JP2014173081A - Ink for inkjet recording, ink container, inkjet recording apparatus, method of producing recorded products, and recorded products - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink for inkjet recording that exhibits high image density and excellent storage stability.SOLUTION: An ink contains a polymer including structures of the specified general formulas (1) and (2). [In the general formula (1), R1 represents a hydrogen atom or a methyl group, and Mrepresents at least one selected from an alkali metal ion, an organic amine ion, and a hydrogen ion. In the general formula (2), R2 represents a methyl group or a hydrogen atom.]

Description

  The present invention relates to an ink for ink jet recording (hereinafter sometimes simply referred to as “ink”), an ink container, an ink jet recording apparatus, a method for producing a recorded matter, and a recorded matter.

  The inkjet recording method is popular because it has the advantage that the process is simpler than other recording methods, full color is easy, and even high-resolution images can be obtained even with a simple configuration. Have been doing. In this ink jet recording method, a small amount of ink is ejected by pressure generated using bubbles generated by heat, piezo or electrostatic, 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 such an ink jet recording system, 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. For this reason, research on pigment inks that use water-insoluble pigments instead of water-soluble dyes is underway. 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 of OA printers, high image density is required even when plain paper is used as a recording medium in pigment ink. However, when the plain ink is used as the recording medium, the pigment ink has a problem that the pigment density on the paper surface is lowered by permeating into the paper and the image density is lowered.

  In recent years, the demand for industrial applications has increased, and high-speed printing is desired. An ink jet printer equipped with a line head has been proposed along with such high-speed printing. In order to achieve high-speed printing, in order to increase the drying speed of the ink adhering to the recording medium, means for increasing the drying speed by adding a penetrant to the ink and allowing water to penetrate into the recording medium has been tried. In addition to this, there is a problem that the permeability of the pigment into the recording medium is increased and the image density is lowered.

  In addition, when plain paper is used as a recording medium, there is a problem that immediately after printing, the surface of the plain paper is swollen by water as an ink solvent, the difference in elongation between the front and back is increased, and curling occurs. Since such a phenomenon disappears as drying progresses, it has not been a problem in low-speed printing. However, with the increase in printing speed, it is necessary to transport the recording medium without eliminating curling after printing, which may cause a paper jam problem. As for curling, a means for increasing the content of the organic solvent in the ink is effective, but since the ink is more hydrophobic, it is difficult to ensure the storage stability of the ink.

In order to solve the above problems, for example, an ink-jet ink composition containing a liquid vehicle, a colorant, and a polymer having at least one functional group having a specific calcium index value has been proposed (see Patent Document 1). In this proposal, 4-methacrylamide-1-hydroxybutane-1,1-diphosphonic acid is shown as a monomer constituting the polymer, and when the colorant comes into contact with the paper, the diphosphonic acid group of the polymer and the paper It is said that the printed image can be improved by making it unstable with the Ca salt therein.
However, in the proposed technique, the polymer is not used as a dispersant and an additive for a pigment dispersion, but the polymer is coated with a colorant, and the functional group of the polymer includes a diphosphonic acid group and a hydroxyl group. Are adjacent to each other, and hydrogen bonds between the diphosphonic acid group and the hydroxyl group are likely to occur, or the dispersion stability of the ink is low and the image density on plain paper cannot be obtained sufficiently.

  In addition, an ink jet recording method has been proposed in which a receiving liquid containing a Ca salt is attached to paper, and an ink containing a pigment having a phosphorus-containing group bonded thereto, a resin emulsion, and a surfactant is printed (see Patent Document 2). This proposal describes that bisphosphonic acid is preferable as the phosphorus-containing group, and describes that the Ca salt of the receiving solution reacts with the phosphorus-containing group and has an effect of improving feathering and fixing properties. Yes. However, in the proposed technique, a phosphonic acid group-containing polymer is not used as a dispersant and an additive for a pigment dispersion, but a pigment bonded with phosphoric acid is used, and an image when recorded on plain paper is used. The effect of increasing the concentration is not sufficient.

  Further, an aqueous ink containing a colorant, water, a water-soluble organic solvent, a surfactant, and a chelating agent has been proposed (see Patent Document 3). In this proposal, hydroxyethylidene diphosphonic acid or a salt thereof, which is a low molecular compound, is used as the chelating agent. The chelating agent is said to be able to remove calcium and the like contained in a dispersion such as a pigment and improve discharge stability and storage stability. However, the proposal only describes a low molecular weight compound, hydroxyethylidene diphosphonic acid, and does not describe a polymer containing phosphonic acid, and improves the image density when recorded on a chelating agent and plain paper. It also does not describe the relationship with effects.

  Therefore, it is desired to provide an ink for ink jet recording which can obtain a high image density even when recorded on plain paper and has excellent storage stability even when the content of the water-soluble organic solvent is increased.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide an ink for ink jet recording which can obtain a high image density even when recorded on plain paper and has excellent storage stability even when the content of a water-soluble organic solvent is increased. .

［一般式（１）中、Ｒ1は、水素原子、及びメチル基のいずれかを表す。Ｍ⁺は、アルカリ金属イオン、有機アミンイオン、及び水素イオンから選択される少なくとも１種を表す。］

［一般式（２）中Ｒ2はメチル基または水素原子を表す。］ The ink for inkjet recording of the present invention as a means for solving the above problems is represented by water, a water-soluble organic solvent, a pigment, a structural unit represented by the following general formula (1), and a general formula (2). And a polymer containing a structural unit.

[In General Formula (1), R1 represents either a hydrogen atom or a methyl group. M ⁺ represents at least one selected from alkali metal ions, organic amine ions, and hydrogen ions. ]

[R2 in the general formula (2) represents a methyl group or a hydrogen atom. ]

  According to the present invention, the conventional problems can be solved, the object can be achieved, a high image density can be obtained even when recorded on plain paper, and storage can be performed even when the content of the water-soluble organic solvent is increased. An ink for inkjet recording excellent in stability can be provided.

FIG. 1 is a schematic diagram illustrating an example of an ink cartridge. FIG. 2 is a schematic view including the case of the ink cartridge of FIG. FIG. 3 is a perspective view showing an example of an ink jet recording apparatus. FIG. 4 is a diagram illustrating an example of an ink jet recording apparatus. FIG. 5 is a schematic enlarged view showing an example of an ink jet head of the ink jet recording apparatus.

［一般式（１）中、Ｒ1は、水素原子、及びメチル基のいずれかを表す。Ｍ⁺は、アルカリ金属イオン、有機アミンイオン、及び水素イオンから選択される少なくとも１種を表す。］

［一般式（２）中Ｒ2はメチル基または水素原子を表す。］ (polymer)
The polymer of the present invention includes a structural unit represented by the following general formula (1) and a structural unit represented by the general formula (2), and further includes other structural units as necessary.

[In General Formula (1), R1 represents either a hydrogen atom or a methyl group. M ⁺ represents at least one selected from alkali metal ions, organic amine ions, and hydrogen ions. ]

[R2 in the general formula (2) represents a methyl group or a hydrogen atom. ]

Examples of the alkali metal in the M ⁺ alkali metal ion in the general formula (1) include lithium, sodium, and potassium.
Examples of the organic amine in the M ⁺ organic amine ion include alkylamines such as mono-, di- or trimethylamine, mono-, di- or triethylamine; ethanolamine, diethanolamine, triethanolamine, methylethanolamine, methyldiethanolamine, dimethylethanol Alcohol amines such as amine, monopropanolamine, dipropanolamine, tripropanolamine, isopropanolamine, trishydroxymethylaminomethane, 2-amino-2-ethyl-1,3propanediol (AEPD); choline, morpholine, N -Cyclic amines such as methylmonoformin, N-methyl-2-pyrrolidone and 2-pyrrolidone.
In particular, potassium ion is desirable from the viewpoints of both image density and storage stability.
As M ⁺ , more than half or all of them are preferably alkali metal ions or organic amine ions, and the rest are preferably hydrogen ions (protons).

［一般式（５）中、Ｍ⁺は、アルカリ金属イオン、有機アミンイオン、及び水素イオンから選択される少なくとも１種を表す。］

The structural unit represented by the general formula (1) of the polymer is preferably a structural unit represented by the following general formula (5). Moreover, as a structural unit represented by General formula (2), the structural unit represented by following Structural formula (6) is preferable. By including the structural units represented by the general formula (5) and the structural formula (6), the image density and the storage stability of the pigment dispersion are further improved.

[In General Formula (5), M ⁺ represents at least one selected from alkali metal ions, organic amine ions, and hydrogen ions. ]

In addition to the structural units represented by the general formulas (1) and (2), the polymer preferably further includes a structural unit derived from a polymerizable monomer.
There is no restriction | limiting in particular as said polymerizable monomer, According to the objective, it can select suitably, For example, a polymerizable hydrophobic monomer, a polymerizable hydrophilic monomer, etc. are mentioned.

