JP6255922B2 - Ink jet recording ink, ink jet recording ink manufacturing method, ink container, ink jet recording apparatus, recorded matter manufacturing method, and recorded matter - Google Patents

Description

  The present invention relates to an ink for ink jet recording, 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, for example, 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.

  In addition, an ink jet recording method has been proposed in which a receiving liquid containing a Ca salt is attached to paper and ink containing a pigment, a resin emulsion, and a surfactant having a phosphorus-containing group bonded thereto is printed (see, for example, 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.

  In addition, an aqueous ink containing a colorant, water, a water-soluble organic solvent, a surfactant, and a chelating agent has been proposed (for example, 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 that provides a high image density and is excellent in storage stability.

  In order to solve the above problems, the ink for inkjet recording of the present invention as a means for solving the above problems includes water, a water-soluble organic solvent, a pigment, and a structural unit represented by the following general formula (1): And a polymer containing a structural unit represented by the following general formula (2) and a structural unit represented by the following general formula (3) or general formula (4).

(In general formula (1), R 1 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.)

(In the general formula (2), R2 represents a methyl group or a hydrogen atom.)

(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.)

According to the present invention, the conventional problems can be solved, the object can be achieved, a high image density can be obtained, and an ink for ink jet recording excellent in storage stability can be provided.

It is the schematic which shows an example of an ink cartridge. FIG. 2 is a schematic view including a case of the ink cartridge of FIG. 1. 1 is a perspective view showing an embodiment of an ink jet recording apparatus according to the present invention. It is a figure which shows other one Embodiment of the inkjet recording device which concerns on this invention. It is a schematic enlarged view showing an example of an ink jet head of an ink jet recording apparatus.

  The ink for ink jet recording according to the present invention (hereinafter sometimes simply referred to as “ink”) includes water, a water-soluble organic solvent, a pigment, a structural unit represented by the following general formula (1), and the following general formula ( The polymer contains the structural unit represented by 2) and the structural unit represented by the following general formula (3) or general formula (4).

(In general formula (1), R 1 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.)

(In the general formula (2), R2 represents a methyl group or a hydrogen atom.)

(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.)

(polymer)
The polymer of the present invention is represented by the structural unit represented by the general formula (1), the structural unit represented by the general formula (2), and the general formula (3) or the general formula (4). And other structural units (a structural unit derived from a polymerizable monomer) as necessary.

Examples of the alkali metal in the M ⁺ alkali metal ion in the general formula (1) include lithium, sodium, and potassium. In particular, potassium ion is desirable from the viewpoints of both image density and storage stability.
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.
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).

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 the said General formula (2), the structural unit represented by following Structural formula (6) is preferable. Moreover, as a structural unit represented by the said General formula (3), the structural unit represented by following Structural formula (7) is preferable. Moreover, as a structural unit represented by the said General formula (4), the structural unit represented by following Structural formula (8) is preferable.
Including a structural unit represented by the following structural formula (5), a structural unit represented by the following structural formula (6), and a structural unit represented by the following structural formula (7) or (8). As a result, the image density and the storage stability of the pigment dispersion can be further improved.

(In the general formula (5), M ⁺ represents at least one selected from alkali metal ions, organic amine ions, and hydrogen ions.)

In addition to the structural unit represented by the general formula (1), general formula (2), general formula (3), or general formula (4), the polymer further includes a structural unit derived from a polymerizable monomer. Is possible.
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. When a structural unit derived from a polymerizable hydrophobic monomer is included, an effect such as ink storability is observed. When a structural unit derived from a polymerizable hydrophilic monomer is included, an effect such as ink storability is exhibited. Seen.

  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% are still more preferable, and 20 mass%-40 mass% are the most 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.

  The mass ratio of the structural unit represented by the general formula (2) of the copolymer is not particularly limited and can be appropriately selected depending on the purpose, but is 5 to 90% by mass with respect to the total amount of the polymer. It is preferable to set within the range.

  The mass ratio of the structural unit represented by the general formula (3) or the general formula (4) in the polymer is after the mass ratio of the general formula (1) and the mass ratio of the general formula (2) are set. Although it is set in the remaining ratio, it is usually preferably 5 to 90% by mass, and more preferably 10 to 80% by mass. Thereby, it is possible to achieve both the image density and the storage stability of the inkjet ink on plain paper.

  A polymer comprising a structural unit represented by the general formula (1), a structural unit represented by the general formula (2), and a structural unit represented by the general formula (3) or the general formula (4) Can be produced by the polymer production method of the present invention described below. The polymer is not particularly limited and can be widely used in various fields. However, the polymer is preferably used as a pigment dispersant, a pigment concentration improver, a pigment binder resin, a viscosity modifier, etc. in ink for inkjet recording. Can do.

<Method for producing polymer>
The method for producing a polymer used in the present invention includes at least a compound represented by the following general formula (9), a compound represented by the following general formula (10), and the following general formula (11) or general formula (12). After the polymerization of the starting material containing at least the compound represented by the formula (1), the step of treating the resulting polymer with either an alkali metal base or an organic amine base, and further including other steps as necessary. Good.

  The polymer containing the structural unit represented by the general formula (1) includes a compound represented by the following general formula (9), a compound represented by the following general formula (10), and the following general formula (11) or After polymerizing the compound represented by the general formula (12), or a compound represented by the following general formula (9), a compound represented by the following general formula (10), and the following general formula (11) or After the compound represented by the general formula (12) and the polymerizable monomer are copolymerized, they can be synthesized by neutralizing with either an alkali metal base or an organic amine base. In addition, the structural unit represented by the following general formula (9) is previously neutralized with either an alkali metal base or an organic amine base, and the structural unit represented by the following general formula (10) and the following general formula (11) or It can also be synthesized by copolymerizing the structural unit represented by the general formula (12).

（一般式（９）中、Ｒ9はメチル基又は水素原子を表す。）

(In general formula (9), R9 represents a methyl group or a hydrogen atom.)

（一般式（１０）中、Ｒ10はメチル基又は水素原子を表す。）

(In general formula (10), R10 represents a methyl group or a hydrogen atom.)

