JP6018000B2 - Ink jet recording ink, ink cartridge, ink jet recording method, ink jet recording apparatus, ink recorded matter - Google Patents

Description

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

In recent years, as an image forming method, since the process is simple and full color can be easily obtained as compared with other recording methods, there is an advantage that a high-resolution image can be obtained even with an apparatus having a simple configuration. The method has become widespread.
Inkjet recording is a method in which a small amount of ink is ejected with bubbles generated by heat, pressure generated by using piezoelectricity or static electricity, and the ink is attached to a recording medium such as paper and dried quickly (or recording). This is a method of forming an image (by penetrating into a medium), and its application has been expanded to personal and industrial printers and printing.
In the ink jet recording apparatus, water-based ink using a water-soluble dye as a coloring material is mainly used, but the dye ink has a defect that it is inferior in weather resistance and water resistance. Therefore, in recent years, research on pigment inks using pigments instead of water-soluble dyes has been advanced.

However, pigment inks are inferior in color development, ink ejection stability, and storage stability to dye inks. In addition, with the improvement of image quality improvement technology for OA printers, even higher image density is required even when pigment ink is used for plain paper. However, when using plain paper, the pigment ink has a problem that when it penetrates into the paper, the pigment concentration on the paper surface becomes low and the image density becomes low.
In recent years, demand for industrial applications has increased, and high-speed printing is desired. Ink jet printers equipped with line heads have been proposed along with high-speed printing. In order to increase the drying speed of the ink adhering to the recording medium for high-speed printing, a means for adding a penetrant to the ink and allowing water to penetrate into the recording medium is taken. There is a problem that the permeability is increased and the image density is further decreased.

  In the case of plain paper, immediately after printing, the surface of the plain paper is swollen by water, which is a solvent for the ink, and the difference in elongation between the front and back is increased to cause curling. Since this phenomenon disappears as drying progresses, it has not become a problem in low-speed printing. However, with high-speed printing, it is necessary to transport the recording medium without curling after printing, which causes a paper jam problem. For curling, a means for increasing the amount of the water-soluble organic solvent contained in the ink is effective. However, since the ink is more hydrophobic, it is difficult to ensure the storage stability of the ink.

Patent Document 1 describes an ink excellent in ink ejection properties and image blocking resistance, which contains an aqueous solvent, a pigment, a water-insoluble polymer dispersant, and a self-dispersing polymer. Moreover, the monomer which has a phosphoric acid group is described as a monomer of the said water-insoluble polymer. However, there is no exemplification of a copolymer using the monomers of (Formula 7) and (Formula 8) of the present invention, and the effect of improving the dispersibility and image density of the self-dispersing polymer is not described.
Patent Document 2 discloses an ultraviolet curable ink jet comprising a white pigment and a polymer dispersant made of a vinyl polymer having a substituent consisting of an acid or a salt thereof at the end and a sulfonyl group or a phosphonyl group in the molecule. White ink compositions are described. Examples of the polymer dispersant include terminal ammonium phosphate salts of polymethacrylic acid derivatives, but there are no examples of copolymers using the monomers of (Formula 7) and (Formula 8) of the present invention, The effect of improving the image density when the polymer dispersant is used is not described.
Further, Patent Document 3 discloses that the fixing property and the printing paper containing the polyvalent water-soluble metal salt, the pigment, and the ink containing the compound having a specific phosphoric acid group having no surfactant ability are combined. It is described that the image density is improved. However, the effect of improving the dispersibility and image density of the ink is not described, and examples of the copolymer of the phosphate group-containing monomer and (Formula 6), (Formula 7) or (Formula 8) of the present invention are also exemplified. Absent.

  The present invention solves the above-mentioned conventional problems, and a high image density can be obtained even on plain paper having a low content of water-soluble polyvalent metal salt, and storage stability is maintained even when the water-soluble organic solvent exceeds 20% by mass. An object of the present invention is to provide an ink for inkjet recording excellent in the above.

（式１）中、Ｍ^＋は半数以上がアルカリ金属イオン、有機アンモニウムイオンであり、残りはプロトンである。Ｒ１はメチル基又は水素原子を表す。ｎ、ｍは、それぞれ０〜６の整数を表す（但し、ｎ、ｍは同時に０であってはならない）。

（式２）中、Ｒ２はメチル基又は水素原子を表す。

（式３）中、Ｒ３はメチル基又は水素原子を表す。

（式４）中、Ｒ４はメチル基又は水素原子を表す。 The above problem is solved by the following invention 1).
1) In an inkjet recording ink containing at least water, a water-soluble organic solvent, a pigment, and a copolymer having a phosphoric acid group, the copolymer comprises a structural unit represented by the following (formula 1) and the following ( An ink for inkjet recording, comprising at least a structural unit represented by Formula 2) and a structural unit represented by the following (Formula 3) or (Formula 4).

In (Formula 1), more than half of M ⁺ are alkali metal ions and organic ammonium ions, and the rest are protons. R1 represents a methyl group or a hydrogen atom. n and m each represent an integer of 0 to 6 (provided that n and m must not be 0 at the same time).

In (Formula 2), R2 represents a methyl group or a hydrogen atom.

In (Formula 3), R3 represents a methyl group or a hydrogen atom.

In (Formula 4), R4 represents a methyl group or a hydrogen atom.

  According to the present invention, an ink for ink jet recording which can obtain a high image density even on plain paper having a small content of water-soluble polyvalent metal salt and has excellent storage stability even when the water-soluble organic solvent exceeds 20% by mass. Can be provided.

FIG. 3 is an explanatory diagram illustrating an example of an ink cartridge according to the invention. FIG. 2 is an explanatory diagram including the case (exterior) of the ink cartridge of FIG. 1 is a schematic diagram showing an example of a serial type ink jet recording apparatus of the present invention. FIG. 4 is a partially enlarged explanatory view of the inkjet recording apparatus shown in FIG. 3. FIG. 4 is another partially enlarged explanatory view of the ink jet recording apparatus shown in FIG. 3.

（式５）中、Ｒ５はメチル基又は水素原子を表す。ｎ、ｍは、それぞれ０〜６の整数を表す（但し、ｎ、ｍは同時に０であってはならない）。

（式６）中、Ｒ６はメチル基又は水素原子を表す。

（式７）中、Ｒ７はメチル基又は水素原子を表す。

（式８）中、Ｒ８はメチル基又は水素原子を表す。
５） １）〜４）のいずれかに記載のインクジェット記録用インクを容器中に収容したことを特徴とするインクカートリッジ。
６） ５）記載のインクカートリッジを搭載したことを特徴とするインクジェット記録装置。
７） １）〜４）のいずれかに記載のインクジェット記録用インクに刺激を印加し飛翔させて画像を記録するインク飛翔工程を少なくとも含むことを特徴とするインクジェット記録方法。
８） 記録媒体上に、１）〜４）のいずれかに記載のインクジェット記録用インクにより記録された画像を有することを特徴とするインク記録物。 Hereinafter, the present invention 1) will be described in detail, but the following 2) to 8) are also included in the embodiments of the present invention, and these will be described together.
2) The ink for inkjet recording according to 1), wherein the content of the structural unit of (Formula 1) in the copolymer is 10 to 60% by mass.
3) The ink for inkjet recording according to 1) or 2), wherein the copolymer has a mass average molecular weight of 5,000 to 50,000.
4) In an inkjet recording ink containing at least water, a water-soluble organic solvent, a pigment, and a copolymer having a phosphate group, the copolymer includes at least a monomer represented by the following (formula 5), An ink for inkjet recording, which is obtained by copolymerizing a monomer represented by formula (6) and a monomer represented by formula (7) or (8) below.

In (Formula 5), R5 represents a methyl group or a hydrogen atom. n and m each represent an integer of 0 to 6 (provided that n and m must not be 0 at the same time).

In (Formula 6), R6 represents a methyl group or a hydrogen atom.

In (Formula 7), R7 represents a methyl group or a hydrogen atom.

In Formula 8, R8 represents a methyl group or a hydrogen atom.
5) An ink cartridge comprising the ink for ink jet recording according to any one of 1) to 4) contained in a container.
6) An ink jet recording apparatus comprising the ink cartridge according to 5).
7) An ink jet recording method comprising at least an ink flying step of recording an image by applying a stimulus to the ink for ink jet recording according to any one of 1) to 4) and flying the ink.
8) An ink recorded matter having an image recorded with the ink for inkjet recording according to any one of 1) to 4) on a recording medium.

