JP6024329B2 - Ink jet recording ink, ink cartridge, ink jet recording apparatus, ink jet recording method, and ink recorded matter - Google Patents

Description

  The present invention relates to an ink for ink jet recording, an ink cartridge, an ink jet recording apparatus, an ink jet recording method, and an ink recorded matter.

In recent years, as an image forming method, since the process is simple and full color can be easily obtained as compared with other recording methods, there is an advantage that a high-resolution image can be obtained even with an apparatus having a simple configuration. The method has become widespread.
Inkjet recording is a method in which a small amount of ink is ejected with bubbles generated by heat, pressure generated by using piezoelectricity or static electricity, and the ink is attached to a recording medium such as paper and dried quickly (or recording). This is a method of forming an image (by penetrating into a medium), and its application has been expanded to personal and industrial printers and printing.

In the ink jet recording apparatus, a water-based ink using a water-soluble dye as a colorant is mainly used. However, the dye ink has a defect that it is inferior in weather resistance and water resistance.
Therefore, in recent years, research on pigment inks using pigments instead of water-soluble dyes has been advanced.

  However, the pigment ink is still inferior in color development, ink ejection stability, and storage stability to the dye ink. In addition, with the improvement of image quality improvement technology for OA printers, image density equivalent to that of dye ink is required for both pigment ink and plain paper as a recording medium. However, when plain paper is used as a recording medium, the pigment ink has a problem that the pigment concentration on the paper surface is lowered by penetrating into the paper and the image density is lowered.

  In recent years, demand for industrial applications has been increasing, and high-speed printing is desired. Ink jet printers equipped with line heads have been proposed along with high-speed printing. In order to increase the drying speed of the ink adhering to the recording medium for high-speed printing, a means of increasing the drying speed by adding a penetrant to the ink and allowing water to penetrate into the recording medium is taken. The penetrability of the pigment into the recording medium increases, and the image density further decreases.

  Various methods have been proposed for improving the image density. For example, in Patent Document 1, the rate of increase in viscosity (mPa · s /%) accompanying water evaporation of ink is 5.0 or less when the amount of water evaporation relative to the total ink weight is 30% by mass or less, and the amount of water evaporation is There has been proposed an ink configured to have a point where the viscosity increase rate exceeds 50 between 30% and 45% by mass. According to this proposed ink, when the ink lands on the plain paper and the water evaporates, the viscosity rapidly increases. Therefore, even if printing is performed at high speed, the penetration of the pigment into the paper is suppressed and high image density is indicated. Yes. However, since the proposed ink rapidly increases in viscosity when the water evaporates, if the evaporation of water occurs in the ink jet recording apparatus, particularly in the nozzle, the ink ejection stability decreases due to the increased viscosity, and the periphery of the nozzle There is a problem that ink adheres to the surface.

  Patent Document 2 proposes an ink containing polymer gel microspheres whose viscosity increases due to swelling when the proton concentration is on the acidic side. That is, in the storage state and in the recording apparatus, the proton concentration on the alkaline side is adjusted, and when landed on plain paper, the proton concentration changes to the acidic side due to proton donation from plain paper as the recording medium, and the polymer gel microspheres It is said that the viscosity of the toner increases and the pigment is prevented from penetrating into the paper. According to this, even if moisture evaporates in the nozzles of the ink jet recording apparatus, there is no increase in viscosity, and the ink ejection stability does not deteriorate. However, the image density is still not sufficient and further improvement is necessary.

  Further, Patent Document 3 proposes addition to resin particles containing core / shell type unsaturated acrylic acid alkyl ester and unsaturated acrylic acid as constituents in clear ink, and examples of other monomers are not essential. Styrene, N-dimethylaminopropyl acrylate, and N-vinylformamide are described, but there is no description about the image density improvement by the combination, and no knowledge about the effect of the combination is obtained, and the image density is still sufficient. The effect is not obtained.

  Furthermore, Patent Document 4 describes a resin containing n-dodecyl methacrylate, N, N-dimethylaminoethyl methacrylate methoxypolyethylene glycol methacrylate as an example of resin particles encapsulating a pigment. There are few.

  The present invention has been made in view of the problems in the prior art described above, and has good ink storage stability, high image density can be obtained with plain paper, ink ejection stability is good, and the nozzle periphery. An object of the present invention is to provide an ink for ink jet recording without ink fixation, an ink cartridge using the ink, an ink jet recording apparatus, an ink jet recording method, and an ink recorded matter.

Ink jet recording ink according to the present invention for solving the above-mentioned problems contains water, a wetting agent, a colorant and polymer fine particles, and is ejected onto plain paper having a pH of 4 to 7 on the paper surface. The inkjet recording ink has a pH of 8 to 10, and the polymer fine particles are a structural unit represented by the following formula A or the following formula B and a structural unit represented by the following formula 2. And a structural unit represented by the following formula 3 or formula 4 below, are copolymerized at least , and do not include the colorant, and the volume average particle diameter of the polymer fine particles is the ink for inkjet recording The pH is 8.5 or more and 10 to 300 nm .

[In Formula A, R ₁ represents an alkyl group having 1 to 4 carbon atoms, and R ₂ represents H or a lower alkyl group having 1 or 2 carbon atoms. ]

[In Formula 2, R ₃ is the same and represents a lower alkyl group having 1 or 2 carbon atoms. ]

[In the said Formula 3, l represents the integer of 1-300. ]

[In the above formula 4, R ₄ and R ₅ represent H or a lower alkyl group having 1 or 2 carbon atoms, and m represents an integer of 1 to 90. ]

  According to the present invention, the storage stability of ink is good, a high image density is obtained with plain paper, the ink ejection stability is good, and the ink does not stick around the nozzles.

Schematic showing the production process of polymer fine particles. FIG. 3 is an explanatory diagram illustrating an example of an ink cartridge according to the invention. FIG. 3 is an explanatory view including the case (exterior) of the ink cartridge of FIG. 1 is a schematic diagram showing an example of a serial type ink jet recording apparatus of the present invention. FIG. 5 is a partially enlarged explanatory view of the ink jet recording apparatus shown in FIG. 4. FIG. 5 is another partially enlarged explanatory view of the ink jet recording apparatus shown in FIG. 4. Relationship between pH and average particle diameter in Synthesis Examples 1-9 and Comparative Synthesis Examples 1-3. The relationship between pH and average particle diameter in Synthesis Examples 11-16 and Comparative Synthesis Examples 11-13.

<Ink for inkjet recording>
The ink for ink jet recording of the present embodiment (hereinafter sometimes referred to as ink) contains at least water, a wetting agent, a colorant and polymer fine particles, and further contains other components as necessary. The polymer fine particle is a copolymer containing a specific structural unit.
The ink for ink jet recording of the present invention has a large particle diameter when the polymer fine particles land on a recording medium such as plain paper, and the penetration of the ink into the paper can be suppressed to obtain a high image density.

Hereinafter, the present invention will be described in more detail.
Although the embodiments described below are preferred embodiments of the present invention, various technically preferable limitations are attached thereto, but the scope of the present invention is intended to limit the present invention in the following description. Unless otherwise described, the present invention is not limited to these embodiments.

(water)
As water used in the present invention, pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water can be used.
20-60 mass% is preferable with respect to the total amount of ink.

(Polymer fine particles)

  The polymer fine particles used in the present invention include a structural unit represented by the following formula A or the following formula B, a structural unit represented by the following formula 2, and a structure represented by the following formula 3 or the following formula 4. The unit is a polymer fine particle formed by copolymerizing at least.

[In Formula A, R ₁ represents an alkyl group having 1 to 4 carbon atoms, and R ₂ represents H or a lower alkyl group having 1 or 2 carbon atoms. ]

[In Formula 2, R ₃ is the same and represents a lower alkyl group having 1 or 2 carbon atoms. ]

[In the said Formula 3, l represents the integer of 1-300. ]

[In the above formula 4, R ₄ and R ₅ represent H or a lower alkyl group having 1 or 2 carbon atoms, and m represents an integer of 1 to 90. ]

  The polymer fine particle has at least a structure represented by the following formula A1 or the following formula B1, a structural unit represented by the following formula 12, and a structural unit represented by the following formula 13 or the following formula 14. It is a polymer fine particle formed by copolymerization.

[In Formula A, R ₁₁ represents an alkyl group having 1 to 4 carbon atoms, and R ₁₂ represents H or a lower alkyl group having 1 or 2 carbon atoms. ]

[In Formula 12, R ₁₃ is the same and represents a lower alkyl group having 1 or 2 carbon atoms. ]

[In said Formula 13, n represents the integer of 1-300. ]

[In the above formula 14, R ₁₄ and R ₁₅ represent H or a lower alkyl group having 1 or 2 carbon atoms, and o represents an integer of 1 to 90. ]

Formula A (Formula A1) is a hydrophobic monomer and is an alkyl (meth) acrylate having 1 to 4 carbon atoms.
Specifically, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate,
Examples of propyl methacrylate and butyl methacrylate are commercially available.