（一般式（１１）中Ｒ11はメチル基又は水素原子を表す。）

(In the general formula (11), R11 represents a methyl group or a hydrogen atom.)

（一般式（１２）中Ｒ12はメチル基又は水素原子を表す。）

(In the general formula (12), R12 represents a methyl group or a hydrogen atom.)

  Examples of the compound represented by the general formula (9) include 1-methacryloxyethane-1,1-diphosphonic acid represented by the following structural formula (13) in which R9 is a methyl group, and R9 is a hydrogen atom. There may be mentioned 1-acryloxyethane-1,1-diphosphonic acid represented by the following structural formula (14). 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 (10) include diacetone acrylamide represented by the following structural formula (15) in which R10 is a hydrogen atom, and the following structural formula (16) in which R9 is a methyl group. And diacetone methacrylamide.

  Examples of the compound represented by the general formula (11) include stearyl methacrylate represented by the following structural formula (17) in which R 11 is a methyl group, and represented by the following structural formula (18) in which R 11 is a hydrogen atom. And stearyl acrylate.

  Examples of the compound represented by the general formula (12) include benzyl methacrylate represented by the following structural formula (19) in which R12 is a methyl group, and the following structural formula (20) in which R12 is a hydrogen atom. And benzyl acrylate.

A polymer comprising the structural unit represented by the general formula (1), the structural unit represented by the general formula (2), and the structural unit represented by the general formula (3) or the general formula (4). As the synthesis method, a method using a radical polymerization initiator is preferable because the polymerization operation and the molecular weight can be easily adjusted, and a solution polymerization method in which polymerization is performed in an organic 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.

  A polymer comprising the structural unit represented by the general formula (1), the structural unit represented by the general formula (2), and the structural unit represented by the general formula (3) or the general formula (4). More specifically, an example of a synthesis method will be described below. In a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, a solvent, a compound represented by the general formula (9), a compound represented by the general formula (10), and the general formula (11) Alternatively, the compound represented by the general formula (12) and, if necessary, a polymerizable monomer are reacted at a temperature of 60 ° C. to 150 ° C. under reflux of nitrogen gas in the presence of a polymerization initiator, and then an alkali metal base and an organic compound are reacted. It can be synthesized by neutralizing with any 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.
For example, when the compound represented by the general formula (3) is the 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.

A polymer comprising the structural unit represented by the general formula (1), the structural unit represented by the general formula (2), and the structural unit represented by the general formula (3) or the general formula (4). The weight average molecular weight is not particularly limited and can be appropriately selected according to the purpose, but is preferably 2,000 to 70,000, more preferably 4,000 to 50,000, and 6,000 to 30,000. 000 is more preferable.
The weight average molecular weight can be measured, for example, by gel permeation chromatography (GPC).

A polymer comprising the structural unit represented by the general formula (1), the structural unit represented by the general formula (2), and the structural unit represented by the general formula (3) or the general formula (4). The weight average molecular weight of 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 at a high temperature in a short time, and a high molecular weight polymer tends to be obtained when polymerized at a low temperature for a long time.
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 inkjet recording ink of the present invention includes water, a water-soluble organic solvent, a structural unit represented by the general formula (1) of the present invention, a structural unit represented by the general formula (2), and the general formula. It contains a polymer containing the structural unit represented by (3) or general formula (4), and may contain other components as necessary.

<Polymer Containing Structural Unit Represented by General Formula (1), Structural Unit Represented by General Formula (2), and Structural Unit Represented by General Formula (3) or General Formula (4)>
The inkjet recording ink of the present invention includes a structural unit represented by the general formula (1), a structural unit represented by the general formula (2), and the general formula (3) or the general formula (4). It contains the polymer containing the structural unit represented.
The polymer has a dibasic acid structure in which phosphonic acid groups are adjacent to each other, and unlike a low molecular weight compound, the polymer has many diphosphonic acid groups in the molecule. As a result, the polymer can add more hydrophilic groups in the polymer molecule than the monobasic acid, and exhibits good hydrophilicity. 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.

The structural unit represented by the general formula (3) or the general formula (4) has a function to prevent the association of phosphonic acid groups in the polymer, although the reason is not clear, and storage stability in water-based ink Is further improved.
The reason for this is also uncertain, but by having the structural unit represented by the general formula (3) or the general formula (4), the general formula (1), the general formula (2), and the general formula (3) ) Or the adsorptivity of the polymer containing the structural unit represented by the general formula (4) to the pigment. As its secondary effect, it can be used as a pigment dispersant.

  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 association of phosphonic acid groups in the polymer, and is stable in aqueous ink. There is an effect of further improving the property.

  Therefore, the structural unit represented by the general formula (1), the structural unit represented by the general formula (2), and the structural unit represented by the general formula (3) or the general formula (4). When the containing polymer is used for an ink for ink jet recording, good dispersion stability and storage stability of the ink are exhibited. In addition, when ink is printed on paper, the structure represented by the general formula (1) is generated by Ca ions eluted from the paper into the ink even if the plain paper has a small Ca ion content. Since the unit is hydrophobized, and the structural unit represented by the general formula (3) or (4) has a high adsorptivity to the pigment, the pigment stays on the paper surface due to the inclusion of the pigment and aggregation. A high image density can be realized. Furthermore, the storage stability of the ink can be further enhanced by having the structure of the general formula (2).

  The structural unit represented by the general formula (1), the structural unit represented by the general formula (2), and the structural unit represented by the general formula (3) or the general formula (4) are polymerized. The content of the ink for ink jet recording is not particularly limited and may be appropriately selected depending on the intended purpose. However, the solid content is preferably 0.05% by mass to 10% by mass, and preferably 0.5% by mass to 5%. % By mass is more preferable, and 1% by mass to 3% by 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.