  The polymerizable hydrophobic monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aromatics such as styrene, α-methylstyrene, 4-t-butylstyrene, and 4-chloromethylstyrene. Unsaturated ethylene monomer having an aromatic ring; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, dimethyl maleate, dimethyl itaconate, dimethyl fumarate, lauryl (meth) acrylate (C12), tridecyl (meth) acrylate (C13), tetradecyl (meth) acrylate (C14), pentadecyl (meth) acrylate (C15), hexadecyl (meth) acrylate (C16), heptadecyl (meth) acrylate (C17), nonadecyl (meth) acrylate (C19), (meth) acrylic acid ray Alkyl (meth) acrylates such as syl (C20), heicosyl (meth) acrylate (C21), docosyl (meth) acrylate (C22); 1-heptene, 3,3-dimethyl-1-pentene, 4,4 -Dimethyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 1-octene, 3,3-dimethyl-1-hexene, 3,4-dimethyl -1-hexene, 4,4-dimethyl-1-hexene, 1-nonene, 3,5,5-trimethyl-1-hexene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene , 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene, 1-docose, etc. Monomer, and the like. These may be used individually by 1 type and may use 2 or more types together.

  The polymerizable hydrophilic monomer is not particularly limited and may be appropriately selected depending on the purpose. For example, (meth) acrylic acid or a salt thereof, maleic acid or a salt thereof, monomethyl maleate, itaconic acid, Anionic unsaturated ethylene monomers such as monomethyl itaconic acid, fumaric acid, 4-styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid; (meth) acrylic acid-2-hydroxyethyl, diethylene glycol mono (meth) acrylate, Triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) acrylamide, N-methylol (meth) acrylamide, N-vinylformamide, N-vinylacetamide N- vinylpyrrolidone, acrylamide, N, N- dimethylacrylamide, N-t-butylacrylamide, N- octyl acrylamide, nonionic ethylenically unsaturated monomers such as N-t-octyl acrylamide, and the like. These may be used individually by 1 type and may use 2 or more types together.

The mass ratio of the structural unit represented by the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5% by mass to 80% by mass with respect to the total amount of the polymer. 10 mass%-60 mass% is still more preferable. When the mass ratio is within the more preferable range, it is advantageous in that when used for an ink jet recording ink, a high image density is obtained, and dispersion stability and storage stability are improved.
Further, the mass ratio of the structural unit represented by the general formula (2) in the polymer is not particularly limited as long as it is set in the remaining ratio after the ratio of the general formula (1) is set, depending on the purpose. Can be selected as appropriate. 20 mass%-95 mass% are preferable with respect to the said polymer whole quantity especially, and 40 mass%-70 mass% are still more preferable. When the mass ratio is in the preferred range, it is advantageous in that when used for an ink jet recording ink, a high image density is obtained, and dispersion stability and storage stability are good.

  The polymer containing the structural unit represented by the general formula (1) and the general formula (2) can be produced by the polymer production method of the present invention described below. The polymer containing the structural units represented by the general formula (1) and the general formula (2) is not particularly limited and can be widely used in various fields. It can be suitably used as a concentration improver, a binder resin for pigment, a viscosity modifier, and the like.

<Method for producing polymer>
In the method for producing a polymer used in the present invention, at least a compound represented by the following general formula (3) and general formula (4) is polymerized, and then the obtained polymer is either an alkali metal base or an organic amine base. And a step of neutralizing with, and further including other steps as necessary.

［一般式（３）中、Ｒ3はメチル基または水素原子を表す。］

［一般式（４）中Ｒ4はメチル基または水素原子を表す。］ The polymer containing the structural unit represented by the general formula (1) is obtained by polymerizing the compounds represented by the following general formula (3) and the general formula (4), or the following general formula (3) and the general formula After the compound represented by (4) and the polymerizable monomer are copolymerized, they can be synthesized by neutralizing with either an alkali metal base or an organic amine base.

[In general formula (3), R3 represents a methyl group or a hydrogen atom. ]

[In the general formula (4), R4 represents a methyl group or a hydrogen atom. ]

Examples of the compound represented by the general formula (3) include 1-methacryloxyethane-1,1-diphosphonic acid represented by the following structural formula (7) in which R 3 is a methyl group, and R 3 is a hydrogen atom. There may be mentioned 1-acryloxyethane-1,1-diphosphonic acid represented by the following structural formula (8). These compounds can be synthesized, for example, by the method described in JP-A-58-2222095.

Examples of the compound represented by the general formula (4) include diacetone acrylamide represented by the following structural formula (9) in which R 4 is a hydrogen atom, and the following structural formula (10) in which R 4 is a methyl group. And diacetone methacrylamide.

As a method for synthesizing the polymer containing the structural units represented by the general formula (1) and the general formula (2), a method using a radical polymerization initiator is preferable because the polymerization operation and the adjustment of the molecular weight are easy. A solution polymerization method in which polymerization is performed in a solvent is more preferable.
The solvent for performing radical polymerization by the solution polymerization method is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ketone solvents such as methanol, ethanol, acetone, methyl ethyl ketone, and methyl isobutyl ketone; Examples thereof include acetate solvents such as ethyl acetate and butyl acetate; aromatic hydrocarbon solvents such as benzene, toluene and xylene; isopropanol, ethanol, cyclohexane, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoamide and the like. Among these, ketone solvents, acetate solvents, and alcohol solvents are preferable.

The radical polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. For example, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxyester Cyano azobisisobutyronitrile, azobis (2-methylbutyronitrile), azobis (2,2′-isovaleronitrile), non-cyano dimethyl-2,2′-azobisisobutyrate, Etc. Among these, organic peroxides and azo compounds are preferable, and azo compounds are particularly preferable from the viewpoint of easy control of molecular weight and low decomposition temperature.
The content of the polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1% by mass to 10% by mass with respect to the total mass of the polymerizable monomer.

In order to adjust the molecular weight of the polymer, an appropriate amount of a chain transfer agent may be added.
Examples of the chain transfer agent include mercaptoacetic acid, mercaptopropionic acid, 2-propanethiol, 2-mercaptoethanol, thiophenol, dodecyl mercaptan, 1-dodecanethiol, thioglycerol, and the like.
There is no restriction | limiting in particular in superposition | polymerization temperature, Although it can select suitably according to the objective, 50 to 150 degreeC is preferable and 60 to 100 degreeC is more preferable. The polymerization time is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 hours to 48 hours.

The obtained polymer is neutralized with either an alkali metal base or an organic amine base.
The neutralization treatment can be performed by neutralizing some or all of the phosphonic acid groups of the polymer with an alkali metal base or an organic amine base.
The neutralization treatment of the alkali metal base or organic amine base can also be performed in a state where the pigment and the polymer are mixed in the ink production process.

  More specifically, the polymer containing the structural units represented by the general formula (1) and the general formula (2) includes a solvent, the general formula in a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube. After reacting the compound represented by (3) and general formula (4), and if necessary, a polymerizable monomer in the presence of a polymerization initiator at a temperature of 60 ° C. to 150 ° C. under reflux of nitrogen gas, an alkali metal It can be synthesized by neutralizing with either a base or an organic amine base.

In the present invention, the neutralization rate of the phosphonic acid group in the polymer obtained by the neutralization treatment is defined as the neutralization rate as determined by the following method. This is different from the ratio in which protons are substituted with metal ions or organic amine ions.
When the compound represented by the general formula (3) is monomer 1,
Neutralization rate X (%) = (number of moles of base added x valence of base cation)
÷ (number of moles of monomer 1 contained in polymer × 4) × 100
Number of moles of base added = amount of base added Yg ÷ molecular weight of base Number of moles of monomer 1 contained in polymer
= Charge amount of monomer 1 Zg / Molecular weight of monomer 1 Therefore, the amount of base necessary to obtain the neutralization rate X% is: Base addition amount Yg = Neutralization rate X (%) x (Feed amount of monomer 1 Zg × 4)
X base molecular weight / (base cation valence x 100 x monomer 1 molecular weight)
It becomes.

The weight average molecular weight of the polymer containing the structural units represented by the general formula (1) and the general formula (2) is not particularly limited and may be appropriately selected depending on the intended purpose. 000 is preferable, 5,000 to 50,000 is more preferable, and 6,000 to 30,000 is still more preferable.
The weight average molecular weight can be measured, for example, by gel permeation chromatography (GPC).

The weight average molecular weight of the polymer containing the structural units represented by the general formulas (1) and (2) can be controlled to some extent by the polymerization temperature, the polymerization initiator amount, and the monomer concentration during the reaction.
Regarding the polymerization temperature, a low molecular weight polymer tends to be obtained when polymerized in a short time at a high temperature, and a high molecular weight polymer tends to be easily obtained when polymerized over a long time at a low temperature.
As for the content of the polymerization initiator, a larger amount tends to obtain a low molecular weight polymer, and a smaller amount tends to obtain a high molecular weight polymer.
As for the monomer concentration during the reaction, a high concentration tends to provide a low molecular weight polymer, and a low concentration tends to provide a high molecular weight polymer.

(Inkjet recording ink)
The ink for inkjet recording of the present invention contains water, a water-soluble organic solvent, and a polymer containing the structural unit represented by the general formula (1) and the general formula (2) of the present invention, and further if necessary. It contains other components.