  Formula B (Formula B1) is a hydrophobic monomer, specifically styrene (St), which is commercially available.

Formula 2 (Formula 12) is dialkylaminoethyl methacrylate, which exhibits hydrophobicity in a high pH environment, but in a low pH environment, the dialkylamino group site is cationic and hydrophilic (having pH sensitivity). It has a characteristic.
Specific examples include dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, which are commercially available under the names of Kyoeisha Chemical Industry's Light Ester DM and Light Ester DE, for example.

Formula 3 (Formula 13) is an N-vinylformamide (NVF) polymer in which a vinylbenzyl group is introduced at the terminal, and a long chain nonionic hydrophilic group at the terminal (vinylbenzyl moiety) having a double bond. It has a structure provided with a certain NVF polymer.
The compound of the formula 3 can be synthesized by first synthesizing an NVF polymer having a carboxy group at the terminal from NVF and mercaptoacetic acid, and further chemically reacting with p-chloromethylstyrene.
Details of the synthesis are described in the examples.

Formula 4 (Formula 14) represents alkoxy polyethylene glycol methacrylate, alkoxy polyethylene glycol methacrylate, polyethylene glycol methacrylate, or polyethylene glycol acrylate.
It has a structure in which polyethylene glycol, which is a long-chain nonionic hydrophilic group, is added to a terminal (acrylate or methacrylate moiety) having a double bond.

  The compound of the formula 4 is, for example, as a polyethylene glycol methacrylate from NOF Corporation, Blemmer E (m = 1), Blemmer PE90 (m = 2), Blemmer PE200 (m = 5), Blemmer PE350 (m = 8) polyethylene glycol As the acrylate, Blemmer AE90 (m = 2), Blemmer AE200 (m = 5), Blemmer AE400 (m = 10), As the alkoxy polyethylene glycol methacrylate, Blemmer PME100 (m = 2), Blemmer PME200 (m = 4), Blemmer PME400 (m = 9), Blemmer PME550 (m = 9), Blemmer PME1000 (m = 23), Blemmer PME4000 (m = 90) As an alkoxy polyethylene glycol acrylate, Blemmer AME Which is commercially available under the product name of 00 (m = 9).

The polymer fine particles used in the present invention include a hydrophobic monomer represented by the formula A or B, a monomer having a pH sensitivity represented by the formula 2, and a long-chain hydrophilic compound represented by the formula 3. It can be obtained by copolymerizing a monomer having a group in a polar solvent.
At that time, the structural unit of the formula A or B showing hydrophobicity and the structural unit of the formula 2 are localized on the particle surface (corona). Thus, the polymer fine particles have a structure as if the long-chain hydrophilic group represented by Formula 3 was grafted to the styrene / dimethylaminoethyl methacrylate copolymer. In addition, it becomes a structure as illustrated in E of FIG.

Furthermore, it demonstrates in detail with the schematic (FIG. 1) of a production | generation process.
In FIG. 1, the hydrophobic monomer (formula A or B) is represented by 2, the monomer having pH sensitivity (formula 2) is represented by 3 and the monomer having the long-chain hydrophilic group (formula 3) or (formula 4) is represented by 1. ing. Further, a long-chain hydrophilic group site of (Formula 3) or (Formula 4) is denoted by 1a, and a terminal site having a double bond is denoted by 1b.

First, when monomer 1, monomer 2 and monomer 3 are mixed (step A) and polymerized, copolymerization of monomer 2 and monomer 3 (step B) occurs partially. Copolymerization (step C) occurs simultaneously with the monomer 2 and the monomer 3 so that the monomer 1a (long-chain hydrophilic group site) is grafted to the copolymerization of the monomer 2 and the monomer 3. Become.
Since the reaction is carried out in a polar medium, the hydrophobic site selectively accumulates on the inside and the monomer 1 having a long-chain hydrophilic group accumulates selectively on the outside (step D).
When the polymerization is completed in this way, polymer fine particles 6 in which the monomer 1a (long-chain hydrophilic group site) is located on the surface of the core part 4 of the monomer 2 / monomer 3 unit are obtained (step E).

  Unlike conventional core / shell type resin particles, such a particle structure can realize a small particle diameter of 10 to 300 nm under high pH conditions, and long-chain hydrophilic sites are accumulated on the surface, so It has the feature that dispersion is very stable because it is easy to cause trouble.

  Ink-jet recording inks require a particle size of 500 nm or less for the stability of the discharge properties of the ink nozzles, and even if they are used in inks containing polyhydric alcohol compounds as ink materials, they have nonionic hydrophilic groups. The resin particles of the present invention are very excellent in dispersion stability.

Furthermore, the polymer fine particle used in the present invention is also characterized by having a pH-sensitive site (formula 2) at the core site.
That is, in the high pH range, the core maintains a small particle size because it exhibits hydrophobicity, but in the medium pH to low pH range, the above-mentioned formula 2 site having pH sensitivity becomes hydrophilic and the core expands. The particle diameter increases.

When the polymer fine particles of the present invention are used in an ink jet recording ink, the ink jet recording ink is usually adjusted to a high pH of 8 to 10, so the polymer particle size contained in the ink is about 10 to 300 nm. Ink ejection properties and storage stability are good.
However, when the ink lands on the plain paper recording medium, the pH of the paper surface is 4 to 7, so the ink pH varies from the middle to the low range. At this time, the particle diameter of the polymer particles contained in the ink increases and stays on the paper surface, so that the ink penetration into the paper is suppressed, and the colorant concentration on the paper surface increases and the image density increases.

In order to increase the image density, it is necessary to increase the particle size variation of the polymer fine particles, and as a result of intensive studies, the carbon number of R _{3 in} the above formula 2 which is a constituent unit of the polymer fine particles used in the present invention is important. I found out that
R ₃ is preferably an alkyl group having 1 to 2 carbon atoms, and alkyl having 2 carbon atoms can maximize the particle diameter. When the number of carbon atoms exceeds 3, the steric hindrance increases, so that the hydrogen ions in the solvent are difficult to approach the dialkylamine moiety, making it difficult to become hydrophilic. Therefore, the effect of increasing the particle size is reduced.

In addition, a repeating unit of a long-chain hydrophilic group part of a hydrophobic monomer (formula A or B), a pH-sensitive monomer (formula 2) and a monomer having a long-chain hydrophilic group (formula 3 or formula 4) The structural ratio is also important. Among the structural units represented by the formula A or B, the structural unit represented by the formula 2, and the structural unit represented by the formula 3 or 4, the repeating unit of the long-chain hydrophilic group moiety. And a molar ratio of 1 / 0.1 to 5 / 0.1 to 5 is preferable, and 1 / 0.5 to 3 / 0.5 to 3 is more preferable.

The polymer fine particles used in the present invention are preferably added in an amount of 0.05 to 2.0% by weight as a solid content with respect to the total amount of ink.
If it is less than 0.05%, the increase in particle diameter due to a sufficient pH response may not be obtained, and the ink may penetrate into the recording medium. If it exceeds 2.0%, the polymer fine particles aggregate. In some cases, the viscosity of the ink becomes high, and it becomes difficult to obtain the viscosity of the ink that can be ejected by the ink jet recording apparatus.

The volume average particle diameter of the polymer fine particles of the present invention is preferably pH 8.5 or more and 10 to 300 nm.
When the volume average particle size is less than 10 nm, the viscosity of the polymer fine particles themselves becomes too high, and it becomes difficult to obtain the viscosity of the ink that can be ejected by the ink jet recording apparatus.
When the volume average particle size exceeds 300 nm, particles may be clogged in the nozzle of the ink jet recording apparatus, resulting in ejection failure.

(Wetting agent)
The wetting agent used in the present invention is necessary for improving ejection stability by providing a moisturizing effect in the ink composition.
The content is preferably 10 to 50% by mass with respect to the total amount of ink.
If the content is less than 10% by mass, the ink easily evaporates, and thickened ink may be clogged due to evaporation of the ink in the ink supply system in the inkjet recording apparatus.
If the content is more than 50% by mass, clogging of thickened ink is less likely to occur in the ink jet recording apparatus, but it is necessary to reduce the amount of solids such as pigments and resins in order to make the ink have a desired viscosity. In this case, the image density of the recorded matter may be lowered.