A polymer comprising the structural unit represented by the general formula (1), the structural unit represented by the general formula (2), and the structural unit represented by the general formula (3) or the general formula (4). Is used as a pigment dispersant, further improvement in image density on plain paper and storage stability in inks containing a large amount of water-soluble organic solvent are recognized.
When used as the pigment dispersant, the structural unit represented by the general formula (1), the structural unit represented by the general formula (2), the general formula (3), or the general formula (4) It is preferable that the structural unit derived from a hydrophobic polymerizable monomer other than the structural unit represented by this is represented. As the hydrophobic polymerizable monomer, those described above can be used.

  A polymer comprising the structural unit represented by the general formula (1), the structural unit represented by the general formula (2), and the structural unit represented by the general formula (3) or the general formula (4). When used as a pigment dispersant, the content of is not particularly limited and can be appropriately selected according to the purpose, but is preferably 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the pigment. 5 mass parts-80 mass parts are more preferable, and 10 mass parts-50 mass parts are still more preferable. When the content is within the preferred range, it is advantageous in that a high image density is obtained and the 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.

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.

(Dispersant)
As the pigment dispersant in the pigment dispersion, the structural unit represented by the general formula (1), the structural unit represented by the general formula (2), the general formula (3), or the general formula (4) The polymer containing the structural unit represented by this is preferable. Other usable dispersants include, for example, various surfactants such as anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, naphthalenesulfonic acid Na formalin condensate, polymer type And the like. 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 oleate, polyoxyethylene distearate, 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).

_{CF 3 CF 2 (CF 2 CF} 2) m-CH 2 CH 2 O (CH 2 CH 2 O) n H General Formula (I)
(However, in said general formula (I), m represents the integer of 0-10. N represents the integer of 1-40.)

(In the general formula (II), Rf represents a fluorine-containing group and is preferably a perfluoroalkyl group. M, n, and p each represents an integer, n is 1-4, m is 6-25, p. Is preferably 1 to 4.)
The perfluoroalkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms, such as -CnF _{2n + 1-} (where n represents an integer of 1 to 10). It is done. 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.

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 are preferably exemplified.
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 according to 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 though they are smaller than the nozzle opening, the ejection stability is deteriorated. Therefore, the average particle diameter (D50) is more preferably 200 nm or less in order not to disturb the ink ejection stability.

The water-dispersible resin has a function of fixing the water-dispersed colorant on the paper surface, and is preferably formed into a film at room temperature to improve the fixability of the color material.
Therefore, 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. Therefore, the water-dispersible resin has a glass transition temperature of −30 ° C. or higher. It is preferable.
The content of the water-dispersible resin in the inkjet 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 ink jet recording ink production method of the present invention includes, for example, water, a water-soluble organic solvent, a pigment, the structural unit represented by the general formula (1), and the structural unit represented by the general formula (2). In addition, a polymer containing the structural unit represented by the general formula (3) or the general formula (4) and, if necessary, other components may be dispersed or dissolved in an aqueous medium, and stirred and mixed. it can.
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.

The viscosity of the inkjet recording ink at 25 ° C. is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 mPa · s to 20 mPa · s, more preferably 5 mPa · s to 10 mPa · s. . 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, and 20 mN / m-30 mN / m are more preferable. When the surface tension is less than 20 mN / m, bleeding on the paper becomes remarkable and stable jetting may not be obtained. When the surface tension exceeds 40 mN / m, the ink does not sufficiently penetrate into the paper. , Drying time may be prolonged.

The stimulus for causing the ink droplets to fly can be generated, for example, by the stimulus generating means, and the stimulus is not particularly limited and can be appropriately selected according to the purpose, and includes heat (temperature), pressure , Vibration, light, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, heat and pressure are preferable.
Examples of the stimulus generating means include a heating device, a pressurizing device, a piezoelectric element, a vibration generating device, an ultrasonic oscillator, a light, and the like. Specifically, for example, a piezoelectric actuator such as a piezoelectric element, a heating resistor, etc. Examples thereof include a thermal actuator that uses a phase change caused by film boiling of a liquid using an electrothermal conversion element such as a body, a shape memory alloy actuator that uses a metal phase change caused by a temperature change, and an electrostatic actuator that uses an electrostatic force.

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

  The size of the droplets of the ink jet recording ink to be ejected is preferably 3 pl to 40 pl, for example, and the ejection speed is preferably 5 m / s to 20 m / s. The drive frequency is preferably 1 kHz or higher, and the resolution is preferably 300 dpi or higher.

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

  As described above, the ink for ink jet recording of the present invention is an ink jet head that uses a piezoelectric element as pressure generating means for pressurizing ink in an ink flow path and deforms a diaphragm that forms the wall surface of the ink flow path. A so-called piezo type that discharges ink droplets by changing the volume in the flow path (see Japanese Patent Laid-Open No. 2-51734), or generates air bubbles by heating ink in the ink flow path using a heating resistor. A so-called thermal type (see Japanese Patent Application Laid-Open No. 61-59911), a diaphragm that forms a wall surface of an ink flow path and an electrode are arranged to face each other, and the diaphragm is generated by an electrostatic force generated between the diaphragm and the electrode By changing the volume of the ink flow path, it is possible to change the volume of the ink flow path to discharge ink droplets (see JP-A-6-71882). It can be satisfactorily used in the printer for mounting Toheddo.

  The ink for ink jet recording of the present invention can be suitably used in various fields, and can be suitably used in an image forming apparatus (printer or the like) using an ink jet recording method. The ink for ink jet recording is heated at 50 ° C. to 200 ° C. and can be used for a printer or the like having a function of accelerating printing and fixing. ), An ink jet recording apparatus, a recorded material, and the recorded material.

<Ink container>
The ink container of the present invention includes an ink container for storing 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 method / recording apparatus>
The ink jet recording apparatus of the present invention records information or an image on a recording medium by ejecting the ink of the present invention from an ink jet head. This ink jet recording apparatus includes at least ink flying means, and further includes other means appropriately selected as necessary, for example, stimulus generation means, control means, and the like.
The ink jet recording method of the present invention includes at least an ink flying process, and further includes other processes appropriately selected as necessary, for example, a stimulus generation process, a control process, and the like. The ink jet recording method of the present invention can be preferably carried out by the ink jet recording apparatus of the present invention, and the ink flying step can be suitably carried out by the ink flying means. Moreover, the said other process can be suitably performed by the said other means.

