection head unless otherwise limited.
Further, this recording device is not limited to a desktop type, but can be used as a wide recording device capable of printing on an A0 size recording medium, or a continuous paper wound in a roll, for example. It also includes a continuous form printer.
An example of the recording device will be described with reference to FIGS. FIG. 1 is a perspective explanatory view of the device. FIG. 2 is a perspective view of the main tank. The image forming apparatus 400 as an example of the recording apparatus is a serial type image forming apparatus. A mechanical section 420 is provided in the exterior 401 of the image forming apparatus 400. Each ink storage portion 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is packed with, for example, an aluminum laminate film. It is formed of a member. The ink container 411 is housed in a container case 414 made of plastics, for example. As a result, the main tank 410 is used as an ink cartridge for each color.
On the other hand, a cartridge holder 404 is provided on the inner side of the opening when the cover 401c of the apparatus main body is opened. The main tank 410 is detachably attached to the cartridge holder 404. As a result, the ink discharge ports 413 of the main tank 410 communicate with the ejection heads 434 for the respective colors via the supply tubes 436 for the respective colors, and ink can be ejected from the ejection heads 434 to the recording medium.

The method of using the ink is not limited to the ink jet recording method and can be widely used. In addition to the inkjet recording method, for example, a blade coating method, a gravure coating method, a bar coating method, a roll coating method, a dip coating method, a curtain coating method, a slide coating method, a die coating method, a spray coating method and the like can be mentioned.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, "part" represents "mass part" and "%" represents "mass %".

Preparation example 1
-Preparation of black pigment dispersion-
90 g of carbon black having a CTAB specific surface area of 150 m ² /g and a DBP oil absorption of 100 mL/100 g was added to 3,000 mL of 2.5N sodium sulfate solution, stirred at a temperature of 60° C. and a speed of 300 rpm, and reacted for 10 hours. Oxidation treatment was performed. The obtained reaction solution was filtered, the filtered carbon black was neutralized with a sodium hydroxide solution, and subjected to ultrafiltration. The carbon black obtained was washed with water, dried, and dispersed in pure water so that the pigment concentration was 15% by mass. As described above, the black pigment dispersion liquid of Preparation Example 1 was prepared.

Preparation example 2
-Preparation of yellow pigment dispersion-
As a yellow pigment, C.I. I. Pigment Yellow 128 was subjected to low temperature plasma treatment to prepare a yellow pigment having a carboxylic acid group introduced therein. A dispersion of this in ion-exchanged water was desalted and concentrated with an ultrafiltration membrane to obtain a yellow pigment dispersion of Preparation Example 2 having a pigment concentration of 15% by mass.

Preparation Example 3
-Preparation of magenta pigment dispersion-
C. I. Pigment Yellow 128 instead of C.I. I. A surface-modified magenta pigment was produced in the same manner as in Preparation Example 2 except that Pigment Red 122 was used. A dispersion of this in ion-exchanged water was desalted and concentrated with an ultrafiltration membrane to obtain a magenta pigment dispersion of Preparation Example 3 having a pigment concentration of 15% by mass.

Preparation Example 4
-Preparation of cyan pigment dispersion-
C. I. Pigment Yellow 128 instead of C.I. I. A surface-modified cyan pigment was produced in the same manner as in Preparation Example 2 except that Pigment Blue 15:3 was used. A dispersion of this in ion-exchanged water was desalted and concentrated by an ultrafiltration membrane to obtain a cyan pigment dispersion of Preparation Example 4 having a pigment concentration of 15% by mass.

Examples 1-6, Comparative Examples 1-8
Adjustment of each ink <Black, cyan, magenta, yellow>
The materials having the following formulations were mixed and stirred, and then filtered with a 1.5 μm polypropylene filter to prepare each ink of Examples 1 to 6 and Comparative Examples 1 to 8. The types of pigment dispersion, organic solvent, resin, etc. used for each ink, and the blending ratio of the organic solvent are as shown in Examples of Table 1-1 and Comparative Examples of Table 1-2. Moreover, the numerical value of the addition amount shown in Tables 1-1 and 1-2 is "mass %."
Pigment dispersion: any of the black, yellow, magenta, and cyan pigment dispersions
: 20.0%
-Water-soluble organic solvent (a) 1,3-butanediol: 15.0%
(B) 3-Methyl-1,3-butanediol: 15.0%
(C) Glycerin: 8.0%
(D) 2-Ethyl-1,3-hexanediol: 2.0%
-Surfactant (e) FS-3100: 0.2%
(Fluorosurfactant containing perfluoroalkyl group, manufactured by Du Pont)
・Preservative: 0.1%
・Water: Adjust to 100%.
Resin (f) Movinyl 5450 (styrene acrylic resin: D ₅₀ particle size 50 nm)
(G) Movinyl 6600 (styrene acrylic resin: D ₅₀ particle size 140 nm)
(H) Movinyl 6969D (styrene acrylic resin: D ₅₀ particle size 100 nm)
(I) Passcor AD-1 (urethane resin: D ₅₀ particle size 15 nm Tg 45° C.)
(J) Superflex 150
(Urethane resin: D ₅₀ particle size 30 nm, Tg 40°C)
(K) Superflex 150HS
(Urethane resin: D ₅₀ particle size 80 nm Tg 32°C)
(L) Superflex 470
(Urethane resin: D ₅₀ particle size 50 nm Tg-31°C)