Although the following are illustrated as a wetting agent used by this invention, It is not limited to these.
For example, ethylene glycol, diethylene glycol, 1,3-butanediol, 3-methyl-1,3-butyl glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol, glycerin 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2,4-butanetriol, 1,2,3 -Polyhydric alcohols such as butanetriol and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetra Polyhydric alcohol alkyl ethers such as tylene glycol monomethyl ether and propylene glycol monoethyl ether, 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, 1,3-dimethylimidazolidinone, nitrogen-containing heterocyclic compounds such as ε-caprolactam, γ-butyrolactone, amides such as formamide, N-methylformamide, N, N-dimethylformamide , Amines such as monoethanolamine, diethanolamine, triethylamine, sulfur-containing compounds such as dimethyl sulfoxide, sulfolane, thiodiethanol, propylene carbonate, ethylene carbonate, etc. That.
These wetting agents can be used alone or in admixture of two or more. Among these, the inclusion of 1,3-butanediol, diethylene glycol, 2,2,4-trimethyl-1,3-pentanediol, triethylene glycol and / or glycerin is excellent in preventing discharge failure due to moisture evaporation. Effect.

(Coloring agent)
The content of the pigment as the colorant used in the present invention in the recording ink is preferably 0.1% by mass or more and 20.0% by mass or less.
The volume average particle diameter (D50%) of the pigment is preferably 150 nm or less.
Here, the 50% average particle diameter of the pigment indicates a value of D50% measured by a dynamic light scattering method with Microtrac UPA manufactured by Nikkiso Co., Ltd. in an environment of 23 ° C. and 55% RH.
There is no restriction | limiting in particular as these pigments, According to the objective, it can select suitably, For example, any of an inorganic pigment and an organic pigment may be sufficient.
These may be used individually by 1 type and may use 2 or more types together.

Examples of the inorganic pigment include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, bitumen, cadmium red, chrome yellow, metal powder, and carbon black.
Among these, carbon black is preferable.
In addition, as said carbon black, what was manufactured by well-known methods, such as a contact method, a furnace method, and a thermal method, is mentioned, for example.

Examples of the organic pigment include azo pigments, azomethine pigments, polycyclic pigments, dye chelates, nitro pigments, nitroso pigments, and aniline black.
Among these, azo pigments and polycyclic pigments are more preferable.
Examples of the azo pigments include azo lakes, insoluble azo pigments, condensed azo pigments, and chelate azo pigments.
Examples of the polycyclic pigment include 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 quinofullerone pigment, and a rhodamine B lake pigment. It is done.
Examples of the dye chelates include basic dye chelates and acidic dye chelates.

Examples of black materials include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11), titanium oxide, and the like. And organic pigments such as aniline black (CI Pigment Black 1).
As the carbon black, a furnace method, a carbon black produced by the channel method, primary particle diameter of, 15Nm～40nm, specific surface area by BET ^{method, 50m 2 / g~300m 2 / g} , DBP oil absorption amount 40ml / 100 g to 150 ml / 100 g, those having a volatile content of 0.5% to 10% and a pH value of 2 to 9 are preferred.
As the carbon black, commercially available products can be used. 2300, no. 900, MCF-88, no. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B (all manufactured by Mitsubishi Chemical Corporation); Raven700, 5750, 5250, 5000, 3500, 1255 (all manufactured by Columbia); Regal400R, 330R, 660R, Mogu L, Monarch700, 800, 880, 900, 1000, 1100, 1300, Monarch 1400 (all manufactured by Cabot); Color Black FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Printex 35, U, V, 140U, 140V, Special Black 6, 5, 4A, and 4 (all manufactured by Degussa).

  There is no restriction | limiting in particular as a pigment which can be used for yellow ink as the thing for said colors, According to the objective, it can select suitably, for example, C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 2, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 73, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 75, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 98, C.I. I. Pigment yellow 114, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 180, and the like.

  The pigment that can be used in the magenta ink is not particularly limited and may be appropriately selected depending on the intended purpose. I. Pigment red 5, C.I. I. Pigment red 7, C.I. I. Pigment red 12, C.I. I. Pigment red 48 (Ca), C.I. I. Pigment red 48 (Mn), C.I. I. Pigment red 57 (Ca), C.I. I. Pigment red 57: 1, C.I. I. Pigment red 112, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 146, C.I. I. Pigment red 168, C.I. I. Pigment red 176, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, pigment violet 19, and the like.

  The pigment that can be used in the cyan ink is not particularly limited and may be appropriately selected depending on the purpose. I. Pigment blue 1, C.I. I. Pigment blue 2, C.I. I. Pigment blue 3, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15:34, C.I. I. Pigment blue 16, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 63, C.I. I. Pigment blue 66; C.I. I. Bat Blue 4, C.I. I. Bat Blue 60 and the like.

In addition, the pigment contained in each ink used in the present invention may be newly produced for the present invention.
By using Pigment Yellow 74 as the yellow pigment, Pigment Red 122, Pigment Bio Red 19 as the magenta pigment, and Pigment Blue 15: 3 as the cyan pigment, it is possible to obtain a well-balanced ink with excellent color tone and light resistance. it can.

(Other ingredients)
Other components are not particularly limited and may be appropriately selected as necessary. For example, a dispersant, a penetrant, a pH adjuster, a water-dispersible resin, an antiseptic / antifungal agent, a chelating reagent, and a rust inhibitor , Antioxidants, ultraviolet absorbers, oxygen absorbers, light stabilizers, and the like.

  Examples of the dispersant include various surfactants such as an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant, and polymer-type dispersants. These may be used alone or in combination of two or more.

  Examples of the anionic surfactant include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acyl methyl taurate, polyoxyalkyl ether sulfates. Salt, polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester salt, lauryl alcohol sulfate ester salt, alkylphenol type phosphate ester, naphthalenesulfonate formalin condensate, alkyl type phosphate ester, alkylallylsulfone hydrochloride, diethyl Examples include sulfosuccinate, diethylhexyl sulfosuccinate, and dioctyl sulfosuccinate.

Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.
Examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, imidazoline. Derivatives and the like.

Examples of nonionic surfactants include the following.
Ether-based interfaces such as polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyallylalkyl alkyl ether Active agent;
Polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate Ester surfactants such as
2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyn-3-ol And acetylene glycol-based surfactants.

The penetrant preferably contains either a polyol compound having 8 to 11 carbon atoms or a glycol ether compound having 8 to 11 carbon atoms.
The penetrant is different from the wetting agent and has a relatively low wettability compared to the wetting agent. Therefore, the penetrating agent can be referred to as a non-wetting agent. It is a meaning. These preferably have a solubility of between 0.2% and 5.0% by weight in 25 ° C. water.

Among these, 2-ethyl-1,3-hexanediol [solubility: 4.2% (25 ° C.)], 2,2,4-trimethyl-1,3-pentanediol [solubility: 2.0% (25 ° C)] is particularly preferred.
As other polyol compounds, as aliphatic diols, for example, 2-ethyl-2-methyl-1,3-propanediol, 3,3-dimethyl-1,2-butanediol, 2,2-diethyl-1, 3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol, 5-hexene- 1,2-diol and the like can be mentioned.
Other penetrants that can be used in combination are not particularly limited as long as they can be dissolved in the ink and adjusted to the desired physical properties, and can be appropriately selected according to the purpose. For example, diethylene glycol monophenyl ether, ethylene Glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, alkyl and aryl ethers of polyhydric alcohols such as tetraethylene glycol chlorophenyl ether, lower alcohols such as ethanol, etc. Is mentioned.

  The content of the penetrant in the inkjet ink is preferably 0.1% by mass to 4.0% by mass. When the content is less than 0.1% by mass, a fast-drying property cannot be obtained and a blurred image may be obtained. When the content exceeds 4.0% by mass, the dispersion stability of the colorant is impaired, and the nozzle May become clogged easily, or the permeability to a recording medium may be increased more than necessary, resulting in a decrease in image density or through-through.

The pH adjuster is not particularly limited as long as the pH can be adjusted to 8.5 to 11 and preferably 9 to 11 without adversely affecting the ink jet ink to be prepared. For example, alcohol amines, hydroxides of alkali metal elements, ammonium hydroxides, phosphonium hydroxides, alkali metal carbonates, and the like can be used.
When the pH is less than 8.5 or more than 11, the amount of the ink-jet head or ink supply unit that melts out is large, and problems such as ink deterioration, leakage, and ejection failure may occur. When it is less than 8.5, the ink pH may decrease during storage of the ink, and the polymer fine particles may aggregate due to an increase in the particle diameter.
The pH can be measured by, for example, a pH meter HM-30R (manufactured by TOA-DKK).

Examples of the alcohol amines include diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol, and the like.
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.
Examples of the ammonium hydroxide include ammonium hydroxide, quaternary ammonium hydroxide, quaternary phosphonium hydroxide, and the like.
Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, and potassium carbonate.