-Ink flying process and ink flying means-
The ink flying step is a step of forming an image by applying a stimulus to the inkjet recording ink of the present invention and causing the recording ink to fly.
The ink flying means is means for forming an image by applying a stimulus to the ink for ink jet recording of the present invention and causing the ink for recording to fly. The ink flying means is not particularly limited, and examples thereof include various nozzles for ejecting ink.
In the present invention, it is preferable that at least a part of the liquid chamber portion, the fluid resistance portion, the vibration plate, and the nozzle member of the ink jet head is formed of a material containing at least one of silicon and nickel.
The nozzle diameter of the inkjet nozzle is preferably 30 μm or less, and preferably 1 μm to 20 μm.

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 feed tray 102, a half-moon roller (feeding) that separates and feeds the paper 142 one by one from the paper stacking unit 141 A separation pad 144 made of a material having a large coefficient of friction is provided facing the paper roller 143) and the paper feed roller 143, and the separation pad 144 is urged toward the paper feed roller 143 side.
As a transport unit for transporting the paper 142 fed from the paper feed unit below the recording head 134, a transport belt 151 for transporting the paper 142 by electrostatic adsorption and a guide 145 from the paper feed unit. The counter roller 152 for transporting the paper 142 fed via the transport belt 151 with the transport belt 151 and the paper 142 fed substantially vertically upward are changed by approximately 90 ° so as to follow the transport belt 151. 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. Further, 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, but the present invention can be similarly applied to a line type ink jet recording apparatus having a line type head.

  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 according to the purpose. Any paper can be used, but plain paper defined as follows is preferable.
That is, the ink of the present invention is preferably used for paper having an amount of Ca ions eluted from the paper of 1.0 × 10 ^{−4 to} 5.0 × 10 ⁻⁴ [g / g]. . When the amount of Ca ions is 1.0 × 10 ⁻⁴ [g / g] or more, the effect of improving the image density by reaction aggregation with the pigment dispersant is improved. Further, when the Ca ion amount is 5.0 × 10 ⁻⁴ [g / g] or less, since the ink penetration into the paper is not inhibited, the drying property of the ink is improved, and the scratch resistance and the marker resistance are also improved. .

The amount of Ca ions eluted from the paper can be calculated, for example, by the following method.
That is, the paper is filtered into a 2.5 cm (± 0.5 cm) × 3.5 cm (± 0.5 cm) square piece of paper and the cut pure water is filtered through a 0.8 μm cellulose acetate filter (manufactured by Advantech Co., Ltd.). Then, the Ca ions contained in the immersion liquid are quantified by an ICP emission spectroscopic analyzer. The Ca ion concentration [ppm] obtained here is multiplied by 200 g, which is the weight of high-purity water, and is further divided by 16 g, which is the weight of the immersed paper. The amount of Ca ions eluted from the paper [g / g ] Can be calculated.

Examples of the plain paper include MyPaper (manufactured by Ricoh Co., Ltd., the amount of Ca ions is 4.3 × 10 ⁻⁴ [g / g]), Xerox 4024 (manufactured by Fuji Xerox Co., Ltd., and the amount of Ca ions is 1.7 × 10 ^{− 4} [g / g]) and the like.

Besides the plain paper, for example, coated paper for printing, glossy paper, special paper, cloth, film, OHP sheet and the like can be mentioned. The said recording media may be used individually by 1 type, and may use 2 or more types together. 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.

<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. The column used was an aqueous SEC column TSKgel G3000PWXL (exclusion limit molecular weight 2 × 10 5) manufactured by Tosoh Corporation, TSKgel G5000PWXL (exclusion limit molecular weight 2.5 × 10 6), and TSKgel G6000PWXL (exclusion limit molecular weight 5 × 10 7). The sample was prepared to a concentration of 2 g / 100 mL with an eluent and used for measurement. As an eluent, an aqueous solution 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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) 30.0 parts by mass of R9 in the general formula (9), and a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom. 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 60.0 parts by mass, a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile was 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 (14) (1-acryloxyethane-1,1-diphosphonic acid) In the general formula (9), 30.0 parts by mass of R9 is a hydrogen atom, a compound represented by the structural formula (16) (diacetone methacrylamide, in the general formula (10), R10 is methyl. 10.0 parts by weight of the group), 60.0 parts by weight of the compound represented by the structural formula (20) (benzyl acrylate, R12 is a hydrogen atom in the general formula (12)), a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile was 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 30000.

(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 (14) (1-acryloxyethane-1,1-diphosphonic acid) In the general formula (9), R9 is a hydrogen atom. 30.0 parts by mass The compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom. 10.0 parts by mass, a compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom), 60.0 parts by mass, a polymerization initiator (azobisiso) Butyronitrile) 4.0 parts by mass was 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 28000.

(Synthesis Example 4)
-Synthesis of polymer 4-
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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) 30.0 parts by mass of R9 in the general formula (9), and a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom. 10.0 parts by mass of the compound represented by the structural formula (19) (benzyl methacrylate, R12 is a methyl group in the general formula (12)), 60.0 parts by mass of a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile was 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 4 in which phosphonic acid groups were neutralized 100% was synthesized. The weight average molecular weight of the obtained polymer 4 was 31,000.

(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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) 30.0 parts by mass of R9 in the general formula (9), and a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom. 10.0 parts by mass of the compound represented by the structural formula (18) (stearyl acrylate, R11 is a hydrogen atom in the general formula (11)) 60.0 parts by mass of a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile was 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 5 in which phosphonic acid groups were neutralized 100% was synthesized. The weight average molecular weight of the obtained polymer 5 was 32000.

(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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) 30.0 parts by mass of R9 in the general formula (9) and a compound represented by the structural formula (16) (diacetone methacrylamide, in the general formula (10), R10 is methyl. 10.0 parts by mass of the group), 60.0 parts by mass of the compound represented by the structural formula (18) (stearyl acrylate, R11 is a hydrogen atom in the general formula (11)), Azobisisobutyronitrile) (4.0 parts by mass) was 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 6 in which phosphonic acid groups were neutralized 100% was synthesized. The weight average molecular weight of the obtained polymer 6 was 29000.