<Polymer including structural units represented by general formula (1) and general formula (2)>
The ink for inkjet recording of the present invention contains a polymer containing the structural unit represented by the general formula (1) and the general formula (2).
The polymer containing the structural units represented by the general formula (1) and the general formula (2) has a dibasic acid structure in which phosphonic acid groups are adjacent to each other. It has many diphosphonic acid groups. As a result, the polymer containing the structural unit represented by the general formula (1) and the general formula (2) can add more hydrophilic groups in the polymer molecule than the monobasic acid, and has good hydrophilicity. Indicates. Moreover, since it has a phosphonic acid group that easily reacts with Ca ions, and the phosphonic acid group is a dibasic acid, it has the effect of chelating Ca ions, and shows stronger bonds when contacted with Ca ions. Can be hydrophobized.
Although the structural unit represented by the general formula (2) brings hydrophilicity to the polymer and the reason is not clear, it has a function of preventing the association of phosphonic acid groups in the polymer, and storage stability in water-based inks. Is further improved.
The reason for this is not clear, but by having the structural unit represented by the general formula (2), the adsorptivity to the polymer pigment containing the structural unit represented by the general formula (1) and the general formula (2) is high It seems to improve. As a secondary effect, it can be used as a dispersant.

  Therefore, when the polymer containing the structural unit represented by the general formula (1) and the general formula (2) is used for the ink for ink jet recording, only good dispersion stability and storage stability of the ink are exhibited. However, when ink is printed on paper, the structural unit represented by the general formula (1) is hydrophobized by Ca ions eluted from the paper into the ink even if the plain paper has a small Ca ion content. Furthermore, since the structural unit represented by the general formula (2) has a high adsorptivity to the pigment, the pigment stays on the paper surface by aggregating and aggregating the pigment, and it is possible to realize a higher image density. Become.

  The content of the polymer containing the structural units represented by the general formula (1) and the general formula (2) in the ink for inkjet recording is not particularly limited and may be appropriately selected depending on the intended purpose. In terms of minutes, 0.05 mass% to 10 mass% is preferable, 0.5 mass% to 5 mass% is more preferable, and 1 mass% to 3 mass% is particularly preferable. When the content is 0.05% by mass or more, an effect of improving the image density is recognized, and when the content is 10% by mass or less, it is possible to make the viscosity range suitable for ejecting ink from the head.

If the polymer containing the structural units represented by the general formula (1) and the general formula (2) is used as a pigment dispersant, the ink has a higher image density on a plain paper and a higher content of a water-soluble organic solvent. Further improvement in storage stability is observed.
When used as the pigment dispersant, it is preferable to include a structural unit derived from a hydrophobic polymerizable monomer in addition to the structural units represented by the general formulas (1) and (2). As the hydrophobic polymerizable monomer, those described above can be used.
The content of the polymer containing the structural units represented by the general formula (1) and the general formula (2) is not particularly limited when used as a pigment dispersant, and can be appropriately selected according to the purpose. However, 1-100 mass parts is preferable with respect to 100 mass parts of said pigments, 5-80 mass parts is more preferable, 10-50 mass parts is still more preferable. When the content is within the more preferable range, it is advantageous in that a high image density is obtained and dispersion stability and storage stability are improved.

<Water>
As said water, pure water, such as ion-exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water can be used, for example.
There is no restriction | limiting in particular in content in the said ink for inkjet recording of the said water, According to the objective, it can select suitably.

<Pigment>
There is no restriction | limiting in particular as said pigment, According to the objective, it can select suitably, For example, the inorganic pigment, organic pigment, etc. for black or color are mentioned. These may be used alone or in combination of two or more.
Examples of the inorganic pigment include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow, as well as a known method such as a contact method, a furnace method, and a thermal method. Carbon black can be used.

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. Is mentioned.
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, the BET specific surface area of ^{50m 2 / g~300m 2 / g,} DBP oil absorption amount 40 mL / 100 g Those having ~ 150 mL / 100 g, volatile content of 0.5% to 10%, and pH 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.

  There is no restriction | limiting in particular as a pigment which can be used for a magenta ink, According to the objective, it can select suitably, For example, C.I. 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 intended 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 used in the present invention may be newly produced for the present invention.
In addition, C.I. I. Pigment Yellow 74, C.I. I. Pigment red 122, C.I. I. Pigment Bio Red 19 and C.I. I. By using CI Pigment Blue 15: 3, a well-balanced ink having excellent color tone and light resistance can be obtained.

The volume average particle diameter (D50) of the pigment is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 150 nm or less, and more preferably 100 nm or less. When the volume average particle diameter (D50) is 150 nm or less, ejection stability is improved, and occurrence of nozzle clogging and ink bending may be prevented.
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.

  The content of the pigment in the ink for inkjet recording is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1% by mass to 20% by mass, and 1% by mass to 20% by mass. More preferred.

  The pigment is preferably mixed with water, a pigment, and, if necessary, a dispersant, dispersed with a disperser to adjust the particle size, and then the pigment dispersion is contained in the ink.

The pigment dispersion is obtained by mixing water, a pigment, a pigment dispersant, and, if necessary, other components, and then dispersing the mixture with a disperser and adjusting the particle size.
The obtained pigment dispersion is preferably degassed by filtering coarse particles with a filter, a centrifugal separator or the like, if necessary.

There is no restriction | limiting in particular in content of the pigment at the time of producing the said pigment dispersion, Although it can select suitably according to the objective, 0.1 mass%-50 mass% are preferable, 0.1 mass%- 30 mass% is more preferable.
The pigment dispersion is preferably degassed by filtering coarse particles with a filter, a centrifugal separator or the like, if necessary.

  As the pigment dispersant in the pigment dispersion, a polymer containing the structural unit represented by the general formula (1) and the general formula (2) is preferable. Other usable dispersants include, for example, an anionic interface. Examples of the surfactant include various surfactants such as a surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant, a naphthalenesulfonic acid Na formalin condensate, and a polymer type dispersant. 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 taurates, polyoxyalkyl ethers. Sulfate, polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate, lauryl alcohol sulfate, alkylphenol phosphate, naphthalenesulfonate formalin condensate, alkyl phosphate, alkylallylsulfone hydrochloride, Examples include diethylsulfosuccinate, diethylhexylsulfosuccinate, dioctylsulfosuccinate, and the like.

  Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.

  Examples of the amphoteric surfactant include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, And imidazoline derivatives.

  Examples of the nonionic surfactant include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ether, Ether type surfactants such as oxyallylalkyl alkyl ethers; polyoxyethylene oleic acid, polyoxyethylene oleic acid ester, polyoxyethylene distearic acid ester, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate Ester surfactants such as polyoxyethylene monooleate and polyoxyethylene stearate; 2,4,7,9-tetramethyl Acetylene glycol surfactants such as lu-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyn-3-ol, Etc.

Among these, naphthalenesulfonic acid Na formalin condensate is particularly preferable.
The total content of naphthalenesulfonic acid dimer, trimer, and tetramer in the naphthalenesulfonic acid Na formalin condensate is not particularly limited and can be appropriately selected according to the purpose. It is preferable that it is -80 mass%. When the content is 20% by mass or more, the dispersibility is improved and the storage stability of the ink is improved. As a result, the occurrence of nozzle clogging can be prevented. On the other hand, when the content is 80% by mass or less, the viscosity range of the ink is appropriate and the dispersibility may be good.

<Water-soluble organic solvent>
The water-soluble organic solvent has at least one of an effect as a wetting agent for preventing ink drying and an effect as a penetrating agent.

There is no restriction | limiting in particular as said water-soluble organic solvent, According to the objective, it can select suitably, For example, glycerol, ethylene glycol, diethylene glycol, isopropylideneglycerol, 1, 3- butanediol, 3-methyl-1, 3-butanediol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylolpropane, trimethylolethane, ethylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol 1,5-pentanediol, 1,6-hexanediol, 1,2,6-hexanetriol, 1,2,4-butanetriol, 1,2,3-butyl Polyhydric alcohols such as Ntriol and Petriol; many 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, 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 -Nitrogen-containing heterocyclic compounds such as dimethyl imidazolidinone, ε-caprolactam, γ-butyrolactone; Amides such as amide, N-methylformamide, N, N-dimethylformamide, N, N-dimethyl-β-methoxypropionamide, N, N-dimethyl-β-butoxypropionamide; monoethanolamine, diethanolamine, triethanol Examples include amines such as amine, monoethylamine, diethylamine, and triethylamine; sulfur-containing compounds such as dimethyl sulfoxide, sulfolane, and thiodiethanol; 3-ethyl-3-hydroxymethyloxetane, propylene carbonate, and ethylene carbonate. These may be used individually by 1 type and may use 2 or more types together.
Among these, 3-ethyl-3-hydroxymethyloxetane, isopropylideneglycerol, N, N-dimethyl-β-methoxypropionamide, N, N-dimethyl-β-butoxypropion from the viewpoint of preventing curling in plain paper Amides are particularly preferred.