The water-dispersible resin has excellent film-forming properties (image formability), high water repellency, high water resistance, and high weather resistance, and has high water resistance and high image density (high color development). Useful for.
Specific examples of the water-dispersible resin include condensation-type synthetic resins, addition-type synthetic resins, natural polymer compounds, and the like.
Examples of the condensed synthetic resin include polyester resin, polyurethane resin, polyepoxy resin, polyamide resin, polyether resin, poly (meth) acrylic resin, acrylic-silicone resin, and fluorine-based resin.
Examples of the addition type synthetic resin include polyolefin resins, polystyrene resins, polyvinyl alcohol resins, polyvinyl ester resins, polyacrylic acid resins, unsaturated carboxylic acid resins, and the like.
Examples of the natural polymer compound include celluloses, rosins, and natural rubber.
Among these, polyurethane resin fine particles, acrylic-silicone resin fine particles, and fluorine-based resin fine particles are particularly preferable.

The average particle size (D50) of the water-dispersible resin is related to the viscosity of the dispersion, and for the same composition, the viscosity at the same solid content increases as the particle size decreases.
The average particle diameter (D50) of the water-dispersible resin is preferably 50 nm or more so that the ink does not have an excessively high viscosity.
Further, when the particle size is several tens of μm, it becomes larger than the nozzle opening of the ink jet head and cannot be used.
If particles having a large particle diameter are present in the ink even though they are smaller than the nozzle opening, the ejection stability is deteriorated.
Therefore, the average particle diameter (D50) is more preferably 200 nm or less in order not to disturb the ink ejection stability.

The water-dispersible resin has a function of fixing the water-dispersed colorant on the paper surface, and is preferably formed into a film at room temperature to improve the fixability of the color material.
Therefore, it is preferable that the minimum film-forming temperature (MFT) of the water-dispersible resin is 30 ° C. or less.
Further, when the glass transition temperature of the water-dispersible resin is -40 ° C. or lower, the resin film becomes more viscous and the printed matter is tacky. Therefore, the water-dispersible resin has a glass transition temperature of −30 ° C. or higher. It is preferable.
The content of the water-dispersible resin in the inkjet ink is preferably 1 to 15% by mass, more preferably 2 to 7% by mass in terms of solid content.

  Examples of the antiseptic / antifungal agent include sodium dehydroacetate, sodium sorbate, 2-pyridinethiol-1-oxide sodium, sodium benzoate, sodium pentachlorophenol, and the like.

  Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate, and the like.

  Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

  Examples of the antioxidant include phenolic antioxidants (including hindered phenolic antioxidants), amine-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and the like.

  Examples of the ultraviolet absorber include a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a salicylate ultraviolet absorber, a cyanoacrylate ultraviolet absorber, and a nickel complex ultraviolet absorber.

(Inkjet recording ink manufacturing method)
The ink for inkjet recording of this embodiment is prepared by dispersing or dissolving water, a wetting agent, a colorant and polymer fine particles, and other components in an aqueous medium as necessary, and further stirring and mixing as necessary. To manufacture.
The dispersion can be performed by, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, and the like. be able to.

The physical properties of the ink for ink jet recording of the present invention are not particularly limited and may be appropriately selected depending on the intended purpose. For example, the viscosity, surface tension and the like are preferably in the following ranges.
The viscosity of the inkjet ink at 25 ° C. is preferably 3 mPa · s to 20 mPa · s. By setting the ink viscosity to 3 mPa · s or more, the effect of improving the printing density and the character quality can be obtained. On the other hand, by suppressing the ink viscosity to 20 mPa · s or less, it is possible to ensure the discharge performance.
The viscosity can be measured at 25 ° C. using, for example, a viscometer (RL-550, manufactured by Toki Sangyo Co., Ltd.).
The surface tension of the inkjet ink is preferably 40 mN / m or less at 25 ° C.
When the surface tension exceeds 40 mN / m, leveling of the ink on the recording medium is difficult to occur and the drying time may be prolonged.

(ink cartridge)
The ink cartridge of the present invention accommodates the ink for ink jet recording of the present invention in a container, and can also constitute other members appropriately selected as necessary.
The shape, structure, size, and material of the container are not particularly limited and can be appropriately selected according to the purpose.
Preferred examples include those having at least an ink bag formed of an aluminum laminate film, a resin film, or the like.

One embodiment of the ink cartridge of the present invention will be described with reference to FIGS.
FIG. 2 is a view showing an example of the ink cartridge of the present invention, and FIG. 3 is a view including a case (exterior) of the ink cartridge 200 of FIG.
As shown in FIG. 2, the ink cartridge 200 is filled into the ink bag 241 from the ink inlet 242 and exhausted, and then the ink inlet 242 is closed by fusion.
In use, the needle of the apparatus main body is pierced into the ink discharge port 243 made of a rubber member and supplied to the apparatus.
The ink bag 241 is formed of a packaging member such as a non-permeable aluminum laminate film.
As shown in FIG. 3, the ink bag 241 is usually housed in a plastic cartridge case 244 and is detachably mounted on various ink jet recording apparatuses.

(Inkjet recording apparatus and inkjet recording method)
The ink jet recording apparatus of the present invention includes at least ink flying means, and further includes other means appropriately selected as necessary, for example, stimulus generation means, control means, and the like.
The inkjet recording method of the present invention includes at least an ink flying process, and further includes other processes appropriately selected as necessary, for example, a stimulus generation process, a control process, and the like.
The ink jet recording method of the present invention can be preferably carried out by the ink jet recording apparatus of the present invention, and the ink flying step can be suitably carried out by the ink flying means. Moreover, the said other process can be suitably performed by the said other means.

The ink flying step is a step of forming an image by applying a stimulus to the ink jet ink of the present invention and causing the ink jet ink to fly.
The ink flying means is means for forming an image by applying a stimulus to the ink-jet ink of the present invention and causing the ink-jet ink to fly. The ink flying means is not particularly limited, and examples thereof include various nozzles for ejecting ink.

The stimulus can be generated, for example, by the stimulus generating means, and the stimulus is not particularly limited and can be appropriately selected according to the purpose, such as heat (temperature), pressure, vibration, light, etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, heat and pressure are preferable.
Examples of the stimulus generating means include a superheater, a pressurizer, a piezoelectric element, a vibration generator, an ultrasonic oscillator, and a light.
Specifically, a piezoelectric actuator such as a piezoelectric element such as a piezoelectric element, a thermal actuator that uses a phase change due to liquid film boiling using an electrothermal transducer such as a heating resistor, a shape that uses a metal phase change due to a temperature change Memory alloy actuators, electrostatic actuators using electrostatic force, and the like can be mentioned.

There is no particular limitation on the mode of the ink flying, and it varies depending on the type of the stimulus. For example, when the stimulus is “heat”, the thermal energy corresponding to the recording signal is output to the ink in the recording head. For example, using a thermal head or the like, generating bubbles in the ink by the thermal energy, and ejecting and ejecting the ink as droplets from the nozzle holes of the recording head by the pressure of the bubbles. It is done.
Further, when the stimulus is “pressure”, for example, by applying a voltage to a piezoelectric element bonded to a position called a pressure chamber in an ink flow path in the recording head, the piezoelectric element bends and the volume of the pressure chamber is increased. And a method of ejecting and ejecting the ink as droplets from the nozzle holes of the recording head.

  The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as sequencers and computers.

Here, one aspect of carrying out the ink jet recording method of the present invention by the ink jet recording apparatus of the present invention will be described with reference to the drawings.
FIG. 4 is a schematic view showing an example of the serial type ink jet recording apparatus of the present invention.
The ink jet recording apparatus shown in FIG. 4 stocks an apparatus main body 101, a paper feed tray 102 for loading paper mounted on the apparatus main body 101, and paper on which an image is recorded (formed) mounted on the apparatus main body 101. A paper discharge tray 103 and an ink cartridge loading unit 104.
On the upper surface of the ink cartridge loading unit 104, an operation unit 105 such as operation keys and a display is arranged.
The ink cartridge loading unit 104 has a front cover 115 that can be opened and closed for attaching and detaching the ink cartridge 201.

In the apparatus main body 101, as shown in FIGS. 5 and 6, a carriage 133 is slid in the main scanning direction by a guide rod 131 and a stay 132, which are guide members horizontally mounted on left and right side plates (not shown). The main scanning motor (not shown) moves and scans in the direction of the arrow in FIG.
The carriage 133 is provided with a recording head 134 composed of four ink jet recording heads that eject ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk). Are arranged in a direction crossing the main scanning direction, and the ink droplet ejection direction is directed downward.

As the ink jet recording head constituting the recording head 134, a piezoelectric actuator such as a piezoelectric element, a thermal actuator using phase change due to liquid film boiling using an electrothermal transducer such as a heating resistor, a metal phase due to temperature change, etc. A shape memory alloy actuator using a change, an electrostatic actuator using an electrostatic force, or the like provided as energy generating means for discharging ink can be used.
In addition, the carriage 133 is equipped with a sub tank 135 for each color for supplying ink of each color to the recording head 134.
The sub tank 135 is supplied with the ink from the ink cartridge 201 of the present invention loaded in the ink cartridge loading unit 105 via an ink supply tube (not shown) and is replenished.