(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 (14) (1-acryloxyethane-1,1-diphosphonic acid) 30.0 parts by mass of R9 in the general formula (9), and a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom. 10.0 parts by mass of the compound represented by the structural formula (18) (stearyl acrylate, R11 is a hydrogen atom in the general formula (11)) 60.0 parts by mass of a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile was 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, a polymer 7 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 7 was 33000.

(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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) 30.0 parts by mass of R9 in the general formula (9), and a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom. 10.0 parts by mass, a compound represented by the structural formula (17) (stearyl methacrylate, in the general formula (11), R 11 is a methyl group), 60.0 parts by mass, a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile was 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, a polymer 8 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 8 was 32,000.

(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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) 30.0 parts by mass of R9 in the general formula (9), and a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom. 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 60.0 parts by mass, a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile was 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, a polymer 9 having 50% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 9 was 30000.

(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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) 30.0 parts by mass of R9 in the general formula (9), and a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom. 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 60.0 parts by mass, a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile was 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, a polymer 10 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 10 was 31,000.

(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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) 30.0 parts by mass of R9 in the general formula (9) and a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom. 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 60.0 parts by mass, a polymerization initiator (azo Bisisobutyronitrile) 4.0 parts by mass was charged and the temperature was raised to 75 ° C. Next, after carrying out a polymerization reaction for 2 hours in 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 11 in which phosphonic acid groups were neutralized 100% was synthesized. The weight average molecular weight of the obtained polymer 11 was 2100.

(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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) 30.0 parts by mass of R9 in the general formula (9), and a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom. 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 60.0 parts by mass, a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile was charged and the temperature was raised to 65 ° C. Next, after conducting a polymerization reaction for 2.5 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 further drying. A polymer was obtained.
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 4200.

(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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) 30.0 parts by mass of R9 in the general formula (9), and a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom. 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 60.0 parts by mass, a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile) was 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 50000.

(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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) 30.0 parts by mass of R9 in the general formula (9), and a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom. 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 60.0 parts by mass, a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile) was 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 70000.

(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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (9), 5.0 parts by mass of R9 is a methyl group, and a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom. 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 85.0 parts by mass, a polymerization initiator (azo Bisisobutyronitrile) 4.0 parts by mass was charged and the temperature was raised to 75 ° C. Next, after carrying out a polymerization reaction for 2 hours in 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 15 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 15 was 2000.

(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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (9), 5.0 parts by mass of R9 is a methyl group, and a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom. 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 85.0 parts by mass, a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile was charged and the temperature was raised to 65 ° C. Next, after conducting a polymerization reaction for 2.5 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 further drying. A polymer was obtained.
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 4000.

(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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (9), 5.0 parts by mass of R9 is a methyl group, and a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom. 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 85.0 parts by mass, a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile) was 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 49000.

(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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (9), 5.0 parts by mass of R9 is a methyl group, and a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom. 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 85.0 parts by mass, a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile) was charged, and the temperature was raised to 50 ° C. Next, after carrying out the polymerization reaction for 48 hours in 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 69000.

(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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (9), 10.0 parts by mass of R9 is a methyl group, a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, R12 is a hydrogen atom in the general formula (12)), 80.0 parts by mass, a polymerization initiator (azo Bisisobutyronitrile) 4.0 parts by mass was charged and the temperature was raised to 75 ° C. Next, after carrying out a polymerization reaction for 2 hours in 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 19 in which phosphonic acid groups were neutralized 100% was synthesized. The weight average molecular weight of the obtained polymer 19 was 2200.

(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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (9), 10.0 parts by mass of R9 is a methyl group, a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, R12 is a hydrogen atom in the general formula (12)), 80.0 parts by mass, a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile was charged and the temperature was raised to 65 ° C. Next, after conducting a polymerization reaction for 2.5 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 further drying. A polymer was obtained.
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 4300.

(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 the compound represented by the structural formula (13) (1-methacryloxyethane-1,1-diphosphonic acid, In the general formula (9), 10.0 parts by mass of R9 is a methyl group, a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom 10.0 parts by mass, compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom), 80.0 parts by mass, a polymerization initiator (azobis) 4.0 parts by mass of (isobutyronitrile) was 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 50000.

(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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (9), 10.0 parts by mass of R9 is a methyl group, a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, R12 is a hydrogen atom in the general formula (12)), 80.0 parts by mass, a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile) was 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 68,000.

(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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (9), 60.0 parts by mass of R9 is a methyl group, a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 30.0 parts by mass, a polymerization initiator (azo Bisisobutyronitrile) 4.0 parts by mass was charged and the temperature was raised to 75 ° C. Next, after carrying out a polymerization reaction for 2 hours in 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 23 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 23 was 2100.

(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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (9), 60.0 parts by mass of R9 is a methyl group, a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 30.0 parts by mass, a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile was charged and the temperature was raised to 65 ° C. Next, after conducting a polymerization reaction for 2.5 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 further drying. A polymer was obtained.
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 4000.

(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 the compound represented by the structural formula (13) (1-methacryloxyethane-1,1-diphosphonic acid, In the general formula (9), 60.0 parts by mass of R9 is a methyl group, and the compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom. 10.0 parts by mass, compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom), 30.0 parts by mass, a polymerization initiator (azobis) 4.0 parts by mass of (isobutyronitrile) was 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 48,000.

(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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (9), 60.0 parts by mass of R9 is a methyl group, a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 30.0 parts by mass, a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile) was 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.

(Synthesis Example 27)
-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 represented by the structural formula (13) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (9), 80.0 parts by mass of R9 is a methyl group, a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 10.0 parts by mass, a polymerization initiator (azo Bisisobutyronitrile) 4.0 parts by mass was charged and the temperature was raised to 75 ° C. Next, after carrying out a polymerization reaction for 2 hours in 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 27 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 27 was 2200.