  In addition, 1,3-butanediol, diethylene glycol, 2,2,4-trimethyl-1,3-pentanediol, triethylene glycol, and glycerin are excellent in preventing discharge failure due to moisture evaporation.

  Examples of the water-soluble organic solvent having relatively low wettability and permeability include 2-ethyl-1,3-hexanediol [solubility: 4.2% (25 ° C.)], 2, 2, 4 -Trimethyl-1,3-pentanediol [solubility: 2.0% (25 ° C)], and the like.

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.
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 desired physical properties, and can be appropriately selected according to the purpose. For example, diethylene glycol monophenyl ether, ethylene Alkyl and aryl ethers of polyhydric alcohols such as glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, tetraethylene glycol chlorophenyl ether, lower alcohols such as ethanol, etc. Is mentioned.

In addition, saccharides can be contained as a wetting agent that is not a water-soluble organic solvent. Examples of the saccharide include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), polysaccharides, and the like. Specific examples include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose, maltotriose, and the like. Here, the polysaccharide means a saccharide in a broad sense, and is used to include a substance that exists widely in nature such as α-cyclodextrin and cellulose. The derivatives of these saccharides are represented by the reducing sugars of the saccharides described above [for example, sugar alcohols [general formula: HOCH ₂ (CHOH) _n CH ₂ OH (where n represents an integer of 2 to 5)). The ], Oxidized sugars (eg, aldonic acid, uronic acid, etc.), amino acids, thioic acids and the like. Among these, sugar alcohol is preferable, and examples of the sugar alcohol include maltitol and sorbit.

The ratio of the pigment to the water-soluble organic solvent has a great influence on the ink ejection stability from the head. If the content of the water-soluble organic solvent is low even though the pigment solid content is high, the evaporation of water near the ink meniscus of the nozzle may progress and cause ejection failure.
The content of the water-soluble organic solvent in the inkjet recording ink is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% by mass to 60% by mass, and more preferably 20% by mass to 60% by mass. Is more preferable. When the content is 10% by mass or more, the ink ejection stability is improved, and when it is 60% by mass or less, the drying property is improved. The ink having the content in the more preferable numerical range has an advantage that the drying property and the ejection reliability are very good.

<Other ingredients>
There is no restriction | limiting in particular as said other component, It can select suitably as needed, For example, surfactant, pH adjuster, water-dispersible resin, antiseptic / antifungal agent, rust inhibitor, antioxidant , Ultraviolet absorbers, oxygen absorbers, light stabilizers, and the like.

-Surfactant-
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, fluorine-based surfactants Agents, etc. Among these, nonionic surfactants and fluorine surfactants are particularly preferable.

  Examples of the anionic surfactant include alkyl allyl, alkyl naphthalene sulfonate, alkyl phosphate, alkyl sulfate, alkyl sulfonate, alkyl ether sulfate, alkyl sulfosuccinate, alkyl ester sulfate, and alkylbenzene. Sulfonate, alkyl diphenyl ether disulfonate, alkyl aryl ether phosphate, alkyl aryl ether sulfate, alkyl aryl ether ester sulfate, olefin sulfonate, alkane olefin sulfonate, polyoxyethylene alkyl ether phosphate, Polyoxyethylene alkyl ether sulfate ester salt, ether carboxylate, sulfosuccinate, α-sulfo fatty acid ester, fatty acid salt, condensate of higher fatty acid and amino acid, naphthene Salt, and the like.

  Examples of the cationic surfactant include alkylamine salts, dialkylamine salts, aliphatic amine salts, benzalkonium salts, quaternary ammonium salts, alkylpyridinium salts, imidazolinium salts, sulfonium salts, phosphonium salts, Etc.

  Examples of the nonionic surfactant include acetylene glycol surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, and the like.

  Examples of the amphoteric surfactant include imidazoline derivatives such as imidazolinium betaine, dimethylalkyl lauryl betaine, alkyl glycine, alkyl di (aminoethyl) glycine, and the like.

  Examples of the fluorine-based surfactant include compounds represented by the following general formulas (I) to (III).

ただし、前記一般式（Ｉ）中、ｍは、０〜１０の整数を表す。ｎは、１〜４０の整数を表す。

However, in the said general formula (I), m represents the integer of 0-10. n represents an integer of 1 to 40.

前記一般式（ＩＩ）において、Ｒｆはフッ素含有基を表し、パーフルオロアルキル基が好ましい。
前記パーフルオロアルキル基としては、炭素数が１〜１０のものが好ましく、１〜３のものがより好ましく、例えば、−Ｃ_nＦ_2n-1（ただし、ｎは１〜１０の整数を表す）などが挙げられる。前記パーフルオロアルキル基としては、例えば、−ＣＦ₃、−ＣＦ₂ＣＦ₃、−Ｃ₃Ｆ₇、−Ｃ₄Ｆ₉、などが挙げられる。これらの中でも、−ＣＦ₃、−ＣＦ₂ＣＦ₃が特に好ましい。
ｍ、ｎ、及びｐは、それぞれ整数を表し、ｎは１〜４、ｍは６〜２５、ｐは１〜４が好ましい。

In the general formula (II), Rf represents a fluorine-containing group and is preferably a perfluoroalkyl group.
Examples of the perfluoroalkyl group preferably has a carbon number of 1 to 10, more preferably those of 1 to 3, for example, -C _n F _2n-1 (where, n is an integer of 1 to 10) Etc. Examples of the perfluoroalkyl group include —CF ₃ , —CF ₂ CF ₃ , —C ₃ F ₇ , —C ₄ F ₉ , and the like. Among these, —CF ₃ and —CF ₂ CF ₃ are particularly preferable.
m, n, and p each represent an integer, n is preferably 1-4, m is preferably 6-25, and p is preferably 1-4.

In the general formula (III), Rf represents a fluorine-containing group, and is preferably a perfluoroalkyl group similar to the above general formula (II). For example, CF ₃ , CF ₂ CF ₃ , C ₃ F ₇ , C ₄ such as F ₉ and the like preferably.
R ₂ ⁺ represents a cationic group, and examples thereof include quaternary ammonium groups; alkali metal ions such as sodium and potassium; triethylamine, triethanolamine, and the like. Among these, a quaternary ammonium group is particularly preferable.
R ₁ ⁻ represents an anionic group, and examples thereof include COO ⁻ , SO ₃ ⁻ , SO ₄ ⁻ , PO ₄ ⁻ , and the like. q is preferably 1-6.

As said fluorosurfactant, what was synthesize | combined suitably may be used and a commercial item may be used.
Examples of the commercially available products include Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, and 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, F1405 , F-474 (all manufactured by DIC Corporation); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR (all manufactured by DuPont); FT-110 , FT-250, FT-251, FT-400S, FT-150, FT-400SW (all manufactured by Neos Corporation); PF-151N (Solution For example).
Among these, Zonyl FS-300, FSN, FSN-100, and FSO (all manufactured by DuPont) are particularly preferable from the viewpoint of improving reliability and color developability.

  The content of the surfactant in the inkjet recording ink is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.01% by mass to 5.0% by mass, and 0.5% by mass. % To 3% by mass is more preferable. When the content is 5.0% by mass or less, the permeability to the recording medium is improved, and it may be possible to prevent a decrease in image density and occurrence of show-through.

-PH adjuster-
The pH adjuster is not particularly limited as long as it can adjust the pH to 8.5 to 11 without adversely affecting the ink to be prepared, and can be appropriately selected according to the purpose. Examples include alcohol amines, alkali metal hydroxides, ammonium hydroxides, phosphonium hydroxides, alkali metal carbonates, and the like.
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.

-Water dispersible resin-
The water-dispersible resin has excellent film-forming properties (image forming properties) and has high water repellency, high water resistance, and high weather resistance, and is used for image recording with high water resistance and high image density (high color development). Useful.
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, natural rubber, and the like.
Among these, polyurethane resin fine particles, acrylic-silicone resin fine particles, and fluorine-based resin fine particles are 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 not particularly limited so that the ink does not have an excessively high viscosity, and can be appropriately selected depending on the purpose, but is preferably 50 nm or more.
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 if 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, the minimum film-forming temperature (MFT) of the water-dispersible resin is not particularly limited and can be appropriately selected according to the purpose, but is preferably 30 ° C. or lower.
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. It is preferable.
The content of the water-dispersible resin in the inkjet recording ink is not particularly limited and may be appropriately selected depending on the intended purpose. However, the solid content is preferably 1% by mass to 15% by mass, and preferably 2% by mass. -7 mass% is more preferable.

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

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

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

-UV absorber-
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.

<Method for producing ink for inkjet recording>
The method for producing an ink for inkjet recording according to the present invention includes, for example, water, a water-soluble organic solvent, a pigment, a polymer containing the structural unit represented by the general formula (1) and the general formula (2), and as necessary. Other components can be produced by dispersing or dissolving in an aqueous medium and stirring and mixing.
The ink is preferably degassed by filtering coarse particles with a filter, a centrifugal separator or the like, if necessary.
The dispersion can be performed by, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, etc., and stirring and mixing are performed by a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser, or the like. be able to.