On the other hand, as a paper feeding unit for feeding the paper 142 stacked on the paper stacking unit (pressure plate) 141 of the paper feeding tray 103, a half-moon roller (feeding) that separates and feeds the paper 142 one by one from the paper stacking unit 141. A separation pad 144 made of a material having a large coefficient of friction is provided facing the paper roller 143) and the paper feed roller 143, and the separation pad 144 is urged toward the paper feed roller 143 side.
As a transport unit for transporting the paper 142 fed from the paper feed unit below the recording head 134, a transport belt 151 for transporting the paper 142 by electrostatic adsorption and a guide 145 from the paper feed unit. The counter roller 152 for transporting the paper 142 fed via the transport belt 151 with the transport belt 151 and the paper 142 fed substantially vertically upward are changed by approximately 90 ° so as to follow the transport belt 151. For this purpose, a conveyance guide 153 and a tip pressure roller 155 urged toward the conveyance belt 151 by a pressing member 154 are provided.

In addition, a charging roller 156 that is a charging unit for charging the surface of the conveyance belt 151 is provided.
The conveyance belt 151 is an endless belt, is stretched between the conveyance roller 157 and the tension roller 158, and can circulate in the belt conveyance direction.
The transport belt 151 includes, for example, a surface layer serving as a sheet adsorbing surface formed of a resin material having a thickness of about 40 μm that is not subjected to resistance control, for example, a copolymer of tetrafluoroethylene and ethylene (ETFE), and the surface layer. It has a back layer (medium resistance layer, earth layer) that is made of the same material and has resistance controlled by carbon.
On the back side of the conveyance belt 151, a guide member 161 is arranged corresponding to a printing area by the recording head 134.

Note that, as a paper discharge unit for discharging the paper 142 recorded by the recording head 134, a separation claw 171 for separating the paper 142 from the conveyance belt 151, a paper discharge roller 172, and a paper discharge roller 173 are provided. The paper discharge tray 103 is disposed below the paper discharge roller 172.
A double-sided paper feeding unit 181 is detachably mounted on the back surface of the apparatus main body 101.

The double-sided paper feeding unit 181 takes in the paper 142 returned by the reverse rotation of the transport belt 151, reverses it, and feeds it again between the counter roller 152 and the transport belt 151.
A manual paper feed unit 182 is provided on the upper surface of the duplex paper feed unit 181.
In this ink jet recording apparatus, the paper 142 is separated and fed one by one from the paper feed unit, and the paper 142 fed substantially vertically upward is guided by the guide 145 and between the transport belt 151 and the counter roller 152. It is sandwiched and conveyed.
Further, the leading end is guided by the conveying guide 153 and pressed against the conveying belt 151 by the leading end pressure roller 155, and the conveying direction is changed by approximately 90 °.
At this time, the conveyance belt 157 is charged by the charging roller 156, and the sheet 142 is conveyed by being electrostatically attracted to the conveyance belt 151.
Therefore, by driving the recording head 134 according to the image signal while moving the carriage 133, ink droplets are ejected onto the stopped paper 142 to record one line, and after the paper 142 is conveyed by a predetermined amount, Record the next line.
Upon receiving a recording end signal or a signal that the trailing edge of the sheet 142 has reached the recording area, the recording operation is terminated and the sheet 142 is discharged onto the discharge tray 103.
When a near-end remaining amount of ink in the sub tank 135 is detected, a required amount of ink is supplied from the ink cartridge 201 to the sub tank 135.

In this ink jet recording apparatus, when the ink in the ink cartridge 201 of the present invention is used up, the casing of the ink cartridge 201 can be disassembled and only the ink bag inside can be replaced.
Further, the ink cartridge 201 can supply ink stably even when the ink cartridge 201 is placed vertically and has a front loading configuration.
Therefore, even when the upper portion of the apparatus main body 101 is closed and installed, for example, when stored in a rack or when an object is placed on the upper surface of the apparatus main body 101, the ink cartridge 201 is used. Can be easily exchanged.
In addition, although it demonstrated in the example applied to the serial type (shuttle type) inkjet recording device which a carriage scans, it can apply similarly to the line type inkjet recording device provided with the line type head.

  The ink jet recording apparatus of the present invention can be applied to various types of recording by the ink jet recording method, and is particularly preferably applied to, for example, an ink jet recording printer, a facsimile apparatus, a copying apparatus, a printer / fax / copier multifunction machine, and the like. Can do.

(Ink record)
The ink recorded matter recorded by the ink jet recording method of the present invention is the ink recorded matter of the present invention.
The ink recorded matter of the present invention has an image formed on the recording medium using the ink in the ink media set of the present invention.
The recording medium is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include plain paper, coated paper for printing, glossy paper, special paper, cloth, film, and OHP sheet. Can be mentioned.
These may be used individually by 1 type and may use 2 or more types together.
Among these, at least one of plain paper and coated paper for printing is preferable.
The plain paper is advantageous in that it is inexpensive.
The coated paper for printing is advantageous in that it provides a smooth glossy image at a relatively low cost as compared with glossy paper.
However, although the drying property is poor and it is generally difficult to use for inkjet, the drying property is improved by the ink of the present invention.
The ink recorded matter has high image quality, no bleeding, excellent temporal stability, and can be suitably used for various purposes as a material on which various prints or images are recorded.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further, this invention is not limited to these examples.
In the examples,% used is based on mass.

<< Examples 1 to 9, Comparative Examples 1 to 3 >>
<Synthesis example of polymer fine particles>
Below, the synthesis example of the polymer fine particle used for this invention is shown.
In addition, the weight average molecular weight of the polymer in the synthesis example was measured according to the following method.

Shimadzu CTO-20A for the column thermostat, Shimadzu RID-10A for the detector, Shimadzu LC-20AD for the eluent flow path pump, Shimadzu DGU-20A for the degasser, autosampler Was measured by GPC method using SIL-20A manufactured by Shimadzu Corporation. The column used was a Tosoh water-based SEC column TSKgelG3000PWXL (exclusion limit molecular weight 2 × 10 ⁵ ), TSKgelG5000PWXL (exclusion limit molecular weight 2.5 × 10 ⁶ ) and TSKgelG6000PWXL (exclusion limit molecular weight 5 × 10 ⁷ ). The sample was prepared to a concentration of 2 g / 100 ml with an eluent and used for measurement. As an eluent, an aqueous solution adjusted to 0.5 mol / liter each of acetic acid and sodium acetate was used. The column temperature was 40 ° C. and the flow rate was 1.0 ml / min. A calibration curve was determined using nine types of polyethylene glycols having molecular weights of 1065, 5050, 24000, 50000, 107000, 140000, 250,000, 540000, and 920000 as standard samples, and the weight average molecular weight of the polymer was determined based on the calibration curve. .

The particle diameter of the pH-responsive polymer particles according to the present invention was measured by a dynamic light scattering method (Malvern: Zetasizer Nano ZS).
The pH at the time of measuring the particle diameter of the pH-responsive polymer fine particles according to the present invention was adjusted with a 0.2% dispersion with hydrochloric acid or sodium hydroxide.

In addition, the following abbreviations mean the following compounds.
AAc: acrylic acid MA: methyl acrylate EA: ethyl acrylate BA: butyl acrylate BMA: butyl methacrylate DMAEMA: dimethylaminoethyl methacrylate DEAEMA: diethylaminoethyl methacrylate NVF: N-vinylformamide PEG: polyethylene glycol DDA: dodecyl acrylate

First, the formula 3, which is a structural unit, was synthesized.
(1) Synthesis of N-vinylformamide (NVF) polymer introduced with vinylbenzyl group (Formula 3) STEP 1: Synthesis of NVF polymer having carboxy group at the terminal Stirrer, reflux condenser, two dropping funnels, In a reaction vessel equipped with a nitrogen gas introduction tube and a thermometer, 463.5 g of water was charged and heated to raise the temperature to 80 ° C. Under a nitrogen stream, a mixed solution of 500 g (5.63 mol) of an 80% by weight aqueous solution of N-vinylformamide (NVF) and 20.3 g (0.22 mol) of mercaptoacetic acid and 16.2 g of a 5% by weight aqueous solution of potassium persulfate. (0.003 mol) was added dropwise simultaneously over 2 hours. After completion of dropping, the mixture was kept at 80 ° C. for 3 hours to obtain an NVF polymer solution having a carboxyl group at the end (solid content concentration 41.8%). After completion of the reaction, re-precipitation was performed several times with acetone to purify the NVF polymer having a carboxy group at the terminal. It calculated | required from GPC (liquid chromatography) of the obtained polymer.
The weight average molecular weight was 28,000, and the number average molecular weight was 14,000.