The mechanism of pigment aggregation when the ink of the present invention is used is not clear, but is presumed as follows.
The phosphate group or phosphate group salt in the structural unit represented by (Formula 1) has high affinity with the polyvalent metal ion, and quickly coordinates to the polyvalent metal ion eluted from the recording medium. To do.
When the copolymer containing a phosphate group salt of the present invention is used as a dispersant, the copolymer is mostly adsorbed on the pigment in the ink. Here, when the phosphate group or the salt of the phosphate group in the structural unit represented by (Formula 1) is coordinated with the polyvalent metal ion eluted from the recording medium, the following (1) to (3) ), The dispersion stability of the pigment in the ink is lowered, and the pigment is aggregated.
(1) Since the valence of the counter ion increases, the electrostatic repulsion between the pigments decreases.
(2) Since the solubility of the copolymer containing the phosphate group salt of the present invention in the ink is reduced, the polymer adsorption layer is reduced and the steric repulsion between the pigments is reduced.
(3) Since the solubility of the copolymer containing the phosphate group salt of the present invention in the ink is lowered, the hydration stability of the pigment including the copolymer containing the phosphate group salt of the present invention is improved. descend.
Further, when the copolymer containing a phosphate group salt of the present invention is used as an additive, it itself coordinates to a polyvalent metal ion eluted from a recording medium to form an insoluble material, which is agglomerated. It becomes the core of and causes pigment aggregation.

[Ink for inkjet recording]
The ink for inkjet recording of the present invention (hereinafter sometimes referred to as ink) includes, as a copolymer, a structural unit having a phosphate group represented by (Formula 1) and a structural unit represented by (Formula 2). And including the structural unit represented by (Formula 3) or (Formula 4). Note that the arrangement of (C ₂ H ₄ O) and (C ₃ H ₆ O) in (Formula 1) may be block-like or random.
Although the structural unit of (Formula 1) exhibits hydrophilicity, it has a characteristic of exhibiting hydrophobicity by binding to a polyvalent metal ion (particularly calcium ion). Therefore, when an ink containing a copolymer having a structural unit of (Formula 1) is used and an image is formed on a printing paper containing a polyvalent water-soluble metal salt, the polyvalent elution from the paper to the ink The structural unit of (Formula 1) is hydrophobized by metal ions, and the pigment is entrapped and aggregated, so that the pigment remains on the paper surface and the image density is improved.
However, in the case of plain paper, the contained polyvalent metal salt is generally poorly water-soluble calcium carbonate, and the amount of calcium ions eluted into the ink is small. Therefore, it is not possible to obtain a sufficient image density only by having the structural unit of (Formula 1).

One method for solving this problem is to increase the ratio of the structural unit (formula 1) in the copolymer having a phosphate group. However, when the ratio of the structural unit of (Formula 1) is increased, the interaction between the phosphoric acid groups becomes stronger, or the gelation of the copolymer occurs and the storage stability of the ink is lowered. Therefore, in the case of using a copolymer having a phosphate group in the prior art, the ratio of the structural unit having a phosphate group has to be less than 20% by mass.
On the other hand, in the present invention, in addition to the structural unit of (Formula 1), the structural unit of (Formula 2) and (Formula 3) or (Formula 4) is combined. The effect of agglomeration was improved, and the storage stability was improved even with an ink containing a large amount of water-soluble organic solvent. Further, the gelation of the copolymer is less likely to occur, the ratio of the structural unit of (Formula 1) can be increased, and the reactivity with polyvalent metal ions (particularly calcium ions) can be further improved. .
The structural unit of (Formula 3) or (Formula 4) is particularly good in the affinity with the pigment. The combined use with the structural unit of (Formula 2) improves the affinity for the pigment and makes the copolymer gelled. The suppression effect appears.
Thus, in the ink of the present invention, the water-soluble polyvalent metal salt is obtained by combining the structural unit of (Formula 1) and (Formula 2) with the structural unit of (Formula 3) or (Formula 4). Even with a small amount of plain paper, a high image density can be obtained.

  The ink of the present invention contains at least water, a water-soluble organic solvent, a pigment, and a copolymer having a phosphate group, and further contains other components as necessary. Hereinafter, each of these components will be described in order.

<Copolymer having phosphate group>
The copolymer having a phosphate group used in the present invention is a structural unit represented by (Formula 1), a structural unit represented by (Formula 2), and a structural unit represented by (Formula 3) or (Formula 4). And at least. This copolymer is obtained by copolymerizing at least the monomer of (Formula 5) and (Formula 6) and the monomer of (Formula 7) or (Formula 8). Note that the arrangement of (C ₂ H ₄ O) and (C ₃ H ₆ O) in (Formula 5) may be block-like or random.
A conventional general method can be used as the copolymerization method. For example, a solvent in a flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, and a monomer of (Formula 5) (Formula 6) and (Formula 7) or (Formula 8), using a polymerization initiator, nitrogen gas What is necessary is just to make it react at the temperature of about 60-150 degreeC under recirculation | reflux.
The molecular weight of the copolymer can be controlled by adjusting the monomer concentration during polymerization and / or the amount of polymerization initiator.

  Examples of the monomer of (Formula 5) to (Formula 8) include the following (Formula 5-1) to (Formula 5-5), (Formula 6-1) (Formula 6-2), and (Formula 7-1). (Formula 7-2), (Formula 8-1) (Formula 8-2) are mentioned.

The ratio of the structural unit of (Formula 1) in the copolymer having a phosphate group is preferably 10 to 80% by mass, more preferably 10 to 60% by mass, based on the mass of the copolymer. Within the above range, the image density, dispersibility, and storage stability are the best. Further, from the viewpoint of affinity to the pigment and suppression of gelation, the ratio of the structural unit of (Formula 2) is preferably 5 to 35% by mass, and the ratio of the structural unit of (Formula 3) or (Formula 4) is 10 to 70. Mass% is preferred.
The mass average molecular weight of the copolymer having a phosphate group is preferably 3000 to 60000, more preferably 5000 to 50000, and still more preferably 6000 to 30000.
The content of the copolymer having a phosphoric acid group is 0.05 to 10.0% by mass, preferably 0.5 to 5% by mass, more preferably 1 to 3% by mass as a solid content with respect to the total mass of the ink. It is.
The effect of improving the image density starts to appear from 0.05% by mass, and by making it 10.0% by mass or less, it is possible to keep the viscosity within a range suitable for ejecting ink from the head.

When a copolymer having a phosphoric acid group is used as a pigment dispersant, the image density on plain paper and the storage stability of an ink having a water-soluble organic solvent of 20% by mass or more are further improved.
When used as a dispersant, the content is 1 to 100% by mass, preferably 5 to 80% by mass, and more preferably 10 to 50% by mass with respect to 100% by mass of the pigment. The most suitable pigment particle diameter within this range is obtained, and the image density, dispersibility and storage stability are good.

  The phosphate group in the copolymer having a phosphate group is preferably partially or completely neutralized with a base and ionized. Bases used for neutralization include alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide, ammonium, mono, di or trimethylamine, mono, di or triethylamine, monoethanolamine, diethanolamine, triethanolamine, methylethanol Amine, methyldiethanolamine, dimethylethanolamine, choline, aminoethanepropanediol, monopropanolamine, dipropanolamine, tripropanolamine, isopropanolamine, trishydroxymethylaminomethane, aminoethylpropanediol, tetramethylammonium, tetraethylammonium, tetra Organic ammonium such as butylammonium, monophorin, N-methylmonoformin, N-methyl-2pyrrolidone, 2 Organic ammonium and cyclic amines pyrrolidone, and the like.

<Water>
The ink of the present invention uses water as a liquid medium. As water, ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or the like can be used.
<Water-soluble organic solvent>
The ink of the present invention uses a water-soluble organic solvent as a wetting agent for preventing drying of the ink, and for the purpose of improving dispersion stability and preventing curling of plain paper. A mixture of a plurality of these water-soluble organic solvents may be used.