<Ink physical properties>
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.
There is no restriction | limiting in particular in the viscosity at 25 degrees C of the said ink for inkjet recording, Although it can select suitably according to the objective, 3 mPa * s-20 mPa * s are preferable. When the ink viscosity is 3 mPa · s or more, the effect of improving the printing density and the character quality can be obtained. On the other hand, when the ink viscosity is 20 mPa · s or less, ink ejection properties may be secured.
The viscosity can be measured at 25 ° C. using, for example, a viscometer (RL-550, manufactured by Toki Sangyo Co., Ltd.).
There is no restriction | limiting in particular as surface tension of the said ink for inkjet recording, Although it can select suitably according to the objective, 40 mN / m or less is preferable at 25 degreeC.

<Ink container>
The ink container of the present invention includes an ink container that stores the ink for ink jet recording of the present invention, and further includes other members appropriately selected as necessary.
The container is not particularly limited, and its shape, structure, size, material and the like can be appropriately selected according to the purpose. For example, at least an ink bag formed of an aluminum laminate film, a resin film, or the like Preferred examples include those possessed.

Next, the ink container will be described with reference to FIGS. Here, FIG. 1 is a diagram illustrating an example of the ink container, and FIG. 2 is a diagram including a case (exterior) of the ink container of FIG.
As shown in FIG. 1, the ink container 200 is filled into the ink container 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 container 241 is formed of a packaging member such as an aluminum laminate film that does not have air permeability. As shown in FIG. 2, the ink storage unit 241 is normally stored in a plastic container case 244 and is detachably mounted on various ink jet recording apparatuses.

<Inkjet recording apparatus>
The ink jet recording apparatus of the present invention is an ink jet recording apparatus that records information or an image on a recording medium using an ink jet head, and the ink is the ink for ink jet recording of the present invention.

Here, an example of the ink jet recording apparatus used in the present invention will be described with reference to the drawings.
The ink jet recording apparatus shown in FIG. 3 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 storage container loading unit 104. Using this paper feed tray 102, various recording media can be fed.
An operation unit 105 such as operation keys and a display is arranged on the upper surface of the ink container loading unit 104. The ink storage container loading unit 104 has a front cover 115 that can be opened and closed for detaching the ink storage container 200.

In the apparatus main body 101, as shown in FIGS. 4 and 5, the carriage 133 is slid in the main scanning direction by guide rods 131 and stays 132 which are horizontally mounted on left and right side plates (not shown). The main scanning motor (not shown) moves and scans in the direction indicated by 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 an inkjet recording head constituting the recording head 134, a piezoelectric actuator 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 metal phase due to a temperature change, etc. A shape memory alloy actuator using a change, an electrostatic actuator using an electrostatic force, or the like as an 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 recording ink from the ink container 200 loaded in the ink container loading unit 104 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 102, a half-moon roller (feeding) that separates and feeds the paper 142 from the paper stacking unit 141 one by one. 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. A conveying guide 153 for pressing, and a tip pressure roller 155 urged to the conveying belt 151 side by a pressing member 154, and a charging roller 156 as a charging means for charging the surface of the conveying belt 151. It has been.

  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 that is 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 polymer of tetrafluoroethylene and ethylene (ETFE), and the same material as the surface layer. It has a back layer (medium resistance layer, earth layer) that has been subjected to resistance control with 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 the ink jet recording apparatus, the sheet 142 is separated and fed one by one from the sheet feeding unit, and the sheet 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 conveying belt 151 is charged by the charging roller 156, and the sheet 142 is electrostatically attracted to the conveying belt 151 and conveyed. 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 the recording ink remaining amount near end in the sub tank 135 is detected, a required amount of recording ink is supplied from the ink container 200 to the sub tank 135.

In the ink jet recording apparatus, when the recording ink in the ink container 200 is used up, the casing of the ink container 200 can be disassembled and only the ink bag inside can be replaced. In addition, the ink container 200 can supply recording ink stably even when the ink container 200 is vertically placed and has a front loading configuration. Accordingly, when the upper portion of the apparatus main body 101 is closed and installed, for example, even when the apparatus main body 101 is stored in a rack or an object is placed on the upper surface of the apparatus main body 101, Exchange can be performed easily.
Here, an example is described in which the present invention is applied to a serial (shuttle type) ink jet recording apparatus that is scanned by a carriage.

  The ink jet recording apparatus and the ink jet recording method used in the present invention can be applied to various types of recording by the ink jet recording system. For example, the ink jet recording apparatus, the facsimile apparatus, the copying apparatus, the printer / fax / copier multifunction machine, etc. It can be used suitably.

(Recorded matter and method for producing recorded matter)
The method for producing a recorded matter of the present invention is a method for producing a recorded matter comprising a step of recording on a recording medium by discharging ink from an inkjet head, wherein the ink is the inkjet ink of the present invention.
The recorded matter of the present invention is a recorded matter in which information or an image is recorded on a recording medium using ink, and the ink is the inkjet ink of the present invention.
That is, in the recorded matter of the present invention, information or an image is recorded on a recording medium (recording medium) using the inkjet ink of the present invention. The recorded matter of the present invention can be produced by a process of recording on a recording medium by ejecting inkjet ink from an inkjet head.
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. It is done. 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. Plain paper and coated paper for printing have poor drying properties and are generally difficult to use for inkjet. However, the ink of the present invention has improved drying properties and can be used.
The recorded matter of the present invention 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 of the present invention will be described below, but the present invention is not limited to these examples.
In addition, the weight average molecular weight of the polymer in the synthesis example was measured according to the following method.

<Weight average molecular weight of polymer>
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. For the column, a water-based SEC column TSKgelG3000PWXL (exclusion limit molecular weight 2 × 10 ⁵ ), TSKgelG5000PWXL (exclusion limit molecular weight 2.5 × 10 ⁶ ) and TSKgel G6000PWXL (exclusion limit molecular weight 5 × 10 ⁷ ) manufactured by Tosoh Corporation is used. It was. 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 in which acetic acid and sodium acetate were adjusted to 0.5 mol / liter each was used. The column temperature was 40 ° C. and the flow rate was 1.0 mL / min.
Calibration curves using 9 types of polyethylene glycols with molecular weights of 1,065, 5,050, 24,000, 50,000, 107,000, 140,000, 250,000, 540,000, 920,000 as standard samples And the weight average molecular weight of the polymer was determined based on the calibration curve.

(Synthesis Example 1)
-Synthesis of polymer 1-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (3), 30.0 parts by mass of R3 is a methyl group, a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 70.0 parts by mass (which is an atom) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 65 ° C. Next, after carrying out a polymerization reaction for 15 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, polymer 1 in which phosphonic acid groups were neutralized 100% was synthesized. The weight average molecular weight of the obtained polymer 1 was 31,000.

(Synthesis Example 2)
-Synthesis of polymer 2-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (8) (1-acryloxyethane-1,1-diphosphonic acid) In the general formula (3), 30.0 parts by mass of R3 is a hydrogen atom, a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 70.0 parts by mass (which is an atom) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 65 ° C. Next, after carrying out a polymerization reaction for 15 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, polymer 2 in which phosphonic acid groups were neutralized 100% was synthesized. The weight average molecular weight of the obtained polymer 2 was 28000.

(Synthesis Example 3)
-Synthesis of polymer 3-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (3), 30.0 parts by mass of R3 is a methyl group, the compound represented by the structural formula (10), (diacetone methacrylamide, in the general formula (4), R4 is 70.0 parts by mass (which is a methyl group) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 65 ° C. Next, after carrying out a polymerization reaction for 15 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, polymer 3 in which phosphonic acid groups were neutralized 100% was synthesized. The weight average molecular weight of the obtained polymer 3 was 32,000.

(Synthesis Example 4)
-Synthesis of polymer 4-
In a flask equipped with a stirrer, thermometer, and nitrogen inlet tube, solvent (ethanol) 500.0
Parts by mass and a compound represented by the structural formula (8) (1-acryloxyethane-1,1-diphosphonic acid, R3 is a hydrogen atom in the general formula (3)), the structural formula (10 ) 70.0 parts by mass (diacetone methacrylamide, in the general formula (4), R4 is a methyl group), 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) The temperature was raised to 65 ° C. Next, after carrying out a polymerization reaction for 15 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, polymer 4 in which phosphonic acid groups were neutralized 100% was synthesized. The weight average molecular weight of the obtained polymer 4 was 33000.

(Synthesis Example 5)
-Synthesis of polymer 5-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (3), 30.0 parts by mass of R3 is a methyl group, a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 70.0 parts by mass (which is an atom) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 65 ° C. Next, after carrying out a polymerization reaction for 15 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 50% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, polymer 5 in which phosphonic acid groups were neutralized by 50% was synthesized. The weight average molecular weight of the obtained polymer 5 was 30000.

(Synthesis Example 6)
-Synthesis of polymer 6-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (3), 30.0 parts by mass of R3 is a methyl group, a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 70.0 parts by mass (which is an atom) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 65 ° C. Next, after carrying out a polymerization reaction for 15 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, ethanolamine was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, polymer 6 in which phosphonic acid groups were neutralized 100% was synthesized. The weight average molecular weight of the obtained polymer 6 was 31,000.