(Synthesis Example 28)
-Synthesis of polymer 28-
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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (9), 80.0 parts by mass of R9 is a methyl group, a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 10.0 parts by mass, a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile was charged and the temperature was raised to 65 ° C. Next, after carrying out the polymerization reaction for 2.5 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 further drying. A polymer was obtained.
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 28 in which phosphonic acid groups were neutralized 100% was synthesized. The weight average molecular weight of the obtained polymer 28 was 4200.

(Synthesis Example 29)
-Synthesis of polymer 29-
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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (9), 80.0 parts by mass of R9 is a methyl group, a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 10.0 parts by mass, a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile) was 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 29 in which phosphonic acid groups were neutralized 100% was synthesized. The weight average molecular weight of the obtained polymer 29 was 49000.

(Synthesis Example 30)
-Synthesis of polymer 30-
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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (9), 80.0 parts by mass of R9 is a methyl group, a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom 10.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 10.0 parts by mass, a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile) was 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 30 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 30 was 70000.

(Synthesis Example 31)
-Synthesis of polymer 31-
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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (9), 5.0 parts by mass of R9 is a methyl group, and a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom. 5.0 parts by mass, 90.0 parts by mass of the compound represented by the structural formula (20) (benzyl acrylate, R12 is a hydrogen atom in the general formula (12)), a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile was 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, a polymer 31 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 31 was 28000.

(Synthesis Example 32)
-Synthesis of polymer 32-
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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (9), 60.0 parts by mass of R9 is a methyl group, a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom 30.0 parts by mass, a compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 10.0 parts by mass, a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile was 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, a polymer 32 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 32 was 31,000.

(Synthesis Example 33)
-Synthesis of polymer 33-
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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (9), 80.0 parts by mass of R9 is a methyl group, a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom 15.0 parts by mass, a compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 5.0 parts by mass, a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile was 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, a polymer 33 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 33 was 29000.

(Synthesis Example 34)
-Synthesis of polymer 34-
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 (13) (1-methacryloxyethane-1,1-diphosphonic acid) In the general formula (9), 5.0 parts by mass of R9 is a methyl group, and a compound represented by the structural formula (15) (diacetone acrylamide, in the general formula (10), R10 is a hydrogen atom. 90.0 parts by mass, a compound represented by the structural formula (20) (benzyl acrylate, in the general formula (12), R12 is a hydrogen atom) 5.0 parts by mass, a polymerization initiator (azo 4.0 parts by mass of bisisobutyronitrile was 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, a polymer 34 having 100% neutralized phosphonic acid groups was synthesized. The weight average molecular weight of the obtained polymer 34 was 32,000.

(Comparative Synthesis Example 1)
-Synthesis of polymer 35-
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 (21) (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 35 was 5,100.

(Comparative Synthesis Example 2)
While diluting hydroxyethylidene diphosphonic acid (HEDP) represented by the following structural formula (22) 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 above synthesis examples and comparative 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-, instead of 20.0 parts by mass of polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, polymer 2 aqueous solution of synthesis example 2 (solid content 10% by mass) 20. An ink was obtained in the same manner as in Example 1 except that 0 part by mass was used.

(Example 3)
In Example 1 -Preparation of ink-, instead of 20.0 parts by mass of the polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, the polymer 3 aqueous solution of synthesis example 3 (solid content 10% by mass) 20. An ink was obtained in the same manner as in Example 1 except that 0 part by mass was used.

Example 4
In Example 1 —Preparation of ink—, instead of 20.0 parts by mass of the polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, 20% of the polymer 4 aqueous solution (solid content 10% by mass) of synthesis example 4 An ink was obtained in the same manner as in Example 1 except that 0 part by mass was used.

(Example 5)
In Example 1 -Preparation of ink-, instead of 20.0 parts by mass of the polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, 20% of the polymer 5 aqueous solution (solid content 10% by mass) of synthesis example 5 An ink was obtained in the same manner as in Example 1 except that 0 part by mass was used.

(Example 6)
In Example 1 -Preparation of ink-, instead of 20.0 parts by mass of the polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, the polymer 6 aqueous solution of synthesis example 6 (solid content 10% by mass) 20. An ink was obtained in the same manner as in Example 1 except that 0 part by mass was used.

(Example 7)
In Example 1 -Preparation of ink-, instead of 20.0 parts by mass of the aqueous polymer 1 solution (solid content 10% by mass) of synthesis example 1, the aqueous polymer 7 solution (solid content 10% by mass) of synthesis example 7 An ink was obtained in the same manner as in Example 1 except that 0 part by mass was used.

(Example 8)
In Example 1 —Preparation of ink—, instead of 20.0 parts by mass of the polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, the polymer 8 aqueous solution of synthesis example 8 (solid content 10% by mass) 20. An ink was obtained in the same manner as in Example 1 except that 0 part by mass was used.

Example 9
-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 using a disk-type bead mill (Shinmaru Enterprises Co., Ltd., KDL type, medium: zirconia ball having a diameter of 0.1 mm). A pigment dispersion of Example 9 was obtained by filtration through a membrane filter having a pore size of 1.2 μm.