Specific examples of the water-soluble organic solvent include the following.
Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1, 5-pentanediol, 1,6-hexanediol, glycerin, isopropylideneglycerol, trimethylolethane, trimethylolpropane, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,2,6- Polyhydric alcohols such as hexanetriol and petriol;
Polyhydric alcohol alkyl ethers 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;
Nitrogen-containing heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, γ-butyrolactone;
Amides such as formamide, N-methylformamide, N, N-dimethylformamide, N, N-dimethyl-β-methoxypropionamide, N, N-dimethyl-β-butoxypropionamide;
Amines such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine;
Sulfur-containing compounds such as dimethyl sulfoxide, sulfolane, thiodiethanol;
3-ethyl-3-hydroxymethyloxetane, propylene carbonate, ethylene carbonate

Among these water-soluble organic solvents, 3-ethyl-3-hydroxymethyloxetane, isopropylideneglycerol, N, N-dimethyl-β-methoxypropionamide, and N, N-dimethyl-β-butoxypropionamide are particularly preferable. These are excellent in preventing curling in plain paper.
In addition, 1,3-butanediol, diethylene glycol, 2,2,4-trimethyl-1,3-pentanediol, triethylene glycol, and / or glycerin are excellent in preventing ejection failure due to moisture evaporation.

In addition to the above, sugar may be included as a wetting agent. Examples of saccharides include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), and polysaccharides. Preferred are 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.
Examples of derivatives of these saccharides include reducing sugars, oxidized sugars, amino acids, and thioacids of the aforementioned saccharides. Sugar alcohol is particularly preferable, and specific examples include maltitol and sorbit.

The ratio of the pigment to the water-soluble organic solvent greatly affects the ejection stability of the ink from the head. If the amount of the water-soluble organic solvent is small even though the pigment solid content is high, the evaporation of water near the ink meniscus of the nozzle advances, resulting in ejection failure.
The blending amount of the water-soluble organic solvent is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, based on the whole ink. Ink within this range has very good drying properties and ejection reliability.

<Pigment>
The content of the pigment used in the present invention in the ink is preferably 0.1 to 20.0% by mass.
If it is 0.01% by mass or more, the image density is low and the printed image does not lack sharpness. If it is 20% by mass or less, the viscosity of the ink becomes too high or nozzle clogging occurs. There is nothing to do.
The 50% volume average particle diameter (D50) of the pigment is preferably 150 nm or less. Here, the 50% volume average particle diameter of the pigment indicates a value of D50 measured by a dynamic light scattering method using a Microtrac UPA manufactured by Nikkiso Co., Ltd. in an environment of 23 ° C. and 55% RH.
There is no restriction | limiting in particular in the kind of pigment, According to the objective, it can select suitably, For example, any of an inorganic pigment and an organic pigment may be sufficient. Moreover, 1 type may be used independently and 2 or more types may be used together.

Examples of the inorganic pigment include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, bitumen, cadmium red, chrome yellow, metal powder, and carbon black. Of these, carbon black is preferred.
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. Can be mentioned.
Examples of the dye chelate include basic dye chelate and acid dye chelate.

Examples of the pigment for black ink include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, copper, iron (CI pigment black 11), and the like. Examples thereof include metal, metal compounds such as titanium oxide, and organic pigments such as aniline black (CI Pigment Black 1).
As carbon black, carbon black produced by a furnace method or a channel method has a primary particle diameter of 15 to 40 nm, a specific surface area by a BET method of 50 to 300 m ² / g, a DBP oil absorption of 40 to 150 mL / 100 g, and volatilization. Those having a content of 0.5 to 10% and a pH value of 2 to 9 are preferred.

  Examples of commercially available carbon black include No. 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 Corporation); 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 for yellow ink, According to the objective, it can select suitably, for example, C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 2, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 73, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 75, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 98, C.I. I. Pigment yellow 114, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 180, and the like.

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

There is no restriction | limiting in particular as a pigment for cyan ink, According to the objective, it can select suitably, for example, C.I. 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.
The pigment used in the ink of the present invention may be newly produced for the present invention.
When pigment yellow 74 is used as the yellow pigment, pigment red 122 and pigment bio red 19 are used as the magenta pigment, and pigment blue 15: 3 is used as the cyan pigment, it is possible to obtain a balanced ink with excellent color tone and light resistance. .

<Other ingredients>
Other components are not particularly limited and can be appropriately selected as necessary. For example, a dispersant, a penetrant, a pH adjuster, a water-dispersible resin, an antiseptic / antifungal agent, a chelating reagent, a rust inhibitor, an oxidation agent Examples thereof include an inhibitor, an ultraviolet absorber, an oxygen absorber, and a light stabilizer.

(Dispersant)
As the dispersant, it is preferable to use a copolymer having a phosphate group, but various surfactants and polymers such as an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant are used. Type dispersants may be used, and these may be used alone or in combination of two or more.
Examples of the anionic surfactant include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acyl methyl taurate, polyoxyalkyl ether sulfates. Salt, polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester salt, lauryl alcohol sulfate ester salt, alkylphenol type phosphate ester, naphthalenesulfonate formalin condensate, alkyl type phosphate ester, alkylallylsulfone hydrochloride, diethyl Examples include sulfosuccinate, diethylhexyl sulfosuccinate, and dioctyl sulfosuccinate.

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

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

(Penetration agent)
Unlike the water-soluble organic solvent used as the wetting agent, a penetrating agent having a relatively low wettability is used. That is, what has the solubility between 0.2-5.0 mass% in 25 degreeC water is preferable.
Specifically, it is preferable to contain either a polyol compound having 8 to 11 carbon atoms or a glycol ether compound having 8 to 11 carbon atoms. Among them, 2-ethyl-1,3-hexanediol [solubility: 4.2 mass% (25 ° C.)], 2,2,4-trimethyl-1,3-pentanediol [solubility: 2.0 mass% (25 ° C)] is particularly preferred.
Examples of aliphatic diols other than the above include 2-ethyl-2-methyl-1,3-propanediol, 3,3-dimethyl-1,2-butanediol, and 2,2-diethyl-1,3-propane Diol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 2,5-dimethyl-2,5-hexanediol, 5-hexene-1,2 -Diol etc. are mentioned.

Other penetrants that can be used in combination are not particularly limited as long as they can be dissolved in the ink and adjusted to the desired physical properties, and can be appropriately selected according to the purpose. For example, diethylene glycol monophenyl ether, ethylene Glycol monophenyl ether, ethylene glycol monoallyl ether, diethylene glycol monophenyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, alkyl and aryl ethers of polyhydric alcohols such as tetraethylene glycol chlorophenyl ether, lower alcohols such as ethanol, etc. Is mentioned.
The content of the penetrant in the ink is preferably 0.1 to 4.0% by mass. If it is less than 0.1% by mass, quick drying may not be obtained and a blurred image may be obtained. On the other hand, if the amount exceeds 4.0% by mass, the dispersion stability of the pigment is impaired, the nozzle is likely to be clogged, the permeability to the recording medium becomes higher than necessary, and the image density is lowered and the back-through occurs. There are things to do.

(PH adjuster)
The pH adjuster is not particularly limited as long as it can adjust the pH to 8.5 to 11 and preferably 9 to 11 without adversely affecting the ink, and can be appropriately selected according to the purpose. When the pH is less than 8.5 or more than 11, the amount of the ink jet head or ink supply unit that melts out increases, and problems such as ink deterioration, leakage, and ejection failure may occur. If it is less than 8.5, the pH of the ink may decrease during storage of the ink, and the particle size of the polymer fine particles may increase to cause aggregation. The pH can be measured, for example, with a pH meter: HM-30R (manufactured by TOA-DKK).

Examples of pH adjusting agents 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 and quaternary ammonium hydroxide.
Examples of the phosphonium hydroxide include quaternary phosphonium hydroxide.
Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, and potassium carbonate.

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

The average particle size (D50) of the water-dispersible resin is related to the viscosity of the dispersion. For the same composition, the viscosity at the same solid content increases as the particle size decreases. The average particle diameter (D50) of the water-dispersible resin is preferably 50 nm or more so that the ink does not have an excessively high viscosity. Further, when the particle size is several tens of μm, it becomes larger than the nozzle opening of the ink jet head and cannot be used. Furthermore, even if the particle size is smaller than that of the nozzle opening, if the particles having a large particle size are present in the ink, 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.
In addition, the water-dispersible resin preferably has a function of fixing the water-dispersed pigment on the paper surface and is formed into a film at room temperature to improve the fixability of the pigment. Therefore, the minimum film-forming temperature (MFT) of the water-dispersible resin is preferably 30 ° C. or lower.
In addition, 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 glass transition temperature is preferably -30 ° C or higher.
The content of the water-dispersible resin in the ink is preferably 1 to 15% by mass, more preferably 2 to 7% by mass in terms of solid content.