(Synthesis Example 7)
-Synthesis of polymer 7-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (3), 30.0 parts by mass of R3 is a methyl group, a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 70.0 parts by mass (which is an atom) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 75 ° C. Next, after carrying out a polymerization reaction for 3 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, polymer 7 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 7 was 3100.

(Synthesis Example 8)
-Synthesis of polymer 8-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (3), 30.0 parts by mass of R3 is a methyl group, a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 70.0 parts by mass (which is an atom) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 65 ° C. Next, after carrying out a polymerization reaction for 3 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, a polymer 8 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 8 was 5200.

(Synthesis Example 9)
-Synthesis of polymer 9-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (3), 30.0 parts by mass of R3 is a methyl group, a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 70.0 parts by mass (which is an atom) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 50 ° C. Next, after carrying out the polymerization reaction for 24 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, a polymer 9 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 9 was 50,000.

(Synthesis Example 10)
-Synthesis of polymer 10-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (3), 30.0 parts by mass of R3 is a methyl group, a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 70.0 parts by mass (which is an atom) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 50 ° C. Next, after carrying out the polymerization reaction for 48 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by further drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, a polymer 10 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 10 was 70000.

(Synthesis Example 11)
-Synthesis of polymer 11-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (3), R3 is a methyl group) 5.0 parts by mass, a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 95.0 parts by mass (which are atoms) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged and the temperature was raised to 75 ° C. Next, after carrying out a polymerization reaction for 3 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, a polymer 11 in which phosphonic acid groups were neutralized 100% was synthesized. The weight average molecular weight of the obtained polymer 11 was 3000.

(Synthesis Example 12)
-Synthesis of polymer 12-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (3), R3 is a methyl group) 5.0 parts by mass, a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 95.0 parts by mass (which is an atom) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 65 ° C. Next, after carrying out a polymerization reaction for 5 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, polymer 12 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 12 was 5000.

(Synthesis Example 13)
-Synthesis of polymer 13-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (3), R3 is a methyl group) 5.0 parts by mass, a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 95.0 parts by mass (which are atoms) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 50 ° C. Next, after carrying out the polymerization reaction for 24 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, a polymer 13 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 13 was 49000.

(Synthesis Example 14)
-Synthesis of polymer 14-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (3), R3 is a methyl group) 5.0 parts by mass, a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 95.0 parts by mass (which are atoms) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 50 ° C. Next, after carrying out the polymerization reaction for 48 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by further drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, a polymer 14 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 14 was 69000.

(Synthesis Example 15)
-Synthesis of polymer 15-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) 10.0 parts by mass of R3 in the general formula (3), a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 90.0 parts by mass (which is an atom) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 75 ° C. Next, after carrying out a polymerization reaction for 3 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, polymer 15 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 15 was 3200.

(Synthesis Example 16)
-Synthesis of polymer 16-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) 10.0 parts by mass of R3 in the general formula (3), a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 90.0 parts by mass (which is an atom) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 65 ° C. Next, after carrying out a polymerization reaction for 3 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, polymer 16 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 16 was 5300.

(Synthesis Example 17)
-Synthesis of polymer 17-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) 10.0 parts by mass of R3 in the general formula (3), a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 90.0 parts by mass (which is an atom) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 50 ° C. Next, after carrying out the polymerization reaction for 24 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, polymer 17 in which phosphonic acid groups were neutralized 100% was synthesized. The weight average molecular weight of the obtained polymer 17 was 50000.

(Synthesis Example 18)
-Synthesis of polymer 18-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) 10.0 parts by mass of R3 in the general formula (3), a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 90.0 parts by mass (which is an atom) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 50 ° C. Next, after carrying out the polymerization reaction for 48 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by further drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, a polymer 18 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 18 was 68,000.

(Synthesis Example 19)
-Synthesis of polymer 19-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (3), 60.0 parts by mass of R3 is a methyl group, a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 40.0 parts by mass (which are atoms) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 75 ° C. Next, after carrying out a polymerization reaction for 3 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, polymer 19 in which phosphonic acid groups were neutralized 100% was synthesized. The weight average molecular weight of the obtained polymer 19 was 3100.

(Synthesis Example 20)
-Synthesis of polymer 20-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (3), 60.0 parts by mass of R3 is a methyl group, a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 40.0 parts by mass (which is an atom) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 65 ° C. Next, after carrying out a polymerization reaction for 3 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, a polymer 20 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 20 was 5000.

(Synthesis Example 21)
-Synthesis of polymer 21-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (3), 60.0 parts by mass of R3 is a methyl group, a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 40.0 parts by mass (which is an atom) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 50 ° C. Next, after carrying out the polymerization reaction for 24 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, polymer 21 in which phosphonic acid groups were neutralized 100% was synthesized. The weight average molecular weight of the obtained polymer 21 was 48,000.

(Synthesis Example 22)
-Synthesis of polymer 22-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (3), 60.0 parts by mass of R3 is a methyl group, a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 40.0 parts by mass (which is an atom) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 50 ° C. Next, after carrying out the polymerization reaction for 48 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by further drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, polymer 22 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 22 was 70000.

(Synthesis Example 23)
-Synthesis of polymer 23-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) 80.0 parts by mass of R3 in the general formula (3), a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 20.0 parts by mass (which is an atom) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 75 ° C. Next, after carrying out a polymerization reaction for 3 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, polymer 23 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 23 was 3200.

(Synthesis Example 24)
-Synthesis of polymer 24-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) 80.0 parts by mass of R3 in the general formula (3), a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 20.0 parts by mass (which is an atom) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 65 ° C. Next, after carrying out a polymerization reaction for 3 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, polymer 24 in which phosphonic acid groups were neutralized 100% was synthesized. The weight average molecular weight of the obtained polymer 24 was 5200.

(Synthesis Example 25)
-Synthesis of polymer 25-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) 80.0 parts by mass of R3 in the general formula (3), a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 20.0 parts by mass (which is an atom) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 50 ° C. Next, after carrying out the polymerization reaction for 24 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, polymer 25 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 25 was 49000.

(Synthesis Example 26)
-Synthesis of polymer 26-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound represented by the structural formula (7) (1-methacryloxyethane-1,1-diphosphonic acid) 80.0 parts by mass of R3 in the general formula (3), a compound represented by the structural formula (9), (diacetone acrylamide, in the general formula (4), R4 is hydrogen. 20.0 parts by mass (which is an atom) and 4.0 parts by mass of a polymerization initiator (azobisisobutyronitrile) were charged, and the temperature was raised to 50 ° C. Next, after carrying out the polymerization reaction for 48 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by further drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, a polymer 26 in which phosphonic acid groups were neutralized 100% was synthesized. The weight average molecular weight of the obtained polymer 26 was 70000.

(Comparative Synthesis Example 1)
-Synthesis of polymer 27-
In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 500.0 parts by mass of a solvent (ethanol) and a compound of the following structural formula (11) (4-methacrylamide-1-hydroxybutane-1,1-diphosphone) Acid) 100.0 parts by mass and a polymerization initiator (azobisisobutyronitrile) 4.0 parts by mass were charged and the temperature was raised to 70 ° C. Next, after carrying out a polymerization reaction for 5 hours under a nitrogen stream, about half of the charged solvent was distilled off from the reaction system, and then the polymer was precipitated by pouring the mixture into acetone, followed by drying. Got.
While diluting the obtained polymer with water, potassium hydroxide was added so as to achieve 100% acid neutralization, and the concentration was adjusted with water so that the solid concentration was 10% by mass. In this way, polymer 27 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 27 was 5,100.

(Comparative Synthesis Example 2)
While diluting hydroxyethylidene diphosphonic acid (HEDP) represented by the following structural formula (12) with water, potassium hydroxide is added so as to achieve 100% acid neutralization, and the solid content concentration becomes 10% by mass. Then, the concentration was adjusted with water. In this way, a potassium hydroxyethylidene diphosphonate aqueous solution (solid content: 10% by mass) was obtained.

Table 1 shows the structural characteristics of the polymers prepared in the synthesis examples.

Example 1
-Preparation of pigment dispersion-
・ Carbon black (NIPEX150, manufactured by Degussa Co., Ltd.) 20.0 mass parts ・ Naphthalenesulfonic acid Na formalin condensate (solid content 10 mass%)
・ ・ ・ 13.0 parts by mass ・ Pure water ・ ・ ・ 67.0 parts by mass After premixing the above mixture, a disk-type bead mill (manufactured by Shinmaru Enterprises, KDL type, media: zirconia having a diameter of 0.1 mm) The mixture was circulated and dispersed at a peripheral speed of 10 m / s for 10 minutes and then filtered through a membrane filter having a pore size of 1.2 μm to obtain pigment dispersion 1 of Example 1.