STEP 2: Synthesis of N-vinylformamide (NVF) polymer with vinylbenzyl group introduced Next, an NVF polymer solution having a carboxy group at the terminal in a reaction vessel equipped with a stirrer, reflux condenser and thermometer (Solid concentration 41.8%) 700.0 g [0.15 mol as a mercaptoacetic acid unit (determined from the previous charge)] was added, 280.0 g of ethanol was added, and 16.7 g of a 48 wt% aqueous solution of sodium hydroxide. (0.20 mol), 13.0 g (0.04 mol) of tetrabutylammonium bromide, and 30.2 g (0.20 mol) of p-chloromethylstyrene were allowed to react at 30 ° C. for 72 hours. Was introduced to obtain an N-vinylformamide (NVF) polymer solution (solid content concentration 31.5%). After completion of the reaction, reprecipitation with acetone was performed to purify an N-vinylformamide (NVF) polymer having a vinylbenzyl group introduced therein. As a result of 1H-NMR measurement, it was found that the introduction rate of vinylbenzyl group at the terminal was almost 100%. Moreover, the number average molecular weight of the N-vinylformamide (NVF) polymer into which the vinylbenzyl group was measured as measured by GPC (liquid chromatography) was 14,100 (l in Formula 3 is 100 to 300).

(Synthesis Example 1) Synthesis of Polymer Fine Particle A Next, N-vinylformamide (NVF) in which a vinylbenzyl group was introduced at the above end in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas introduction tube and a thermometer. ) 158.4 g of polymer (formula 3) [0.60 mol as NVF repeating unit (determined from the previous charge)], dimethylaminoethyl methacrylate (DMAEMA) (formula 2) 94.3 g (0.60 mol), methyl 51.6 g (0.60 mol) of acrylate (formula A) and 614.6 g of water were charged, the pH was adjusted with hydrochloric acid, and the temperature was raised to 60 ° C. Under a nitrogen stream, 81.1 g (0.015 mol) of a 5% by weight aqueous solution of potassium persulfate was added and copolymerized for 6 hours to obtain a milky white dispersion (solid content concentration 22.4%).

(Synthesis Example 2) Synthesis of Polymer Fine Particle B In the synthesis of polymer fine particle A in Synthesis Example 1 above, 51.6 g (0.60 mol) of methyl acrylate was changed to 60.0 g (0.60 mol) of ethyl acrylate. A reaction was carried out in the same manner as in Synthesis Example 1 except that 614.6 g of water was changed to 604.2 g to obtain a milky white dispersion (solid content concentration 23.0%).

(Synthesis Example 3) Synthesis of Polymer Fine Particle C In the synthesis of polymer fine particle A of Synthesis Example 1, 51.6 g (0.60 mol) of methyl acrylate was changed to 76.9 g (0.60 mol) of butyl acrylate. A reaction was carried out in the same manner as in Synthesis Example 1 except that 614.6 g of water was changed to 589.3 g to obtain a milky white dispersion (solid content concentration 23.0%).

(Synthesis Example 4) Synthesis of Polymer Fine Particle D In the synthesis of polymer fine particle A of Synthesis Example 1 above, 51.6 g (0.60 mol) of methyl acrylate was changed to 85.2 g (0.60 mol) of butyl methacrylate. The reaction was performed in the same manner as in Synthesis Example 1 to obtain a milky white dispersion (solid content concentration 23.0%).

(Synthesis Example 5) Synthesis of Polymer Fine Particle E In the synthesis of polymer fine particle A of Synthesis Example 1, 51.6 g (0.60 mol) of methyl acrylate was changed to 76.9 g (0.60 mol) of butyl acrylate. The reaction was carried out in the same manner as in Synthesis Example 1 except that 94.3 g (0.60 mol) of dimethylaminoethyl methacrylate (DMAEMA) was changed to 122.0 g (60 mol) of diethylaminoethyl methacrylate (DEAEMA), and a milky white dispersion ( Solid content concentration 23.0%) was obtained.

(Synthesis Example 6) Synthesis of Polymer Fine Particle F In the synthesis of polymer fine particle E of Synthesis Example 5 above, 158.4 g of N-vinylformamide (NVF) polymer (formula 3) solution into which a vinylbenzyl group was introduced at the terminal. 118.8 g [0.45 mol as NVF repeating unit (determined from the previous charge)], diethylaminoethyl methacrylate (DMAEMA) 122.0 g (0.60 mol) was changed to 181.0 g (0.89 mol). , Except that 76.9 g (0.60 mol) of butyl acrylate was changed to 57.7 g (0.45 mol) and 613.4 g of water, the reaction was carried out in the same manner as in Synthesis Example 5 to obtain a milky white dispersion (solid content concentration 23 0.0%).

(Synthesis Example 7) Synthesis of Polymer Fine Particle G In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas introduction tube, and a thermometer, a PEG macromonomer (methoxypolyethylene glycol methacrylate: Blemmer PME-1000) (Formula 4 ) 55.0 g [1.14 mol as ethylene glycol repeating unit], DEAEMA 116.5 g (0.57 mol), butyl acrylate 73.4 g (0.57 mol), ethanol 100.0 g, water 618.9 g, After adjusting the pH with hydrochloric acid, the temperature was raised to 60 ° C. Under a nitrogen stream, 81.1 g (0.015 mol) of a 5% by weight aqueous solution of potassium persulfate was added and copolymerized for 6 hours to obtain a milky white dispersion (solid content concentration 22.0%).

(Synthesis Example 8) Synthesis of Polymer Fine Particle H In the synthesis of polymer fine particle G of Synthesis Example 7 above, 55.0 g of PEG macromonomer (methoxypolyethylene glycol methacrylate: Blenmer PME-1000) (Formula 4) [as ethylene glycol repeating unit 1.14 mol] was changed to 61.1 g of PEG macromonomer (methoxypolyethylene glycol acrylate: BLEMMER AME-400) [1.14 mol as a repeating unit], and the reaction was performed in the same manner as in Synthesis Example 7 to obtain a milky white dispersion. A liquid (solid content concentration 22.0%) was obtained.

(Synthesis Example 9) Synthesis of Polymer Fine Particle I In the synthesis of polymer fine particle G of Synthesis Example 7 above, 55.0 g of PEG macromonomer (methoxypolyethylene glycol methacrylate: Blemmer PME-1000) (Formula 4) [as ethylene glycol repeating unit 1.14 mol] was reacted in the same manner as in Synthesis Example 4 except that PEG macromonomer (polyethylene glycol monoacrylate: BLEMMER AE-400) was changed to 58.3 g [1.14 mol as an ethylene glycol repeating unit]. A milky white dispersion (solid content concentration 22.0%) was obtained.

(Comparative Synthesis Example 1) Synthesis of Polymer Fine Particle J In the synthesis of polymer microparticle A of Synthesis Example 1 above, the monomer composition was 51.6 g (0.60 mol) of methyl acrylate and 43.2 g (0.60 mol) of acrylic acid. ) The reaction was carried out in the same manner as in Synthesis Example 1 to obtain a milky white dispersion (solid content concentration 23.8%).

(Comparative Synthesis Example 2) Synthesis of Polymer Fine Particle K In the synthesis of polymer microparticle A of Synthesis Example 1 above, the constituent monomer was 65.1 g of PEG macromonomer (Blemmer PME-1000) (Formula 4) [ethylene glycol repeating unit as 1.35 mol], 343.5 g (1.35 mol) of dodecyl acrylate, 100.0 g of ethanol, 618.9 g of water, and the same reaction as in Synthesis Example 1 was carried out to give a milky white dispersion (solid content concentration 21.6). %).

(Comparative Synthesis Example 3)
Gel fine particles described in Example 1 of Japanese Patent No. 3155318 were used.

  The structural units and molar ratios of the synthesis examples and comparative synthesis examples thus obtained are shown in Table 1, and the relationship between the pH of the pH-responsive polymer fine particles and the average particle diameter is shown in FIG.

  From this result, the average particle diameter of the pH-responsive polymer particles used in the present invention increases as the pH decreases. It can be seen that the particle size when the pH is high is small compared to the prior art (Comparative Synthesis Example 3), the pH at which the particle size increases is high, and the saturated particle size is also large. Further, it is also found that when the pH-sensitive monomer (formula 2), which is a constituent material necessary for the present invention, is lacking, the particle diameter does not change even if the pH changes (Comparative Synthesis Examples 1-2).