(Antiseptic and antifungal agent)
Examples of antiseptic and antifungal agents include sodium dehydroacetate, sodium sorbate, 2-pyridinethiol-1-oxide sodium, sodium benzoate, sodium pentachlorophenol, and the like.
(Chelating reagent)
Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate, and the like.

(Rust inhibitor)
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 UV absorber include benzophenone UV absorbers, benzotriazole UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, nickel complex salt UV absorbers, and the like.

[Method for producing ink-jet ink]
The ink of the present invention is produced by dispersing or dissolving water, a water-soluble organic solvent, a pigment, a copolymer having a phosphoric acid group, and, if necessary, other components in an aqueous medium, and further appropriately stirring and mixing.
It is desirable that the pigment is contained in the ink as a pigment dispersion in which water, a pigment, and a dispersant and other materials as necessary are mixed in advance and dispersed by a known disperser to adjust the particle diameter.
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 should be performed with a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser, etc. Can do.
0.1-50 mass% is preferable and, as for the pigment concentration at the time of creating a pigment dispersion, 0.1-30 mass% is especially preferable.
The pigment dispersion and ink are preferably degassed by filtering coarse particles with a filter, a centrifugal separator or the like, if necessary.

The physical properties of the ink of the present invention are not particularly limited, and can be appropriately selected according to the purpose.
For example, the viscosity of the ink at 25 ° C. is preferably 3 to 20 mPa · s. If the viscosity is 3 mPa · s or more, the effect of improving the printing density and the character quality can be obtained. Further, by suppressing the ink viscosity to 20 mPa · s or less, it is possible to ensure the discharge property.
The viscosity can be measured at 25 ° C. using, for example, a viscometer (RL-550, manufactured by Toki Sangyo Co., Ltd.).
The surface tension of the ink is preferably 40 mN / m or less at 25 ° C. If it is 40 mN / m or less, the leveling of the ink on the recording medium does not occur, and the drying time is not prolonged.

[ink cartridge]
The ink cartridge of the present invention accommodates the ink of the present invention in a container, and may further have other members appropriately selected as necessary.
The shape, structure, size, material, etc. of the container are not particularly limited and can be appropriately selected according to the purpose. Examples include those having an ink bag formed of an aluminum laminate film, a resin film, or the like.
An example of the ink cartridge of the present invention will be described with reference to FIGS.
FIG. 1 is a view showing an example of the ink cartridge of the present invention, and FIG. 2 is a view including a case (exterior) of the ink cartridge 200 of FIG. As shown in FIG. 1, the ink cartridge 200 is filled into the ink bag 241 from the ink inlet 242 and exhausted, and then the ink inlet 242 is closed by fusion. In use, the needle of the apparatus main body is pierced into the ink discharge port 243 made of a rubber member and supplied to the apparatus. The ink bag 241 is formed of a packaging member such as a non-permeable aluminum laminate film. As shown in FIG. 2, the ink bag 241 is usually housed in a plastic cartridge case 244 and is detachably mounted on various ink jet recording apparatuses.

[Inkjet recording apparatus and inkjet recording method]
The ink jet recording apparatus of the present invention has at least ink flying means, and further has other means appropriately selected as necessary, for example, stimulus generation means, control means, and the like.
The inkjet recording method of the present invention includes at least an ink flying process, and further includes other processes appropriately selected as necessary, for example, a stimulus generation process, a control process, and the like.
The ink jet recording method of the present invention can be preferably carried out by the ink jet recording apparatus of the present invention, and the ink flying step can be suitably carried out by the ink flying means. Moreover, the said other process can be suitably performed by the said other means.
The ink flying step is a step of forming an image by applying a stimulus to ink and causing it to fly.
The ink flying means is means for applying an stimulus to ink and causing it to fly to form an image. The ink flying means is not particularly limited, and examples thereof include various nozzles for ejecting ink.

The stimulus can be generated by the stimulus generating means, for example. There is no restriction | limiting in particular as this irritation | stimulation, According to the objective, it can select suitably, A heat | fever (temperature), a pressure, a vibration, light, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Of these, heat and pressure are preferred.
Examples of the stimulus generating means include a superheater, a pressurizer, a piezoelectric element, a vibration generator, an ultrasonic oscillator, and a light. Specifically, a piezoelectric actuator such as a piezoelectric element such as a piezoelectric element, a thermal actuator that uses a phase change due to liquid film boiling using an electrothermal transducer such as a heating resistor, a shape that uses a metal phase change due to a temperature change Memory alloy actuators, electrostatic actuators using electrostatic force, and the like can be mentioned.

There are no particular restrictions on the mode of the ink flying, and it varies depending on the type of the stimulus. For example, when the stimulus is “heat”, the thermal energy corresponding to the recording signal is applied to the ink in the recording head. For example, there is a method in which a thermal head or the like is applied, bubbles are generated in the ink by the thermal energy, and the ink is ejected and ejected as droplets from the nozzle holes of the recording head by the pressure of the bubbles.
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 ink as droplets from the nozzle holes of the recording head.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as sequencers and computers.

Here, an aspect of carrying out the ink jet recording method of the present invention by the ink jet recording apparatus of the present invention will be described with reference to the drawings.
FIG. 3 is a schematic view showing an example of the serial type ink jet recording apparatus of the present invention. This ink jet recording apparatus includes an apparatus main body 101, a paper feed tray 102 for loading paper loaded in the apparatus main body 101, and a discharge for stocking paper on which an image is recorded (formed) mounted on the apparatus main body 101. A paper tray 103 and an ink cartridge loading unit 104 are provided. On the upper surface of the ink cartridge loading unit 104, an operation unit 105 such as operation keys and a display is arranged. The ink cartridge loading unit 104 has a front cover 115 that can be opened and closed for attaching and detaching the ink cartridge 201.

In the apparatus main body 101, as shown in FIGS. 4 and 5, a carriage 133 is slidably held in the main scanning direction by a guide rod 131 and a stay 132, which are guide members horizontally mounted on left and right side plates, The main scanning motor moves and scans in the direction indicated by the arrow in FIG.
The carriage 133 is provided with a plurality of ink ejection heads 134 including four inkjet recording heads that eject ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk). The outlets are arranged so as to cross the main scanning direction, and the ink droplet ejection direction is directed downward.
As the ink jet recording head constituting the recording head 134, a piezoelectric actuator such as a piezoelectric element, a thermal actuator using phase change due to liquid film boiling using an electrothermal transducer such as a heating resistor, a metal phase due to temperature change, etc. A shape memory alloy actuator using a change, an electrostatic actuator using an electrostatic force, or the like provided as energy generating means for discharging ink can be used.
In addition, the carriage 133 is equipped with a sub tank 135 for each color for supplying ink of each color to the recording head 134. Ink is supplied to the sub tank 135 from the ink cartridge 201 loaded in the ink cartridge loading unit 105 via the ink supply tube and replenished.

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

In addition, a charging roller 156 that is a charging unit for charging the surface of the conveyance belt 151 is provided. The conveyance belt 151 is an endless belt, is stretched between the conveyance roller 157 and the tension roller 158, and can circulate in the belt conveyance direction. The transport belt 151 includes, for example, a surface layer serving as a sheet adsorbing surface formed of a resin material having a thickness of about 40 μm that is not subjected to resistance control, for example, a copolymer of tetrafluoroethylene and ethylene (ETFE), and the surface layer. It has a back layer (medium resistance layer, earth layer) that is made of the same material and has resistance controlled by carbon. On the back side of the conveyance belt 151, a guide member 161 is arranged corresponding to a printing area by the recording head 134.
Note that, as a paper discharge unit for discharging the paper 142 recorded by the recording head 134, a separation claw 171 for separating the paper 142 from the conveyance belt 151, a paper discharge roller 172, and a paper discharge roller 173 are provided. The paper discharge tray 103 is disposed below the paper discharge roller 172.