-Preparation of ink-
-Pigment dispersion of Example 1 (pigment solid content 20% by mass) ... 40.0 parts by mass-1,3-butanediol (water-soluble organic solvent) ... 20.0 parts by mass-Glycerin (water-soluble) Organic solvent) ... 10.0 parts by mass 2-ethyl-1,3-hexanediol (water-soluble organic solvent) ... 1.0 part by mass 2,2,4-trimethyl-1,3-penta Diol (water-soluble organic solvent)
・ ・ ・ 1.0 part by mass ・ Fluorosurfactant (solid content 40% by mass, manufactured by DuPont, Zonyl FS-300)
... 2.0 parts by mass-Polymer 1 aqueous solution of Synthesis Example 1 (solid content 10% by mass) ... 20.0 parts by mass-Distilled water ... 6.0 parts by mass After stirring for 5 hours, the mixture was filtered through a membrane filter having a pore size of 1.2 μm to obtain an ink.

(Example 2)
In Example 1 -Preparation of ink-, the same procedure as in Example 1 was carried out except that the polymer 2 aqueous solution (solid content 10% by mass) of synthesis example 2 was used instead of the polymer 1 aqueous solution of synthesis example 1. Obtained.

Example 3
In Example 1 -Preparation of ink-, the same procedure as in Example 1 was conducted except that the aqueous polymer 3 solution of synthesis example 3 (solid content 10% by mass) was used instead of the aqueous solution of polymer 1 of synthesis example 1. Obtained.

Example 4
In Example 1 -Preparation of ink-, the same procedure as in Example 1 was carried out except that the aqueous polymer 4 solution of synthesis example 4 (solid content 10% by mass) was used instead of the aqueous polymer 1 solution of synthesis example 1. Obtained.

(Example 5)
-Preparation of pigment dispersion-
Carbon black (NIPEX150, manufactured by Degussa) 20.0 mass parts Polymer 1 aqueous solution of Synthesis Example 1 (solid content 10 mass%) 50.0 mass parts Pure water 30.0 Part by mass After premixing the above mixture, it was circulated and dispersed for 10 minutes at a peripheral speed of 10 m / s with a disk-type bead mill (Shinmaru Enterprises, KDL type, media: zirconia ball with a diameter of 0.1 mm), A pigment dispersion of Example 5 was obtained by filtration through a membrane filter having a pore size of 1.2 μm.
-Preparation of ink-
-Pigment dispersion of Example 5 (pigment solid content 20% by mass) ... 40.0 parts by mass-1,3-butanediol (water-soluble organic solvent) ... 20.0 parts by mass-Glycerin (water-soluble) Organic solvent) ... 10.0 parts by mass 2-ethyl-1,3-hexanediol (water-soluble organic solvent) ... 1.0 part by mass 2,2,4-trimethyl-1,3-penta Diol (water-soluble organic solvent)
・ ・ ・ 1.0 part by mass ・ Fluorosurfactant (solid content 40% by mass, manufactured by DuPont, Zonyl FS-300)
... 2.0 parts by mass Distilled water ... 26.0 parts by mass The above materials were mixed, stirred for 1.5 hours, and then filtered through a membrane filter having a pore size of 1.2 µm to obtain an ink.

(Example 6)
In Example 5 -Preparation of pigment dispersion-, Example 5 was used except that Pigment Blue 15: 3 (manufactured by Dainichi Seika Co., Ltd., chromofine blue cyan pigment) was used instead of carbon black (NIPEX150, manufactured by Degussa). In the same manner as described above, a pigment dispersion of Example 6 was prepared.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 6 was used instead of the pigment dispersion of Example 5.

(Example 7)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was performed except that Pigment Red 122 (Clariant, Toner Magenta EO02 Magenta Pigment) was used instead of carbon black (NIPEX150, manufactured by Degussa). The pigment dispersion of Example 7 was prepared.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 7 was used instead of the pigment dispersion of Example 5.

(Example 8)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was performed except that Pigment Yellow (Daiichi Seika Co., Ltd., First Yellow 531 Yellow Pigment) was used instead of carbon black (NIPEX150, manufactured by Degussa). A pigment dispersion of Example 8 was prepared.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 8 was used instead of the pigment dispersion of Example 5.

Example 9
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out except that the aqueous polymer 2 solution of synthesis example 2 (solid content 10% by mass) was used instead of the aqueous polymer 1 solution of synthesis example 1. The pigment dispersion of Example 9 was prepared.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 9 was used instead of the pigment dispersion of Example 5.

(Example 10)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out except that the aqueous polymer 3 solution of synthesis example 3 (solid content 10% by mass) was used instead of the aqueous polymer 1 solution of synthesis example 1. The pigment dispersion of Example 10 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 10 was used instead of the pigment dispersion of Example 5.

(Example 11)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out, except that the polymer 4 aqueous solution (solid content 10% by mass) of synthesis example 4 was used instead of the polymer 1 aqueous solution of synthesis example 1. The pigment dispersion of Example 11 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 11 was used instead of the pigment dispersion of Example 5.

(Example 12)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was performed, except that the aqueous polymer 5 solution of Synthesis Example 5 (solid content 10% by mass) was used instead of the aqueous polymer 1 solution of Synthesis Example 1. The pigment dispersion of Example 12 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 12 was used instead of the pigment dispersion of Example 5.

(Example 13)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out, except that the polymer 6 aqueous solution of Synthesis Example 6 (solid content 10% by mass) was used instead of the polymer 1 aqueous solution of Synthesis Example 1. The pigment dispersion of Example 13 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 13 was used instead of the pigment dispersion of Example 5.

(Example 14)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out, except that the polymer 7 aqueous solution (solid content 10% by mass) of synthesis example 7 was used instead of the polymer 1 aqueous solution of synthesis example 1. The pigment dispersion of Example 14 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 14 was used instead of the pigment dispersion of Example 5.

(Example 15)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out, except that the polymer 8 aqueous solution (solid content 10% by mass) of synthesis example 8 was used instead of the polymer 1 aqueous solution of synthesis example 1. The pigment dispersion of Example 15 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 15 was used instead of the pigment dispersion of Example 5.

(Example 16)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out, except that the polymer 9 aqueous solution (solid content 10% by mass) of synthesis example 9 was used instead of the polymer 1 aqueous solution of synthesis example 1. The pigment dispersion of Example 16 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 16 was used instead of the pigment dispersion of Example 5.

(Example 17)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out, except that the polymer 10 aqueous solution (solid content 10% by mass) of Synthesis Example 10 was used instead of the polymer 1 aqueous solution of Synthesis Example 1. The pigment dispersion of Example 17 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 17 was used instead of the pigment dispersion of Example 5.

(Example 18)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out except that the polymer 11 aqueous solution (solid content 10% by mass) of synthesis example 11 was used instead of the polymer 1 aqueous solution of synthesis example 1. The pigment dispersion of Example 18 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 18 was used instead of the pigment dispersion of Example 5.

(Example 19)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out, except that the polymer 12 aqueous solution of Synthesis Example 12 (solid content 10% by mass) was used instead of the polymer 1 aqueous solution of Synthesis Example 1. The pigment dispersion of Example 19 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 19 was used instead of the pigment dispersion of Example 5.

(Example 20)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out, except that the polymer 13 aqueous solution of Synthesis Example 13 (solid content 10% by mass) was used instead of the polymer 1 aqueous solution of Synthesis Example 1. The pigment dispersion of Example 20 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 20 was used instead of the pigment dispersion of Example 5.

(Example 21)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out except that the polymer 14 aqueous solution (solid content 10% by mass) of synthesis example 14 was used instead of the polymer 1 aqueous solution of synthesis example 1. The pigment dispersion of Example 21 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 21 was used instead of the pigment dispersion of Example 5.

(Example 22)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out except that the polymer 15 aqueous solution of Synthesis Example 15 (solid content 10% by mass) was used instead of the polymer 1 aqueous solution of Synthesis Example 1. The pigment dispersion of Example 22 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 22 was used instead of the pigment dispersion of Example 5.

(Example 23)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out except that the polymer 16 aqueous solution (solid content 10% by mass) of synthesis example 16 was used instead of the polymer 1 aqueous solution of synthesis example 1. The pigment dispersion of Example 23 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 23 was used instead of the pigment dispersion of Example 5.

(Example 24)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out except that the polymer 17 aqueous solution (solid content 10% by mass) of synthesis example 17 was used instead of the polymer 1 aqueous solution of synthesis example 1. The pigment dispersion of Example 24 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 24 was used instead of the pigment dispersion of Example 5.

(Example 25)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out except that the polymer 18 aqueous solution (solid content 10% by mass) of synthesis example 18 was used instead of the polymer 1 aqueous solution of synthesis example 1. The pigment dispersion of Example 25 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 25 was used instead of the pigment dispersion of Example 5.

(Example 26)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out, except that the polymer 19 aqueous solution (solid content 10% by mass) of synthesis example 19 was used instead of the polymer 1 aqueous solution of synthesis example 1. The pigment dispersion of Example 26 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 26 was used instead of the pigment dispersion of Example 5.