-Preparation of ink-
-Pigment dispersion of Example 9 (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 10)
In Example 9 -Preparation of pigment dispersion-, instead of 20.0 parts by mass of carbon black (NIPEX 150, manufactured by Degussa), Pigment Blue 15: 3 (Dainipei Seika Co., Ltd., Chromofine Blue Cyan Pigment) 20 A pigment dispersion of Example 10 was produced in the same manner as Example 9 except that 0.0 part by mass was used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content of 20% by mass), the pigment dispersion of Example 10 (pigment solid content of 20). (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 11)
In Example 9 -Preparation of pigment dispersion-, instead of 20.0 parts by mass of carbon black (NIPEX 150, manufactured by Degussa), 20.0 parts by mass of Pigment Red 122 (manufactured by Clariant, toner magenta EO02 magenta pigment) A pigment dispersion of Example 11 was produced in the same manner as Example 9 except that was used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content of 20% by mass), the pigment dispersion of Example 11 (pigment solid content of 20). (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 12)
In Example 9 -Preparation of pigment dispersion-, instead of 20.0 parts by mass of carbon black (NIPEX 150, manufactured by Degussa), 20.0 parts by mass of pigment yellow (Daiichi Seika Co., Ltd., First Yellow 531 yellow pigment) A pigment dispersion of Example 12 was produced in the same manner as Example 9 except that the parts were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content of 20% by mass), the pigment dispersion of Example 12 (pigment solid content of 20). (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 13)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of polymer 1 aqueous solution (solid content: 10% by mass) of synthesis example 1, polymer 2 aqueous solution (solid content: 10% by mass) of synthesis example 2 A pigment dispersion of Example 13 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 13 (pigment solid content 20) (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 14)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, polymer 3 aqueous solution of synthesis example 3 (solid content 10% by mass) A pigment dispersion of Example 14 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content of 20% by mass), the pigment dispersion of Example 14 (pigment solid content of 20). (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 15)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of the polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, the polymer 4 aqueous solution (solid content 10% by mass) of synthesis example 4 A pigment dispersion of Example 15 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 15 (pigment solid content 20). (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 16)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, polymer 5 aqueous solution of synthesis example 5 (solid content 10% by mass) A pigment dispersion of Example 16 was produced in the same manner as in Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 16 (pigment solid content 20). (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 17)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, polymer 6 aqueous solution (solid content 10% by mass) of synthesis example 6 A pigment dispersion of Example 17 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 17 (pigment solid content 20) (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 18)
In Example 9 —Preparation of Pigment Dispersion—, instead of 20.0 parts by mass of Polymer 1 aqueous solution (solid content: 10% by mass) of Synthesis Example 1, polymer 7 aqueous solution (solid content: 10% by mass) of Synthesis Example 7 A pigment dispersion of Example 18 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content of 20% by mass), the pigment dispersion of Example 18 (pigment solid content of 20). (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 19)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, polymer 8 aqueous solution of synthesis example 8 (solid content 10% by mass) A pigment dispersion of Example 19 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 19 (pigment solid content 20). (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 20)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, polymer 9 aqueous solution (solid content 10% by mass) of synthesis example 9 A pigment dispersion of Example 20 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion (pigment solid content 20 mass%) of Example 9, the pigment dispersion (pigment solid content 20) of Example 20 was used. (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 21)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, polymer 10 aqueous solution (solid content 10% by mass) of synthesis example 10 A pigment dispersion of Example 21 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content of 20% by mass), the pigment dispersion of Example 21 (pigment solid content of 20). (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 22)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, polymer 11 aqueous solution of synthesis example 11 (solid content 10% by mass) A pigment dispersion of Example 22 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 22 (pigment solid content 20) (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 23)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of polymer 1 aqueous solution (solid content: 10% by mass) of synthesis example 1, polymer 12 aqueous solution of synthesis example 12 (solid content: 10% by mass) A pigment dispersion of Example 23 was produced in the same manner as in Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 23 (pigment solid content 20) (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 24)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, polymer 13 aqueous solution of synthesis example 13 (solid content 10% by mass) A pigment dispersion of Example 24 was produced in the same manner as in Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion (pigment solid content 20% by mass) of Example 9, the pigment dispersion (pigment solid content 20) of Example 24 was used. (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 25)
In Example 9 —Preparation of Pigment Dispersion—, instead of 20.0 parts by mass of Polymer 1 aqueous solution (solid content 10% by mass) of Synthesis Example 1, polymer 14 aqueous solution of Synthesis Example 14 (solid content 10% by mass) A pigment dispersion of Example 25 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 25 (pigment solid content 20) (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 26)
In Example 9 -Preparation of pigment dispersion-, instead of 20.0 parts by mass of polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, polymer 15 aqueous solution of synthesis example 15 (solid content 10% by mass) A pigment dispersion of Example 26 was produced in the same manner as in Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content of 20% by mass), the pigment dispersion of Example 26 (pigment solid content of 20). (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 27)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of the polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, the polymer 16 aqueous solution of synthesis example 16 (solid content 10% by mass) A pigment dispersion of Example 27 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 27 (pigment solid content 20) (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 28)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of the aqueous polymer 1 solution of synthesis example 1 (solid content of 10% by mass), the aqueous solution of polymer 17 of synthesis example 17 (solid content of 10% by mass) A pigment dispersion of Example 28 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 28 (pigment solid content 20). (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 29)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of the aqueous polymer 1 solution of synthesis example 1 (solid content of 10% by mass), the aqueous solution of polymer 18 of synthesis example 18 (solid content of 10% by mass) A pigment dispersion of Example 29 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 29 (pigment solid content 20) (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 30)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, polymer 19 aqueous solution of synthesis example 19 (solid content 10% by mass) A pigment dispersion of Example 30 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 30 (pigment solid content 20) (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 31)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, polymer 20 aqueous solution of synthesis example 20 (solid content 10% by mass) A pigment dispersion of Example 31 was produced in the same manner as in Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 31 (pigment solid content 20) (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 32)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, polymer 21 aqueous solution of synthesis example 21 (solid content 10% by mass) A pigment dispersion of Example 32 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 32 (pigment solid content 20) (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 33)
In Example 9 —Preparation of Pigment Dispersion—, instead of 20.0 parts by mass of the aqueous polymer 1 solution of synthesis example 1 (solid content of 10% by mass), the aqueous solution of polymer 22 of synthesis example 22 (solid content of 10% by mass) A pigment dispersion of Example 33 was produced in the same manner as in Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 —Preparation of ink—, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content of 20% by mass), the pigment dispersion of Example 33 (pigment solid content of 20) (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 34)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of the polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, the polymer 23 aqueous solution of synthesis example 23 (solid content 10% by mass) A pigment dispersion of Example 34 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 34 (pigment solid content 20) (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 35)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, polymer 24 aqueous solution of synthesis example 24 (solid content 10% by mass) A pigment dispersion of Example 35 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 35 (pigment solid content 20) (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 36)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, polymer 25 aqueous solution of synthesis example 25 (solid content 10% by mass) A pigment dispersion of Example 36 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 36 (pigment solid content 20) (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 37)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, polymer 26 aqueous solution of synthesis example 26 (solid content 10% by mass) A pigment dispersion of Example 37 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion (pigment solid content 20 mass%) of Example 9, the pigment dispersion (pigment solid content 20) of Example 37 was used. (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 38)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, polymer 27 aqueous solution of synthesis example 27 (solid content 10% by mass) A pigment dispersion of Example 38 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 38 (pigment solid content 20) (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 39)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of the aqueous polymer 1 solution of synthesis example 1 (solid content of 10% by mass), the aqueous solution of polymer 28 of synthesis example 28 (solid content of 10% by mass) A pigment dispersion of Example 39 was produced in the same manner as in Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion (pigment solid content 20% by mass) of Example 9, the pigment dispersion (pigment solid content 20) of Example 39 was used. (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 40)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of the polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, the polymer 29 aqueous solution of synthesis example 29 (solid content 10% by mass) A pigment dispersion of Example 40 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 40 (pigment solid content 20) (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 41)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of the polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, the polymer 30 aqueous solution of synthesis example 30 (solid content 10% by mass) A pigment dispersion of Example 41 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content of 20% by mass), the pigment dispersion of Example 41 (pigment solid content of 20). (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 42)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of polymer 1 aqueous solution (solid content: 10% by mass) of synthesis example 1, polymer 31 aqueous solution of synthesis example 31 (solid content: 10% by mass) A pigment dispersion of Example 42 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 42 (pigment solid content 20). (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 43)
In Example 9 —Preparation of Pigment Dispersion—, in place of 20.0 parts by mass of Polymer 1 aqueous solution (solid content 10% by mass) of Synthesis Example 1, polymer 32 aqueous solution of Synthesis Example 32 (solid content 10% by mass) A pigment dispersion of Example 43 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 43 (pigment solid content 20) (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 44)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of the aqueous polymer 1 solution of synthesis example 1 (solid content of 10% by mass), the aqueous solution of polymer 33 of synthesis example 33 (solid content of 10% by mass) A pigment dispersion of Example 44 was produced in the same manner as Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 44 (pigment solid content 20) (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Example 45)
In Example 9 -Preparation of pigment dispersion-, in place of 20.0 parts by mass of the polymer 1 aqueous solution (solid content 10% by mass) of synthesis example 1, the polymer 34 aqueous solution of synthesis example 34 (solid content 10% by mass) A pigment dispersion of Example 45 was produced in the same manner as in Example 9 except that 20.0 parts by mass were used.
Subsequently, in Example 9 -Preparation of ink-, instead of 40.0 parts by mass of the pigment dispersion of Example 9 (pigment solid content 20 mass%), the pigment dispersion of Example 45 (pigment solid content 20 (Mass%) An ink was obtained in the same manner as in Example 9 except that 40.0 parts by mass were used.