A double-sided paper feeding unit 181 is detachably mounted on the back surface of the apparatus main body 101. The double-sided paper feeding unit 181 takes in the paper 142 returned by the reverse rotation of the transport belt 151, reverses it, and feeds it again between the counter roller 152 and the transport belt 151. A manual paper feed unit 182 is provided on the upper surface of the duplex paper feed unit 181.
In this ink jet recording apparatus, the 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 is interposed between the transport belt 151 and the counter roller 152. It is sandwiched and conveyed. Further, the leading end is guided by the conveying guide 153 and pressed against the conveying belt 151 by the leading end pressure roller 155, and the conveying direction is changed by approximately 90 °. At this time, the conveyance belt 157 is charged by the charging roller 156, and the sheet 142 is conveyed by being electrostatically attracted to the conveyance belt 151. Therefore, by driving the recording head 134 according to the image signal while moving the carriage 133, ink droplets are ejected onto the stopped paper 142 to record one line, and after the paper 142 is conveyed by a predetermined amount, Record the next line.
Upon receiving a recording end signal or a signal that the trailing edge of the sheet 142 has reached the recording area, the recording operation is terminated and the sheet 142 is discharged onto the discharge tray 103. When a near-end remaining amount of ink in the sub tank 135 is detected, a required amount of ink is supplied from the ink cartridge 201 to the sub tank 135.

In this ink jet recording apparatus, when the ink in the ink cartridge 201 is used up, the casing of the ink cartridge 201 can be disassembled and only the ink bag inside can be replaced. Further, the ink cartridge 201 can supply ink stably even when the ink cartridge 201 is placed vertically and has a front loading configuration.
Therefore, 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, the ink cartridge 201 is replaced. It can be done easily.
In addition, although it demonstrated in the example applied to the serial type (shuttle type) inkjet recording device which a carriage scans, it can apply similarly to the line type inkjet recording device provided with the line type head.
The ink jet recording apparatus of the present invention can be applied to various types of recording by the ink jet recording method, and is particularly preferably applied to, for example, an ink jet recording printer, a facsimile apparatus, a copying apparatus, a printer / fax / copier multifunction machine, and the like. Can do.

[Ink record]
The ink recorded matter of the present invention has an image recorded with the ink of the present invention on a recording medium, has high image quality and excellent stability over time, and is suitably used for various purposes as a material for printing or recording an image. can do.
The recording medium is not particularly limited as long as the ink of the present invention is landed and an image can be formed. For example, plain paper, coated paper for printing, glossy paper, special paper and the like can be mentioned. These papers contain calcium carbonate, talc, kaolin, or aluminum sulfate (sulfate band). When the ink of the present invention lands on these papers, polyvalent metal ions, specifically, Divalent or trivalent metal ions such as calcium, magnesium and aluminum are eluted. That is, the ink of the present invention reacts with the above polyvalent metal ions to aggregate the pigment and obtain a high image density.
Many of fillers, sizing agents, fixing agents and the like contained in plain paper are poorly water-soluble metal salts. Moreover, even if a water-soluble metal salt is contained, the content is small. Therefore, the elution of the polyvalent metal ions is less than that of the paper processed with water-soluble polyvalent metal salt or the like on the paper surface, and the effect of improving the image density cannot be obtained by the conventional technique.
On the other hand, in the present invention, a high image density can be realized not only on the processed paper but also on paper with little elution of polyvalent metal ions such as plain paper.
Examples of commercially available plain paper include high-quality paper My Paper (Ricoh) and Xerox 4024 (Fuji Xerox).

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited to these examples. In the examples, “parts” and “%” are based on mass.

<Synthesis of Copolymers 1 to 45>
Copolymers 1 to 45 were synthesized in the following manner using the materials and blending ratios shown in each column of Synthesis Examples 1 to 45 in Table 1. The numerical value in the content column in the table is “parts by weight”, but the numerical value in () in the content column of (Formula 5) or (Formula 6) in Synthesis Examples 40 to 42 is a blend of styrene or methacrylic acid. Indicates the amount. Moreover, the meaning of the symbol of each material is as follows.
・ Phosmer M: Acid phosphooxyethyl methacrylate (Unichemical Co., Ltd.)
= Compound of (Formula 5-1) DAAM: Diacetone acrylamide = Compound of (Formula 6-1) DAMAM: Diacetone methacrylamide = (Formula 6-2) StA: Stearyl acrylate = (Formula 7- Compound of 1) StMA: Stearyl methacrylate = compound of formula 7-2 BzA: benzyl acrylate = compound of formula 8-1 BzMA: benzyl methacrylate = compound of formula 8-2 P-1A : Acid phosphooxyethyl acrylate (manufactured by Kyoeisha Chemical)
・ Phosmer PE: Acid phosphooxypolyoxyethylene glycol monomethacrylate (manufactured by Unichemical)
・ Phosmer PP: Acid phosphooxypolyoxypropylene glycol monomethacrylate (manufactured by Unichemical)
・ DMEA: Dimethylethanolamine

In addition, the mass mean molecular weight of the copolymers 1-45 in a table | surface was measured with the following method.
Shimadzu CTO-20A for the column thermostat, Shimadzu RID-10A for the detector, Shimadzu LC-20AD for the eluent flow path pump, Shimadzu DGU-20A for the degasser, autosampler Was measured by GPC method using SIL-20A manufactured by Shimadzu Corporation. The column is connected to Tosoh's water-based SEC column TSKgelG3000PWXL (exclusion limit molecular weight 2 × 10 ⁵ ), TSKgelG5000PWXL (exclusion limit molecular weight 2.5 × 10 ⁶ ), and TSKgelG6000PWXL (exclusion limit molecular weight 5 × 10 ⁷ ). Was used. The measurement sample was adjusted to a concentration of 2 g / 100 mL with the eluent. As an eluent, an aqueous solution adjusted to 0.5 mol / L each of acetic acid and sodium acetate was used. The column temperature was 40 ° C. and the flow rate was 1.0 mL / min. Nine kinds of polyethylene glycols having molecular weights of 1065, 5050, 24000, 50000, 107000, 140000, 250,000, 540000, and 920000 were used as standard samples, and the mass average molecular weight was determined based on the obtained calibration curve.

(Synthesis Example 1)
A 1 liter four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen replacement tube and a stirrer was charged with 15 parts of Phosmer M, 35 parts of DAAM, 50 parts of StA, and 500 parts of ethanol. The temperature was raised under a nitrogen stream, 1 part of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 1 was obtained.

(Synthesis Example 2)
200 parts of ethanol was charged into a 1 liter five-necked flask equipped with a reflux condenser, a thermometer, a nitrogen replacement tube, a dropping funnel and a stirrer. Further, Phosmer M: 5 parts, DAAM: 35 parts, StA: 60 parts and ethanol 50 parts were mixed in advance in a dropping funnel. The temperature was raised under a nitrogen stream, 0.5 parts of a radical polymerization initiator was added at 70 ° C., and then the mixture charged in the dropping funnel was added dropwise over 2 hours, and the reaction was further continued at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with an acid monomer and an equimolar amount of potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 2 was obtained.

(Synthesis Example 3)
In the same four-necked flask as in Synthesis Example 1, Phosmer M; 30 parts, DAAM; 10 parts, StA; 60 parts and ethanol 200 parts were charged. The temperature was raised under a nitrogen stream, 2 parts of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 3 was obtained.

(Synthesis Example 4)
The same four-necked flask as in Synthesis Example 1 was charged with Phosmer M; 55 parts, DAAM; 35 parts, StA: 10 parts, and ethanol 500 parts. The temperature was raised under a nitrogen stream, 1 part of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, and a copolymer 4 was obtained.

(Synthesis Example 5)
In the same five-necked flask as in Synthesis Example 2, 200 parts of ethanol was charged. Furthermore, a mixture solution in which Phosmer M; 65 parts, DAAM; 20 parts, StA; 15 parts and ethanol 50 parts were uniformly dissolved and mixed in advance was charged into the dropping funnel. The temperature was raised under a nitrogen stream, 0.5 parts of a radical polymerization initiator was added at 70 ° C., and then the mixture charged in the dropping funnel was added dropwise over 2 hours, and the reaction was further continued at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with an acid monomer and an equimolar amount of potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 5 was obtained.

(Synthesis Example 6)
In the same five-necked flask as in Synthesis Example 2, 200 parts of ethanol was charged. Furthermore, a mixed solution in which Phosmer M; 30 parts, DAAM; 5 parts, StA; 60 parts, 70 parts and ethanol 50 parts were uniformly dissolved and mixed in advance was charged into the dropping funnel. The temperature was raised under a nitrogen stream, 0.5 parts of a radical polymerization initiator was added at 70 ° C., and then the mixture charged in the dropping funnel was added dropwise over 2 hours, and the reaction was further continued at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with an acid monomer and an equimolar amount of potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 6 was obtained.

(Synthesis Example 7)
The same four-necked flask as in Synthesis Example 1 was charged with Phosmer M; 55 parts, DAAM; 35 parts, StA; 10 parts, and ethanol 200 parts. The temperature was raised under a nitrogen stream, 1 part of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 7 was obtained.