<Example of preparation of pigment dispersion>
(Preparation Example 1) Black dispersion / carbon black pigment (carbon black of Preparation Example 1) 15 parts by weight Dispersant (Naphthalene sodium sulfonate formalin condensate) 3 parts by weight (A-45-PN, manufactured by Takemoto Yushi Co., Ltd.)
・ 82 parts by weight of pure water

  After premixing the mixture of carbon black pigment, dispersant and pure water, a disk-type bead mill (Shinmaru Enterprises KDL type, media: using zirconia balls with a diameter of 0.1 mm) at a peripheral speed of 10 m / s. A black pigment dispersion was obtained by circulating and dispersing for a minute.

<Method for Producing Ink of Example 1>
An ink was prepared using the pigment dispersion of the preparation example and the polymer fine particles of the synthesis example, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 1.2 μm to obtain an ink.
The structures of the ink compositions of Examples 1 to 9 and Comparative Examples 1 to 3 are shown in Table 2 below.
In addition, the numerical value of 2 in a table | surface shows weight%.

Here, abbreviations in Table 3 have the following meanings.
Acrylic-silicone resin emulsion: Showa Polymer Co., Ltd., Polysol ROY6312, solid content 37.2% by mass, average particle diameter 171 nm, minimum film-forming temperature (MFT) = 20 ° C.
-Polyurethane emulsion: manufactured by DIC, Hydran APX-101H, solid content 45% by mass, average particle diameter 160 nm, minimum film-forming temperature (MFT) = 20 ° C.
KF-643: polyether-modified silicone compound (manufactured by Shin-Etsu Chemical Co., Ltd., component 100% by mass)
・ Proxel GXL: Antifungal agent mainly composed of 1,2-benzisothiazolin-3-one (manufactured by Avicia, 20% by mass, containing dipropylene glycol)

  Next, each ink-jet ink of Examples 1 to 9 and Comparative Examples 1 to 3 was evaluated by the following evaluation method. The results are shown in Table 3.

<Image density>
In a 23 ° C. and 50% RH environment, an ink jet printer (IPSiO GX5000 manufactured by Ricoh) was filled with ink prepared, and a chart with a 64 point character “■” created by Microsoft Word 2000 (manufactured by Microsoft Corporation) was written on MyPaper (stock) (Ricoh Co., Ltd.), the “■” portion of the printed surface was measured with X-Rite 938, and judged according to the following evaluation criteria.
The printing mode used was a driver attached to the printer, in which the "plain paper-standard fast" mode was changed to "no color correction" from the user setting for plain paper.

[Evaluation criteria]
A: 1.30 or more A: 1.25 or more but less than 1.30 B: 1.20 or more but less than 1.25 Δ: 1.10 or more but less than 1.20 ×: less than 1.1

<Ink storage stability>
Each ink was filled in an ink cartridge and stored at 60 ° C. for 2 weeks, and the change in viscosity after storage relative to the viscosity before storage was evaluated according to the following criteria.

[Evaluation criteria]
◎: Change in viscosity within ± 8% ○: Change in viscosity within ± 10% △: Change in viscosity within ± 30% ×: Change in viscosity exceeds 30%

<Ink ejection stability>
In an environment of 28 ° C. and 15% RH, an ink jet printer (Ricoh's IPSiO GX5000) was filled with ink, and MyPaper (manufactured by Ricoh Co., Ltd.) was able to print 5 sets of 1 set of 200 sheets at a resolution of 600 dpi. went.
Discharge turbulence and non-discharge conditions at this time were evaluated according to the following criteria.
In addition, the printing pattern was printed with 100% duty for each ink in a chart in which each color printing area was 5% in the total area of the paper surface created by Microsoft Word 2000 (manufactured by Microsoft).
The printing conditions were a recording density of 300 dpi and one-pass printing.

[Evaluation criteria]
○: Discharge turbulence and non-ejection are not observed Δ: Slight non-ejection and ejection turbulence are observed ×: Remarkable non-ejection and ejection turbulence are observed

<Nozzle resistance>
Place an inkjet printer (Ricoh's IPSiO GX5000) in a constant temperature and humidity chamber, set the environment in the bath to a temperature of 32 ° C and a humidity of 30%, and print 20 sheets of the following print pattern charts continuously, then print for 20 minutes. The operation was suspended, and this operation was repeated 50 times. After a total of 1,000 copies were printed, the nozzle plate was observed with a microscope to determine whether ink had adhered.
In addition, the printing pattern was printed with 100% duty for each ink in a chart in which each color printing area was 5% in the total area of the paper surface created by Microsoft Word 2000 (manufactured by Microsoft).
The printing conditions were a recording density of 300 dpi and one-pass printing.

[Evaluation criteria]
○: Adherence is not observed near the nozzle. Δ: Adherence is observed near the nozzle. ×: Remarkable adhesion is observed on the entire surface of the nozzle plate.

  The effects of the polymer fine particles used in the ink for ink jet recording according to the present invention are clearly superior in image density, ink storage stability, ink ejection stability, and comparison between Examples 1 to 9 and Comparative Examples 1 to 3. It can be seen that the adhesion to the nozzle is equivalent or better.

<< Examples 11 to 16, Comparative Examples 11 to 13 >>
Next, Examples 11 to 16 and Comparative Examples 11 to 13 will be described. In addition, about the part which overlaps with Examples 1-9 and Comparative Examples 1-3, since it is the same content, description is abbreviate | omitted.

(Synthesis Example 11) Synthesis of Polymer Fine Particle L Next, N-vinylformamide (NVF) in which a vinylbenzyl group was introduced at the above end in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas introduction tube and a thermometer. ) 158.4 g of polymer (formula 3) solution [0.60 mol as NVF repeating unit (determined from the previous charge)], dimethylaminoethyl methacrylate (DMAEMA) (formula 2) 94.3 g (0.60 mol), 62.5 g (0.60 mol) of styrene (St) (formula B) and 603.7 g of water were charged, the pH was adjusted with hydrochloric acid, and the temperature was raised to 60 ° C. Under a nitrogen stream, 81.1 g (0.015 mol) of a 5% by weight aqueous solution of potassium persulfate was added and copolymerized for 6 hours to obtain a milky white dispersion (solid content concentration 22.4%). The pH-responsive polymer fine particles thus obtained had an average particle size at pH 5 of 580 nm.

(Synthesis Example 12) Synthesis of Polymer Fine Particle M In the synthesis of polymer fine particle L of Synthesis Example 11 above, 158.4 g of N-vinylformamide (NVF) polymer (formula 3) solution into which a vinylbenzyl group was introduced at the terminal. 118.8 g [0.45 mol as NVF repeating unit (determined from the previous charge)], dimethylaminoethyl methacrylate (DMAEMA) (formula 2) 94.3 g (0.60 mol) 139.8 g (0.89 The reaction was conducted in the same manner as in Synthesis Example 11 except that 62.5 g (0.60 mol) of styrene (St) (formula B) was changed to 46.9 g (0.45 mol) and water of 613.4 g. Dispersion (solid content concentration 23.0%) was obtained.

(Synthesis Example 13) Synthesis of Polymer Fine Particle N In the synthesis of polymer fine particle L of Synthesis Example 11, 94.3 g (0.60 mol) of dimethylaminoethyl methacrylate (DMAEMA) (Formula 2) was converted to diethylaminoethyl methacrylate (DMAEMA). ) A reaction was carried out in the same manner as in Synthesis Example 11 except that the amount was 111.4 g (0.60 mol) to obtain a milky white dispersion (solid content concentration 23.0%).

(Synthesis Example 14) Synthesis of Polymer Fine Particle O In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas introduction tube, and a thermometer, a PEG macromonomer (methoxypolyethylene glycol methacrylate: Blemmer PME-1000) (formula 4 ) 55.0 g [1.14 mol as ethylene glycol repeating unit], DMAEMA 90.0 g (0.57 mol), styrene 59.6 g (0.57 mol), ethanol 100.0 g, water 618.9 g, and hydrochloric acid After adjusting the pH, the temperature was raised to 60 ° C. Under a nitrogen stream, 81.1 g (0.015 mol) of a 5% by weight aqueous solution of potassium persulfate was added and copolymerized for 6 hours to obtain a milky white dispersion (solid content concentration 22.0%). (The average particle diameter of the pH-responsive polymer particles thus obtained at pH 5 was 1080 nm.)

(Synthesis Example 15) Synthesis of Polymer Fine Particle P In the synthesis of polymer fine particle O of Synthesis Example 14 above, 55.0 g of PEG macromonomer (methoxypolyethylene glycol methacrylate: Blemmer PME-1000) (Formula 4) [as ethylene glycol repeating unit] 1.14 mol] was reacted in the same manner as in Synthesis Example 14 except that 61.1 g of PEG macromonomer (methoxypolyethylene glycol acrylate: Blemmer AME-400) [1.14 mol as an ethylene glycol repeating unit] Dispersion (solid content concentration 22.0%) was obtained.