(Comparative Example 1)
In Example 1 —Preparation of Ink—, instead of 20.0 parts by mass of Polymer 1 aqueous solution (solid content 10% by mass) of Synthesis Example 1, 20 polymer 35 aqueous solution (solid content 10% by mass) 20 of Comparative Synthesis Example 1 An ink was obtained in the same manner as in Example 1 except that 0.0 part by mass was used.

(Comparative Example 2)
In Example 1-Preparation of ink-In place of 20.0 parts by mass of the polymer 1 aqueous solution (solid content: 10% by mass) of Synthesis Example 1, the potassium hydroxyethylidene diphosphonate aqueous solution (Solid content: 10% by mass) of Comparative Synthesis Example 2 %) An ink was obtained in the same manner as in Example 1 except that 20.0 parts by mass were used.

The following evaluations were 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 2 weeks, 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 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 supply 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 (14)

Water, water-soluble organic solvents, pigments,
A polymer comprising a structural unit represented by the following general formula (1), a structural unit represented by the following general formula (2), and a structural unit represented by the following general formula (3) or general formula (4) An ink for inkjet recording, comprising:

(In general formula (1), R 1 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.)

(In the general formula (2), R2 represents a methyl group or a hydrogen atom.)

(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.)   2. The ink for inkjet recording according to claim 1, wherein the content of the structural unit represented by the general formula (1) in 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 the 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 the structural unit represented by the general formula (3) of the polymer is represented by the following structural formula (7).

The ink for inkjet recording according to any one of claims 1 to 5, wherein the structural unit represented by the general formula (4) of the polymer is represented by the following structural formula (8).

The ink for inkjet recording according to any one of claims 1 to 6, wherein M ^{+ of the} structural unit represented by the general formula (1) or the general formula (5) is a potassium ion. The ink for ink jet recording according to any one of claims 1 to 7 , wherein the polymer has a weight average molecular weight of 4,000 to 50,000. The ink for ink jet recording according to any one of claims 1 to 8 , wherein the polymer is a dispersant for the pigment . It is a manufacturing method of the ink for inkjet recording of Claim 1, Comprising:
The polymer includes at least a compound represented by the following general formula (9), a compound represented by the following general formula (10), and a compound represented by the following general formula (11) or the general formula (12). A method for producing an ink for ink jet recording , characterized by being synthesized by copolymerizing a starting material and then treating with any of an alkali metal base and an organic amine base.

(In general formula (9), R9 represents a methyl group or a hydrogen atom.)

(In general formula (10), R10 represents a methyl group or a hydrogen atom.)

(In the general formula (11), R11 represents a methyl group or a hydrogen atom.)

(In the general formula (12), R12 represents a methyl group or a hydrogen atom.) 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 9. Ink container. An ink jet recording apparatus that records information or an image on a recording medium by ejecting ink from an ink jet head, wherein the ink is the ink for ink jet recording according to any one of claims 1 to 9. Inkjet recording device. A method for producing a recorded product comprising a step of recording on a recording medium by discharging ink from an inkjet head, wherein the ink is the inkjet recording ink according to any one of claims 1 to 9. 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 9 .

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