(Synthesis Example 8)
In the same four-necked flask as in Synthesis Example 1, 65 parts of phosmer M, 20 parts of DAAM, 15 parts of StA, and 200 parts of ethanol were charged. The temperature was raised under a nitrogen stream, 1.5 parts of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, and a copolymer 8 was obtained.

(Synthesis Example 9)
The same four-necked flask as in Synthesis Example 1 was charged with Phosmer M; 55 parts, DAAM; 35 parts, StA; 10 parts, and ethanol 200 parts. The temperature was raised under a nitrogen stream, 1.5 parts of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 9 was obtained.

(Synthesis Example 10)
The same four-necked flask as in Synthesis Example 1 was charged with Phosmer M; 15 parts, DAAM; 35 parts, StA; 50 parts, and ethanol 200 parts. The temperature was raised under a nitrogen stream, 1 part of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 10 was obtained.

(Synthesis Example 11)
In the same four-necked flask as in Synthesis Example 1, Phosmer M; 5 parts, DAAM; 35 parts, StA; 60 parts and ethanol 200 parts were charged. The temperature was raised under a nitrogen stream, 1.5 parts of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, and a copolymer 11 was obtained.

(Synthesis Example 12)
The same four-necked flask as in Synthesis Example 1 was charged with Phosmer M; 15 parts, DAAM; 35 parts, StA; 50 parts, and ethanol 200 parts. The temperature was raised under a nitrogen stream, 1.5 parts of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 12 was obtained.

(Synthesis Example 13)
In the same five-necked flask as in Synthesis Example 2, 200 parts of ethanol was charged. Furthermore, a mixture solution in which Phosmer M; 15 parts, DAAM; 35 parts, StA; 50 parts and ethanol 50 parts were uniformly dissolved and mixed in advance was charged into the dropping funnel. The temperature was raised under a nitrogen stream, 0.5 parts of a radical polymerization initiator was added at 70 ° C., and then the mixture charged in the dropping funnel was added dropwise over 2 hours, and the reaction was further continued at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with an acid monomer and an equimolar amount of sodium hydroxide so that the neutralization rate was 100%, whereby a copolymer 13 was obtained.

(Synthesis Example 14)
In the same five-necked flask as in Synthesis Example 2, 200 parts of ethanol was charged. Furthermore, a mixture solution in which Phosmer M; 15 parts, DAAM; 35 parts, StA; 50 parts and ethanol 50 parts were uniformly dissolved and mixed in advance was charged into the dropping funnel. The temperature was raised under a nitrogen stream, 0.5 parts of a radical polymerization initiator was added at 70 ° C., and then the mixture charged in the dropping funnel was added dropwise over 2 hours, and the reaction was further continued at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with an acid monomer and an equimolar amount of lithium hydroxide so that the neutralization rate was 100%, whereby a copolymer 14 was obtained.

(Synthesis Example 15)
In the same four-necked flask as in Synthesis Example 1, Phosmer M; 5 parts, DAAM; 35 parts, StA; 60 parts and ethanol 500 parts were charged. The temperature was raised under a nitrogen stream, 1 part of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, and a copolymer 15 was obtained.

(Synthesis Example 16)
In the same four-necked flask as in Synthesis Example 1, 65 parts of phosmer M, 20 parts of DAAM, 15 parts of StA, and 200 parts of ethanol were charged. The temperature was raised under a nitrogen stream, 1 part of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, and a copolymer 16 was obtained.

(Synthesis Example 17)
In the same five-necked flask as in Synthesis Example 2, 200 parts of ethanol was charged. Furthermore, P-1A; 15 parts, DAAM; 35 parts, StA: 50 parts and ethanol 50 parts were mixed in advance in a dropping funnel. The temperature was raised under a nitrogen stream, 0.5 parts of a radical polymerization initiator was added at 70 ° C., and then the mixture charged in the dropping funnel was added dropwise over 2 hours, and the reaction was further continued at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with an acid monomer and an equimolar amount of potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 17 was obtained.

(Synthesis Example 18)
In the same five-necked flask as in Synthesis Example 2, 200 parts of ethanol was charged. Furthermore, a mixed solution in which Phosmer M: 15 parts, DAAM: 35 parts, BzA: 50 parts and ethanol 50 parts were uniformly dissolved and mixed in advance was charged into the dropping funnel. The temperature was raised under a nitrogen stream, 0.5 parts of a radical polymerization initiator was added at 70 ° C., and then the mixture charged in the dropping funnel was added dropwise over 2 hours, and the reaction was further continued at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with an acid monomer and an equimolar amount of potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 18 was obtained.

(Synthesis Example 19)
In the same five-necked flask as in Synthesis Example 2, 200 parts of ethanol was charged. Furthermore, the dropping funnel was charged with a mixed solution in which Phosmer M: 5 parts, DAAM: 35 parts, BzA: 60 parts and ethanol 50 parts were uniformly dissolved and mixed in advance. The temperature was raised under a nitrogen stream, 0.2 part of a radical polymerization initiator was added at 70 ° C., and then the mixture charged in the dropping funnel was added dropwise over 2 hours, and the reaction was further continued at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with an acid monomer and an equimolar amount of potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 19 was obtained.

(Synthesis Example 20)
In the same five-necked flask as in Synthesis Example 2, 200 parts of ethanol was charged. Furthermore, a mixed solution in which Phosmer M: 15 parts, DAAM: 35 parts, BzA: 50 parts and ethanol 50 parts were uniformly dissolved and mixed in advance was charged into the dropping funnel. The temperature was raised under a nitrogen stream, 0.5 parts of a radical polymerization initiator was added at 70 ° C., and then the mixture charged in the dropping funnel was added dropwise over 2 hours, and the reaction was further continued at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with an acid monomer and an equimolar amount of potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 20 was obtained.

(Synthesis Example 21)
In the same five-necked flask as in Synthesis Example 2, 200 parts of ethanol was charged. Furthermore, a mixed solution in which Phosmer M: 55 parts, DAAM: 35 parts, BzA: 10 parts and ethanol 50 parts were uniformly dissolved and mixed in advance was charged into the dropping funnel. The temperature was raised under a nitrogen stream, 0.5 parts of a radical polymerization initiator was added at 70 ° C., and then the mixture charged in the dropping funnel was added dropwise over 2 hours, and the reaction was further continued at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with an acid monomer and an equimolar amount of potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 21 was obtained.

(Synthesis Example 22)
In the same five-necked flask as in Synthesis Example 2, 200 parts of ethanol was charged. Furthermore, a mixture solution in which Phosmer M: 65 parts, DAAM: 20 parts, BzA: 15 parts and ethanol 50 parts were uniformly dissolved and mixed in advance was charged into a dropping funnel. The temperature was raised under a nitrogen stream, 0.5 parts of a radical polymerization initiator was added at 70 ° C., and then the mixture charged in the dropping funnel was added dropwise over 2 hours, and the reaction was further continued at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with an acid monomer and an equimolar amount of potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 22 was obtained.

(Synthesis Example 23)
In the same five-necked flask as in Synthesis Example 2, 200 parts of ethanol was charged. Furthermore, a mixed solution in which Phosmer M: 55 parts, DAAM: 35 parts, BzA: 10 parts and ethanol 50 parts were uniformly dissolved and mixed in advance was charged into the dropping funnel. The temperature was raised under a nitrogen stream, 0.5 parts of a radical polymerization initiator was added at 70 ° C., and then the mixture charged in the dropping funnel was added dropwise over 2 hours, and the reaction was further continued at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with an acid monomer and an equimolar amount of potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 23 was obtained.

(Synthesis Example 24)
The same four-necked flask as in Synthesis Example 1 was charged with Phosmer M; 55 parts, DAAM; 35 parts, BzA: 10 parts, and ethanol 200 parts. The temperature was raised under a nitrogen stream, 1 part of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, and a copolymer 24 was obtained.

(Synthesis Example 25)
In the same four-necked flask as in Synthesis Example 1, Phosmer M: 65 parts, DAAM: 20 parts, BzA: 15 parts and ethanol 200 parts were charged. The temperature was raised under a nitrogen stream, 1.5 parts of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, and a copolymer 25 was obtained.

(Synthesis Example 26)
The same four-necked flask as in Synthesis Example 1 was charged with Phosmer M; 55 parts, DAAM; 35 parts, BzA: 10 parts, and ethanol 200 parts. The temperature was raised under a nitrogen stream, 1.5 parts of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, and a copolymer 26 was obtained.