Evaluation 1 <Storage stability>
Using E-550L (manufactured by Toki Sangyo Co., Ltd.: cone 1°34′×R24), the storage stability was determined from the viscosity before storage and the viscosity measured after storage at 70° C. for 14 days in a sealed container. It was determined according to the formula and evaluated based on the following criteria. OK rank is only A.
Storage stability=(viscosity after storage/viscosity before storage)×100
A: Within 100±5%.
B: More than 100±5% to less than ±10% C: 100±10% or more

Evaluation 2 <Image density of plain paper>
Printing is performed on NEXT-IJ (plain paper) using an inkjet printer (GXe5500) as shown in FIG. As the print pattern, each of the yellow, magenta, cyan, and black inks of the present invention was printed at 100% duty. The printing conditions were 360 dpi and one-pass printing.
After the printing was dried, the image density of each of the yellow, magenta, cyan, and black solid image portions of the above ink was measured with a reflection-type color spectrophotometric densitometer (manufactured by X-Rite).
The judgment is based on the criteria described below.
<Judgment criteria>
A: Black...1.25 or more
Yellow: 0.85 or higher
Magenta...1.05 or more
Cyan: 1.05 or more B: Black: 1.20 or more, less than 1.25
Yellow: 0.80 or more and less than 0.85
Magenta...more than 1.00 and less than 1.05
Cyan: 1.00 or more, less than 1.05 C:Black: 1.15 or more, less than 1.20
Yellow: 0.75 or more and less than 0.80
Magenta: 0.95 or more but less than 1.00
Cyan ・・・ 0.95 or more, less than 1.00 D: Black ・・・ less than 1.15
Yellow: less than 0.75
Magenta...less than 0.95
Cyan: less than 0.95

Evaluation 3 <Coated paper image gloss>
Using a printer (GXe5500), printing is performed on LumiArtGross90 (coated paper). As the print pattern, the yellow, magenta, cyan, and black color inks of the present invention were printed at 100% duty. The printing conditions were glossy paper/clean mode.
After the print was dried, the 60° gloss of each of the solid images of yellow, magenta, cyan, and black and the non-printed portion of the ink was measured, and the difference in gloss was determined and evaluated according to the following criteria.
<Judgment criteria>
A: Gloss difference... 15 or more B: Gloss difference... 10 or more, less than 15 C: Gloss difference... 5 or more, less than 10 D: Gloss difference... less than 5

Evaluation 4 <Fixability evaluation>
An image obtained by printing a 6 cm square solid image at 100 duty on a Lumi Art Gross (coated paper) using a printer (GXe5500) was mounted on a clock meter (manufactured by Toyo Seiki Co., Ltd.) 24 hours or more after printing. The solid portion printed with Lumi Art Gross was reciprocated 10 times, and the transfer optical density (transfer OD) of stains adhering to the rubbed Lumi Art Gross was measured by X-rite, and evaluated according to the following criteria.
A... Transfer OD is less than 0.05 B... Transfer OD is 0.05 or more and less than 0.15
C... Transfer OD is 0.15 or more and less than 0.20
D: Transfer OD is 0.20 or more

400 image forming apparatus 401 exterior 401c cover 404 cartridge holders 410, 410k, 410c, 410m, 410y main tank 411 ink storage unit 413 ink discharge port 414 storage container case 420 mechanical unit 436 supply tube 434 discharge head

JP, 2006-335858, A JP, 2008-150507, A JP, 2015-98598, A

Claims (9)

An ink comprising pigment particles, an organic solvent, styrene acrylic resin particles, urethane resin particles, and water,
The pigment particles have an average particle diameter (D ₅₀ ) of 90 nm or more and 120 nm or less,
The styrene-acrylic resin particles have an average particle diameter (D ₅₀ ) of 40 nm or more and 60 nm or less,
The average particle diameter (D ₅₀ ) of the urethane resin particles is 10 nm or more and 30 nm or less,
An ink characterized in that the average particle diameter (D ₅₀ ) of the pigment particles, the styrene acrylic resin particles, and the urethane resin particles satisfies the following relationship.
Pigment particles (D _50)> Styrene acrylic resin particles (D _50)> urethane resin particles (D ₅₀₎ The ratio of the average particle diameter (D ₅₀ ) of the pigment, the styrene acrylic resin particles, and the urethane resin particles in the ink is 1.0:0.8:0.5 to 1.0:0.4: 0.1, and the ratio of the average particle diameter (D ₅₀ ) of the styrene acrylic resin and the urethane resin is 1.0:0.9 to 1.0:0.3. Item 2. The ink according to item 1. The ink according to claim 1 or 2 , wherein a content of the styrene acrylic resin particles in the ink is 2.0% by mass or more and 10.0% by mass or less. The content of the urethane resin particle is 1.0% by mass or more in the ink, the ink according to any one of claims 1 to 3, characterized in that at most 5.0 wt%. The ratio (A/B) of the mass-based content A of the styrene-acrylic resin particles in the ink and the mass-based content B of the urethane resin particles in the ink is 2 or more and 5 or less. The ink according to any one of claims 1 to 4 , which is characterized in that. The ink according to any one of claims 1 to 5 , wherein Tg of the urethane resin particles is 45°C or lower. An ink container, wherein the ink according to any one of claims 1 to 6 is contained in a container. An ink jet recording method comprising an ink ejection step of ejecting the ink according to any one of claims 1 to 6 onto a recording medium to perform recording. An ink jet recording apparatus comprising: the ink container according to claim 7 ; and an ink ejecting device that ejects ink in the ink container onto a recording medium to perform recording.

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