(Example 27)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out except that the aqueous polymer 20 solution of synthesis example 20 (solid content 10% by mass) was used instead of the aqueous polymer 1 solution of synthesis example 1. The pigment dispersion of Example 27 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 27 was used instead of the pigment dispersion of Example 5.

(Example 28)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out except that the polymer 21 aqueous solution of Synthesis Example 21 (solid content: 10% by mass) was used instead of the polymer 1 aqueous solution of Synthesis Example 1. The pigment dispersion of Example 28 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 28 was used instead of the pigment dispersion of Example 5.

(Example 29)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out except that the polymer 22 aqueous solution (solid content 10% by mass) of Synthesis Example 22 was used instead of the polymer 1 aqueous solution of Synthesis Example 1. The pigment dispersion of Example 29 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 29 was used instead of the pigment dispersion of Example 5.

(Example 30)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out, except that the polymer 23 aqueous solution (solid content 10% by mass) of Synthesis Example 23 was used instead of the polymer 1 aqueous solution of Synthesis Example 1. The pigment dispersion of Example 30 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 30 was used instead of the pigment dispersion of Example 5.

(Example 31)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out, except that the polymer 24 aqueous solution (solid content 10% by mass) of Synthesis Example 24 was used instead of the polymer 1 aqueous solution of Synthesis Example 1. The pigment dispersion of Example 31 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 31 was used instead of the pigment dispersion of Example 5.

(Example 32)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was performed, except that the polymer 25 aqueous solution (solid content 10% by mass) of Synthesis Example 25 was used instead of the polymer 1 aqueous solution of Synthesis Example 1. The pigment dispersion of Example 32 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 32 was used instead of the pigment dispersion of Example 5.

(Example 33)
In Example 5 -Preparation of pigment dispersion-, the same procedure as in Example 5 was carried out, except that the polymer 26 aqueous solution (solid content 10% by mass) of synthesis example 26 was used instead of the polymer 1 aqueous solution of synthesis example 1. The pigment dispersion of Example 33 was made.
Further, in Example 5 -Preparation of ink-, an ink was obtained in the same manner as in Example 5 except that the pigment dispersion of Example 33 was used instead of the pigment dispersion of Example 5.

(Comparative Example 1)
In Example 1-Preparation of ink-Ink was obtained in the same manner as in Example 1 except that the polymer 27 aqueous solution of Comparative Synthesis Example 1 (solid content 10 mass%) was used instead of the polymer 1 aqueous solution of Synthesis Example 1. It was.

(Comparative Example 2)
In Example 1-Preparation of ink-In the same manner as in Example 1 except that the aqueous hydroxyethylidene diphosphonate solution (solid content 10% by mass) of Comparative Synthesis Example 2 was used instead of the Polymer 1 aqueous solution of Synthesis Example 1, Ink was obtained.

The following evaluation was performed on the pigment dispersions and inks prepared in the examples and comparative examples.
The evaluation results are shown in Table 2.

・ Evaluation method <Image density>
64 points JIS X 0208 (1997), 2223 manufactured by Microsoft Word2000 (manufactured by Microsoft), filled with ink prepared in an ink jet printer (manufactured by Ricoh Co., Ltd., IPSiO GX5000) in an environment of 23 ° C. and 50% RH. Are printed on plain paper 1 (XEROX 4200, about 20% Ca carbonate produced by XEROX) and plain paper 2 (MyPaper, about 4% Ca carbonate produced by Ricoh Co., Ltd.) The general symbol on the printing surface was measured with X-Rite 938 (manufactured by X-Rite Co., Ltd.) 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: 1.25 or more B: 1.2 or more and less than 1.25 C: 1.1 or more and less than 1.2 D: Less than 1.1 E: The pigment gels and cannot be dispersed in the ink and cannot be printed.

<Storage stability of pigment dispersion>
Each pigment dispersion was put in a polyethylene container, sealed, stored at 60 ° C. for 1 week, the change rate of the viscosity after storage with respect to the viscosity before storage was obtained from the following formula, and evaluated according to the following criteria.
Viscosity change rate (%) = {(viscosity of pigment dispersion after storage−viscosity of pigment dispersion before storage)
/ Viscosity of pigment dispersion before storage)} × 100
For measuring the viscosity, a viscometer (RE80L, manufactured by Toki Sangyo Co., Ltd.) was used, and the viscosity at 25 ° C. was measured at 50 revolutions or 100 revolutions.
[Evaluation criteria]
A: Change rate of viscosity is within ± 5% B: Change rate of viscosity is over ± 5% and within ± 8% C: Change rate of viscosity is over ± 8% and within ± 10% D: Change rate of viscosity is Over ± 10% and within ± 30% E: Viscosity change rate exceeds ± 30% (cannot be evaluated due to gelation)

<Ink storage stability>
Each ink was filled in an ink container and stored at 60 ° C. for 1 week. The change rate of the viscosity after storage with respect to the viscosity before storage was obtained from the following formula and evaluated according to the following criteria.
Viscosity change rate (%) = {(Ink viscosity after storage−Ink viscosity before storage)
/ Viscosity of ink before storage)} × 100
For measuring the viscosity, a viscometer (RE80L, manufactured by Toki Sangyo Co., Ltd.) was used, and the viscosity at 25 ° C. was measured at 50 revolutions or 100 revolutions.
[Evaluation criteria]
A: Change rate of viscosity is within ± 5% B: Change rate of viscosity is over ± 5% and within ± 8% C: Change rate of viscosity is over ± 8% and within ± 10% D: Change rate of viscosity is Over ± 10% and within ± 30% E: Viscosity change rate exceeds ± 30% (cannot be evaluated due to gelation)

  From the results shown in Table 2, the ink of the example has a higher image density even on general plain paper than the ink of the comparative example, and the ink can be used even if the content of the water-soluble organic solvent exceeds 20% by mass. It was found that the storage stability of was excellent.

DESCRIPTION OF SYMBOLS 101 Device main body 102 Paper feed tray 103 Paper discharge tray 104 Ink storage container loading part 105 Operation part 111 Upper cover 112 Front surface 115 Front cover 131 Guide rod 132 Stay 133 Carriage 134 Recording head 135 Sub tank 141 Paper mounting part 142 Paper 143 Paper feed Roller 144 Separation pad 145 Guide 151 Conveying belt 152 Counter roller 153 Conveying guide 154 Pressing member 155 Tip pressure roller 156 Charging roller 157 Conveying roller 158 Densation roller 161 Guide member 171 Separating claw 172 Discharging roller 173 Discharging roller 181 Double-sided feeding Paper unit 182 Manual paper feed unit 200 Ink container 241 Ink container 242 Ink inlet 243 Ink outlet 244 Case (exterior)

Special table 2009-513802 JP 2012-51357 A JP 2004-123904 A

Claims (12)

An ink for ink jet recording comprising water, a water-soluble organic solvent, a pigment, and a polymer containing a structural unit represented by the following general formula (1) and a structural unit represented by the general formula (2) .

[In General Formula (1), R1 represents either a hydrogen atom or a methyl group. M ⁺ represents at least one selected from alkali metal ions, organic amine ions, and hydrogen ions. ]

[R2 in the general formula (2) represents a methyl group or a hydrogen atom. ]   2. The ink for inkjet recording according to claim 1, wherein the content of the structural unit represented by the general formula (1) of the polymer is 10% by mass to 60% by mass. The ink for inkjet recording according to claim 1, wherein the structural unit represented by the general formula (1) of the polymer is represented by the following general formula (5).

[In General Formula (5), M ⁺ represents at least one selected from alkali metal ions, organic amine ions, and hydrogen ions. ] The ink for inkjet recording according to any one of claims 1 to 3, wherein the structural unit represented by the general formula (2) of the polymer is represented by the following structural formula (6).

The ink for inkjet recording according to any one of claims 1 to 4, wherein M ^{+ of the} structural unit represented by the general formula (1) of the polymer is a potassium ion. It contains water, a water-soluble organic solvent, a pigment, and a polymer synthesized using at least a compound represented by the following general formula (3) and a compound represented by the general formula (4) as a starting material. Ink for ink jet recording.

[In general formula (3), R3 represents a methyl group or a hydrogen atom. ]

[In the general formula (4), R4 represents a methyl group or a hydrogen atom. ]   The ink for ink jet recording according to any one of claims 1 to 6, wherein the polymer has a weight average molecular weight of 5,000 to 50,000.   The ink for inkjet recording according to any one of claims 1 to 7, wherein the polymer is used as a pigment dispersant.   An ink storage container including an ink storage portion for storing ink, wherein the ink stored in the ink storage portion is the ink for ink jet recording according to any one of claims 1 to 8. Ink container.   An ink jet recording apparatus for recording information or an image on a recording medium using an ink jet head, wherein the ink is the ink for ink jet recording according to any one of claims 1 to 8. Recording device.   A method for producing a recorded matter comprising a step of recording on a recording medium by discharging ink from an ink jet head, wherein the ink is the ink for ink jet recording according to any one of claims 1 to 8. A method for producing recorded material.   A recorded matter in which information or an image is recorded on a recording medium using ink, wherein the ink is the ink for ink jet recording according to any one of claims 1 to 8.

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