(Synthesis Example 27)
In the same four-necked flask as in Synthesis Example 1, Phosmer M: 15 parts, DAAM: 35 parts, BzA: 50 parts and ethanol 200 parts were charged. The temperature was raised under a nitrogen stream, 1 part of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, and a copolymer 27 was obtained.

(Synthesis Example 28)
In the same four-necked flask as in Synthesis Example 1, Phosmer M; 5 parts, DAAM; 35 parts, BzA: 60 parts and ethanol 200 parts were charged. The temperature was raised under a nitrogen stream, 1.5 parts of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, and a copolymer 28 was obtained.

(Synthesis Example 29)
In the same four-necked flask as in Synthesis Example 1, Phosmer M: 15 parts, DAAM: 35 parts, BzA: 50 parts and ethanol 200 parts were charged. The temperature was raised under a nitrogen stream, 1.5 parts of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 29 was obtained.

(Synthesis Example 30)
In the same five-necked flask as in Synthesis Example 2, 200 parts of ethanol was charged. Furthermore, a mixed solution in which Phosmer M: 15 parts, DAAM: 35 parts, BzA: 50 parts and ethanol 50 parts were uniformly dissolved and mixed in advance was charged into the dropping funnel. The temperature was raised under a nitrogen stream, 0.5 parts of a radical polymerization initiator was added at 70 ° C., and then the mixture charged in the dropping funnel was added dropwise over 2 hours, and the reaction was further continued at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with an acid monomer and an equimolar amount of sodium hydroxide so that the neutralization rate was 100%, whereby a copolymer 30 was obtained.

(Synthesis Example 31)
In the same five-necked flask as in Synthesis Example 2, 200 parts of ethanol was charged. Furthermore, a mixed solution in which Phosmer M: 15 parts, DAAM: 35 parts, BzA: 50 parts and ethanol 50 parts were uniformly dissolved and mixed in advance was charged into the dropping funnel. The temperature was raised under a nitrogen stream, 0.5 parts of a radical polymerization initiator was added at 70 ° C., and then the mixture charged in the dropping funnel was added dropwise over 2 hours, and the reaction was further continued at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with an acid monomer and an equimolar amount of lithium hydroxide so that the neutralization rate was 100%, whereby a copolymer 31 was obtained.

(Synthesis Example 32)
In the same five-necked flask as in Synthesis Example 2, 200 parts of ethanol was charged. Furthermore, the dropping funnel was charged with a mixed solution in which Phosmer M: 5 parts, DAAM: 35 parts, BzA: 60 parts and ethanol 50 parts were uniformly dissolved and mixed in advance. The temperature was raised under a nitrogen stream, 0.5 parts of a radical polymerization initiator was added at 70 ° C., and then the mixture charged in the dropping funnel was added dropwise over 2 hours, and the reaction was further continued at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with an acid monomer and an equimolar amount of potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 32 was obtained.

(Synthesis Example 33)
In the same four-necked flask as in Synthesis Example 1, Phosmer M: 65 parts, DAAM: 20 parts, BzA: 15 parts and ethanol 200 parts were charged. The temperature was raised under a nitrogen stream, 1 part of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 33 was obtained.

(Synthesis Example 34)
In the same four-necked flask as in Synthesis Example 1, 30 parts of P-1A, 10 parts of DAAM, 60 parts of BzA, and 200 parts of ethanol were charged. The temperature was raised under a nitrogen stream, 2 parts of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, and a copolymer 34 was obtained.

(Synthesis Example 35)
In the same four-necked flask as in Synthesis Example 1, phosmer PE; 30 parts, DAAM; 10 parts, BzA: 60 parts and ethanol 200 parts were charged. The temperature was raised under a nitrogen stream, 2 parts of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, and a copolymer 35 was obtained.

(Synthesis Example 36)
In the same four-necked flask as in Synthesis Example 1, phosmer PP; 30 parts, DAAM; 10 parts, BzA: 60 parts and ethanol 200 parts were charged. The temperature was raised under a nitrogen stream, 2 parts of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 36 was obtained.

(Synthesis Example 37)
In the same four-necked flask as in Synthesis Example 1, (Formula 5-5); 30 parts, DAAM; 10 parts, BzA: 60 parts and ethanol 200 parts were charged. The temperature was raised under a nitrogen stream, 2 parts of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, and a copolymer 37 was obtained.

(Synthesis Example 38)
In the same four-necked flask as in Synthesis Example 1, Phosmer M; 30 parts, DAAM; 10 parts, BzA: 60 parts, and ethanol 200 parts were charged. The temperature was raised under a nitrogen stream, 2 parts of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 50%, and a copolymer 38 was obtained.

(Synthesis Example 39)
In the same five-necked flask as in Synthesis Example 2, 200 parts of ethanol was charged. Furthermore, a mixed solution in which Phosmer M: 15 parts, DAAM: 35 parts, BzA: 50 parts and ethanol 50 parts were uniformly dissolved and mixed in advance was charged into the dropping funnel. The temperature was raised under a nitrogen stream, 0.5 parts of a radical polymerization initiator was added at 70 ° C., and then the mixture charged in the dropping funnel was added dropwise over 2 hours, and the reaction was further continued at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with an acid monomer and an equimolar amount of dimethylethanolamine so that the neutralization rate was 100%, whereby a copolymer 39 was obtained.

(Synthesis Example 40)
In the same four-necked flask as in Synthesis Example 1, 15 parts of styrene, 85 parts of DAAM, and 100 parts of ethanol were charged. The temperature was raised under a nitrogen stream, 0.5 parts of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, and a copolymer 40 was obtained.

(Synthesis Example 41)
In the same five-necked flask as in Synthesis Example 2, 200 parts of ethanol was charged. Further, Phosmer M: 15 parts: Methacrylic acid; 85 parts and 50 parts of ethanol were previously dissolved and mixed uniformly in a dropping funnel. The temperature was raised under a nitrogen stream, 0.5 parts of a radical polymerization initiator was added at 70 ° C., and then the mixture charged in the dropping funnel was dropped over 2 hours, and the reaction was further continued for 6 hours while maintaining at 70 ° C. . After completion of the reaction, the reaction product was neutralized with an acid monomer and an equimolar amount of potassium hydroxide so that the neutralization rate was 100%, whereby a copolymer 41 was obtained.

(Synthesis Example 42)
In the same four-necked flask as in Synthesis Example 1, 15 parts of styrene, 85 parts of methacrylic acid, and 100 parts of ethanol were charged. The temperature was raised under a nitrogen stream, 0.2 parts of a radical polymerization initiator was added at 70 ° C., and the reaction was further continued for 6 hours while maintaining the temperature at 70 ° C. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, and a copolymer 42 was obtained.

(Synthesis Example 43)
In the same four-necked flask as in Synthesis Example 1, Phosmer M; 30 parts, DAMAM; 10 parts, StA; 60 parts and ethanol 200 parts were charged. The temperature was raised under a nitrogen stream, 2 parts of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, and a copolymer 43 was obtained.

(Synthesis Example 44)
In the same four-necked flask as in Synthesis Example 1, Phosmer M; 30 parts, DAAM; 10 parts, StMA; 60 parts and ethanol 200 parts were charged. The temperature was raised under a nitrogen stream, 2 parts of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, and a copolymer 44 was obtained.

(Synthesis Example 45)
The same four-necked flask as in Synthesis Example 1 was charged with Phosmer M; 30 parts, DAAM; 10 parts, BzMA; 60 parts, and ethanol 200 parts. The temperature was raised under a nitrogen stream, 2 parts of a radical polymerization initiator was added at 70 ° C., and the mixture was further maintained at 70 ° C. for 6 hours. After completion of the reaction, the reaction product was neutralized with potassium hydroxide so that the neutralization rate was 100%, and a copolymer 45 was obtained.