(Synthesis Example 16) Synthesis of Polymer Fine Particle Q In the synthesis of polymer fine particle O of Synthesis Example 14 above, 55.0 g of PEG macromonomer (methoxypolyethyleneglycol methacrylate: Blenmer PME-1000) (Formula 4) [as ethylene glycol repeating unit 1.14 mol] was reacted in the same manner as in Synthesis Example 14 except that PEG macromonomer (polyethylene glycol monoacrylate: BLEMMER AE-400) was changed to 58.3 g [1.14 mol as an ethylene glycol repeating unit]. A milky white dispersion (solid content concentration 22.0%) was obtained.

(Comparative Synthesis Example 11)
In the synthesis of the polymer fine particle L of Synthesis Example 11, 158.4 g [NVF repeating unit 0 as NVF] polymer (formula 3) solution in which a vinylbenzyl group was introduced at the terminal of the constituent monomer was used. .60 mol (determined from the previous charge)] and 62.5 g (0.60 mol) of styrene (formula B), the reaction was carried out in the same manner as in Synthesis Example 11, and a milky white dispersion (solid content concentration 23. 8%).

(Comparative Synthesis Example 12)
Synthesis of Polymer Fine Particle Dispersion with PEG Chains Accumulated on the Surface In the synthesis of polymer fine particle O in Synthesis Example 14, the constituent monomer was 65.1 g of PEG macromonomer (Blemmer PME-1000) (formula 4) [ethylene glycol repeating 1.35 mol as a unit], 140.6 g (1.35 mol) of styrene (formula B), 100.0 g of ethanol, 618.9 g of water, and the reaction was carried out in the same manner as in Synthesis Example 14 to obtain a milky white dispersion (solid Partial concentration 21.6%). (The average particle size of the polymer fine particles thus obtained at pH 5 was 160 nm.)
(Comparative Synthesis Example 13)
Gel fine particles described in Example 1 of Japanese Patent No. 3155318 were used.

  The structural units and molar ratios of Synthesis Examples 11 to 16 and Comparative Synthesis Examples 11 to 13 thus obtained are shown in Table 4, and the relationship between the pH of the pH-responsive polymer fine particles and the average particle diameter is shown in FIG.

  From this result, the average particle diameter of the pH-responsive polymer particles used in the present invention increases as the pH decreases. It can be seen that the particle size when the pH is high is small compared to the prior art (Comparative Synthesis Example 13), the pH at which the particle size increases is high, and the saturated particle size is also large. It can also be seen that when the pH-sensitive monomer (formula 2), which is a constituent material necessary for the present invention, is lacking, the particle diameter does not change even if the pH changes (Comparative Synthesis Examples 11 to 12).

<Example of preparation of pigment dispersion>
(Adjustment Example 11) Black dispersion / carbon black pigment (carbon black of Preparation Example 1) 15 parts by weight Dispersant (Naphthalenesulfonate sodium formalin condensate) 3 parts by weight (A-45-PN, manufactured by Takemoto Yushi Co., Ltd.)
・ 82 parts by weight of pure water

  After premixing the mixture of carbon black pigment, dispersant and pure water, a disk-type bead mill (Shinmaru Enterprises KDL type, media: using zirconia balls with a diameter of 0.1 mm) at a peripheral speed of 10 m / s. A black pigment dispersion was obtained by circulating and dispersing for a minute.

<Method for Producing Ink of Example 11>
An ink was prepared using the pigment dispersion of the preparation example and the polymer fine particles of the synthesis example, stirred for 1 hour and 30 minutes, and then filtered through a membrane filter having a pore size of 1.2 μm to obtain an ink.
The structures of the ink compositions of Examples 11 to 16 and Comparative Examples 11 to 13 are shown in Table 5 below.
In addition, the numerical value in Table 5 shows weight%.

Here, abbreviations in Table 5 have the following meanings.
Acrylic-silicone resin emulsion: Showa Polymer Co., Ltd., Polysol ROY6312, solid content 37.2% by mass, average particle diameter 171 nm, minimum film-forming temperature (MFT) = 20 ° C.
-Polyurethane emulsion: manufactured by DIC, Hydran APX-101H, solid content 45% by mass, average particle diameter 160 nm, minimum film-forming temperature (MFT) = 20 ° C.
KF-643: polyether-modified silicone compound (manufactured by Shin-Etsu Chemical Co., Ltd., component 100% by mass)
・ Proxel GXL: Antifungal agent mainly composed of 1,2-benzisothiazolin-3-one (manufactured by Avicia, 20% by mass, containing dipropylene glycol)

Next, the ink jet inks of Examples 11 to 16 and Comparative Examples 11 to 13 were evaluated using the same evaluation method as in Examples 1 to 9 and Comparative Examples 1 to 3 described above and the same evaluation criteria except the following points. did. The results are shown in Table 6.
[Image Evaluation Criteria]
◎: 1.25 or more ○: 1.20 or more and less than 1.25 Δ: 1.10 or more and less than 1.20 ×: less than 1.1

  The effects of the polymer fine particles used in the ink for ink jet recording according to the present invention are clearly superior in image density, ink storage stability, and ink ejection stability by comparing Examples 11 to 16 and Comparative Examples 11 to 13. In addition, it can be seen that the adhesiveness to the nozzle is equivalent or better.

101 apparatus main body 102 paper feed tray 103 paper discharge tray 104 ink cartridge loading unit 111 upper cover 112 front surface 115 front cover 131 guide rod 132 stay 133 carriage 134 recording head 135 sub tank 141 paper placement unit 142 paper 144 separation pad 151 transport belt 152 Counter roller 156 Charging roller 157 Transport roller 158 Depression roller 171 Separation claw 172 Paper discharge roller 173 Paper discharge roller 181 Double-sided paper feed unit 201 Ink cartridge 241 Ink bag 242 Ink inlet 243 Ink outlet 244 Cartridge exterior

JP 2006-16412 A Japanese Patent No. 3155318 JP 2011-026553 A JP 2001-187851 A

Claims (7)

An ink for ink jet recording which contains water, a wetting agent, a colorant and polymer fine particles, and is ejected onto plain paper having a pH of 4 to 7 on the paper surface,
The pH of the ink for ink jet recording is 8 to 10,
The polymer fine particle includes at least a structural unit represented by the following formula A or the following formula B, a structural unit represented by the following formula 2, and a structural unit represented by the following formula 3 or the following formula 4. It is polymerized and does not include the colorant,
The volume average particle diameter of the polymer fine particles is an ink for ink jet recording, wherein the pH of the ink for ink jet recording is 8.5 or more and 10 to 300 nm .

[In Formula A, R ₁ represents an alkyl group having 1 to 4 carbon atoms, and R ₂ represents H or a lower alkyl group having 1 or 2 carbon atoms. ]

[In Formula 2, R ₃ is the same and represents a lower alkyl group having 1 or 2 carbon atoms. ]

[In the said Formula 3, l represents the integer of 1-300. ]

[In the above formula 4, R ₄ and R ₅ represent H or a lower alkyl group having 1 or 2 carbon atoms, and m represents an integer of 1 to 90. ] The ink for inkjet recording according to claim 1, wherein m in Formula 4 is 9 to 23. An ink for ink jet recording which contains water, a wetting agent, a colorant and polymer fine particles, and is ejected onto plain paper having a pH of 4 to 7 on the paper surface,
The pH of the ink for ink jet recording is 8 to 10,
The polymer fine particle includes at least a structural unit represented by the following formula A1 or the following formula B1, a structural unit represented by the following formula 12, and a structural unit represented by the following formula 13 or the following formula 14. It is polymerized and does not include the colorant,
The volume average particle diameter of the polymer fine particles is an ink for ink jet recording, wherein the pH of the ink for ink jet recording is 8.5 or more and 10 to 300 nm .

[In Formula A, R ₁₁ represents an alkyl group having 1 to 4 carbon atoms, and R ₁₂ represents H or a lower alkyl group having 1 or 2 carbon atoms. ]

[In Formula 12, R ₁₃ is the same and represents a lower alkyl group having 1 or 2 carbon atoms. ]

[In said Formula 13, n represents the integer of 1-300. ]

[In the above formula 14, R ₁₄ and R ₁₅ represent H or a lower alkyl group having 1 or 2 carbon atoms, and o represents an integer of 1 to 90. ] Ink cartridge characterized by comprising accommodating the ink jet recording ink according to the vessel to any one of claims 1 to 3. An ink jet recording method comprising at least an ink flying step of recording an image by applying a stimulus to the ink for ink jet recording according to claim 1 and causing the ink for ink jet recording to fly. An ink jet recording apparatus comprising at least ink jetting means for recording an image by applying a stimulus to the ink for ink jet recording according to claim 1 and causing the ink jet recording ink to fly. An ink recorded matter comprising an image recorded with the ink for ink jet recording according to any one of claims 1 to 3 on a recording medium.

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