<Preparation of pigment dispersions 1 to 55>
Using the materials shown in the respective columns of the pigment dispersions 1 to 55 in Tables 2 to 4 below, first, a mixture slurry was prepared by premixing a mixture of each copolymer, pigment and distilled water. Next, this was circulated and dispersed for 3 minutes at a peripheral speed of 10 m / s and a liquid temperature of 10 ° C. using a 0.05 mm zirconia bead with a filling rate of 55% in a disk type media mill (manufactured by Ashizawa Finetech, DMR type). Then, coarse particles were centrifuged with a centrifuge (Model 7700, manufactured by Kubota Corporation) to obtain each pigment dispersion. Numerical values in Tables 2 to 4 are blending ratios (parts by weight).
In addition, after drying the copolymers 1-45 and removing a solvent, the solid substance was melt | dissolved in water and used as 20% aqueous solution. Details of each material other than the copolymer are as follows.
Carbon black (NIPEX 160, manufactured by degussa, BET specific surface area 150 m ² / g, average primary particle size 20 nm, pH 4.0, DBP oil absorption 620 g / 100 g)
Pigment Blue 15: 3 (Chromofine Blue-A-220JC manufactured by Dainichi Seika Co., Ltd.)
Pigment Red 122 (Clariant, Toner Magenta EO02)
・ Pigment Yellow 74 (Daiichi Seika Co., Ltd., First Yellow 531)

[Examples 1 to 56, Comparative Examples 1 to 3]
<Preparation of ink>
The materials shown in the columns of Examples 1 to 56 and Comparative Examples 1 to 3 in Table 5 and Table 6 below were mixed and stirred for 1 hour to obtain a uniform dispersion. This dispersion was subjected to pressure filtration with a polyvinylidene fluoride membrane filter having an average pore size of 5.0 μm to remove coarse particles and dust to obtain each ink.
In addition, the numerical value in a table | surface is the mass%.

For the inks of the pigment dispersions 1 to 55, Examples 1 to 56, and Comparative Examples 1 to 3, the viscosity and storage stability were evaluated as follows, and the image density was evaluated for each ink.

<Storage stability>
The viscosity of each pigment dispersion and each ink was measured, and storage stability was evaluated using this as an index.
To measure the viscosity, a viscometer RE500L manufactured by Toki Sangyo Co., Ltd. was used. The rotational speed of the rotor was adjusted according to the sample, and the viscosity at 25 ° C. was measured. The results are shown in Table 7.
Moreover, the initial viscosity after preparation of each pigment dispersion and ink was measured and evaluated according to the following criteria. Next, each pigment dispersion and ink are sealed in a polyethylene container, measured for viscosity after being stored at 70 ° C. for 1 week, and stored according to the following criteria based on the rate of change in viscosity after storage based on the initial viscosity. Stability was evaluated. Table 7 shows the evaluation results.

[Evaluation criteria for pigment dispersion]
-Initial viscosity ◎: Initial viscosity is less than 7 mPa · s ○: Initial viscosity is 7 mPa · s or more and less than 20 mPa · s ×: Initial viscosity is 20 mPa · s or more

・ Storage stability ◎: Change rate of viscosity after storage is less than 2% ○: Change rate of viscosity after storage is 2% or more and less than 5% ○ △: Change rate of viscosity after storage is 5% Or more, less than 10% Δ: change rate of viscosity after storage is 10% or more, less than 50% ×: change rate of viscosity after storage is 50% or more

[Ink evaluation criteria]
Initial viscosity ◎: Initial viscosity is less than 9 mPa · s ○: Initial viscosity is 9 mPa · s or more and less than 20 mPa · s ×: Initial viscosity is 20 mPa · s or more

・ Storage stability ◎: Change rate of viscosity after storage is less than 2% ○: Change rate of viscosity after storage is 2% or more, less than 5% ○ △: Change rate of viscosity after storage is 5% or more, 10 Less than% Δ: Change rate of viscosity after storage is 10% or more, less than 50% ×: Change rate of viscosity after storage is 50% or more

<Image density>
Using an ink-jet printer (IPSiO GX3000, manufactured by Ricoh), change the drive voltage of the piezo element so that the discharge amount of each ink is uniform, and set the print medium so that the same amount of ink is attached to the recording medium. Went.
A black chart created using Microsoft Word 2003 and a general symbol of 64 points of JIS X 0208 (1997), 2223 of each color is described. Basis weight is 69.6 g / m ² , size degree is 23.2 seconds, air permeability Printed on high-quality paper of 21.0 seconds: My Paper (manufactured by Ricoh).
Next, the general symbol part of JIS X 0208 (1997), 2223 was measured with X-Rite 938 (manufactured by X-Rite), and the image density was evaluated according to the following criteria. At this time, the printing mode was set to “plain paper-fast” mode with a driver attached to the printer. Note that the general symbols of JIS X 0208 (1997), 2223 are symbols whose outer shape is a regular square and the entire surface of the symbol is filled with ink. Table 7 shows the evaluation results.

〔Evaluation criteria〕
A: OD value Black 1.30 or more
Yellow 0.75 or more
Magenta 0.90 or higher
Cyan 1.00 or more ○: OD value Black 1.20 or more, less than 1.30
Yellow 0.70 or more, less than 0.75
Magenta 0.85 or more, less than 0.90
Cyan 0.90 or more, less than 1.00 ○ △: OD value Black 1.10 or more, less than 1.20
Yellow 0.65 or more, less than 0.70
Magenta 0.70 or more, less than 0.85
Cyan 0.80 or more, less than 0.90 Δ: OD value Black 1.00 or more, less than 1.10
Yellow 0.60 or more, less than 0.65
Magenta 0.65 or more and less than 0.70
Cyan 0.70 or more, less than 0.80 ×: OD value Black Less than 1.00
Yellow Less than 0.60
Magenta less than 0.65
Cyan less than 0.70

From the results shown in Table 7, when Examples 1-56 and Comparative Examples 1-3 are compared, the ink containing the phosphate group-containing copolymer of the present invention is superior in image density and storage stability. I understand that.
Moreover, it turns out that the Example whose content rate of the structural unit represented by (Formula 1) is 10-60 mass% is excellent in both image density and preservability compared with another Example.
Further, it can be seen that the examples in which the molecular weight of the copolymer is 5000 to 50000 are excellent in both image density and storage stability as compared with the other examples.

DESCRIPTION OF SYMBOLS 101 Main body 102 Paper feed tray 103 Paper discharge tray 104 Ink cartridge loading 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 144 Separation pad 151 Conveying belt 152 Counter roller 156 Charging roller 157 Conveyance roller 158 Densation roller 171 Separation claw 172 Paper discharge roller 173 Paper discharge roller 181 Double-sided paper feed unit 201 Ink cartridge 241 Ink bag 242 Ink inlet 243 Ink outlet 244 Cartridge exterior

JP 2010-189478 A JP 2007-270089 A JP 2011-122072 A

Claims (8)

In an inkjet recording ink containing at least water, a water-soluble organic solvent, a pigment, and a copolymer having a phosphoric acid group, the copolymer includes a structural unit represented by the following (formula 1) and the following (formula 2): And at least a structural unit represented by the following (formula 3) or (formula 4).

In (Formula 1), more than half of M ⁺ are alkali metal ions and organic ammonium ions, and the rest are protons. R1 represents a methyl group or a hydrogen atom. n and m each represent an integer of 0 to 6 (provided that n and m must not be 0 at the same time).

In (Formula 2), R2 represents a methyl group or a hydrogen atom.

In (Formula 3), R3 represents a methyl group or a hydrogen atom.

In (Formula 4), R4 represents a methyl group or a hydrogen atom.   2. The ink for ink jet recording according to claim 1, wherein the content of the structural unit of (Formula 1) in the copolymer is 10 to 60% by mass.   The ink for inkjet recording according to claim 1 or 2, wherein the copolymer has a mass average molecular weight of 5,000 to 50,000. In an inkjet recording ink containing at least water, a water-soluble organic solvent, a pigment, and a copolymer having a phosphoric acid group, the copolymer includes at least a monomer represented by the following (formula 5) and the following (formula 6): ) And a monomer represented by the following (formula 7) or (formula 8) are copolymerized.

In (Formula 5), R5 represents a methyl group or a hydrogen atom. n and m each represent an integer of 0 to 6 (provided that n and m must not be 0 at the same time).

In (Formula 6), R6 represents a methyl group or a hydrogen atom.

In (Formula 7), R7 represents a methyl group or a hydrogen atom.

In Formula 8, R8 represents a methyl group or a hydrogen atom.   An ink cartridge, wherein the ink for ink jet recording according to claim 1 is contained in a container.   An ink jet recording apparatus comprising the ink cartridge according to claim 5.   An ink jet recording method comprising at least an ink flying step of recording an image by applying a stimulus to the ink for ink jet recording according to claim 1 and causing the ink to fly.   An ink recorded matter comprising an image recorded with the ink for ink jet recording according to any one of claims 1 to 4 on a recording medium.

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