JP2019006892A - Set, recording method, and recording device - Google Patents

Abstract

To provide a set and a recording method capable of preventing storage stability of an ink from being reduced even when addition amounts of resins or the like are increased, under a condition that problems of smear property leading falling off of an ink film formed on a surface layer is not generated and the falling off of the ink film is suppressed by adding a resin emulsion or a water-soluble resin or the like to the ink, when a recording medium is rubbed since smoothness of a recording medium surface is poor in the case that the ink is added to a coat paper which is a recording medium low in glossiness of a surface layer.SOLUTION: There is provided a set having an ink containing a copolymer and a recording medium having a surface layer containing a cationic material, in which the copolymer has a structural unit represented by one of the general formula (1) or a derivative thereof, and a structural unit having an anionic functional group, and 60 degree glossiness in the surface layer of the recording medium is 13 or less.SELECTED DRAWING: None

Description

  The present invention relates to a set, a recording method, and a recording apparatus.

  A water-based ink using a pigment is known as an ink used in the ink jet recording system. In such an ink, it is necessary to stably disperse a pigment that is difficult to dissolve in water for a long period of time in water. Therefore, it is effective to use a pigment dispersion resin in combination.

  Patent Document 1 discloses a pigment dispersion resin having a structural unit having an anionic site and a structural unit having a naphthyl group at the terminal, and discloses that ink containing this pigment dispersion resin can be discharged onto a predetermined coated paper. ing.

  However, when a recording medium having a low glossiness of the surface layer is used as the coated paper, the smoothness of the surface of the recording medium is inferior, so that the ink film formed on the surface layer is missing when the recording medium is rubbed. The problem arises. In addition, the addition of a resin emulsion or a water-soluble resin to the ink can suppress the loss of the ink film. However, when the amount of the resin added increases, there arises a problem that the storage stability of the ink is lowered.

（上記一般式（１）中、Ｒ^１は水素原子またはメチル基を表し、Ａ_１、Ａ_２、及びＡ_３はそれぞれ独立して−Ｏ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＮＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＮＨ−の群から選ばれる２価の置換基を表し、Ｘ_１、及びＸ_２はそれぞれ独立して単結合、炭素数１以上１２以下のアルキレン基、炭素数１以上１２以下のアルケニレン基、一般式（４）、一般式（５）、及び一般式（６）の群から選ばれる２価の置換基を表し、Ａｒは芳香族基を表す。）

（上記一般式（２）中、Ｒ^１、Ａ_１、Ａ_２、Ｘ_１、Ｘ_２、及びＡｒはそれぞれ独立して一般式（１）と同じものを表す。）

（上記一般式（３）中、Ｒ^１、Ａ_１、Ａ_２、Ａ_３、Ｘ_１、Ｘ_２、及びＡｒはそれぞれ独立して一般式（１）と同じものを表し、Ａ_４は−Ｏ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＮＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＮＨ−の群から選ばれる２価の置換基を表し、Ｚは２価の炭化水素基を表す。）

（上記一般式（４）中、ｌは１以上１０以下の整数を表す。）

（上記一般式（５）中、ｍは１以上１０以下の整数を表す。）

（上記一般式（６）中、ｎは１以上１０以下の整数を表す。） The invention according to claim 1 is a set comprising an ink containing a copolymer and a recording medium having a surface layer containing a cationic substance, wherein the copolymer is represented by the following general formula (1): A set having a structural unit represented by any one of (3) to (3) and a structural unit having an anionic functional group, and the 60 ° glossiness of the surface layer of the recording medium is 13 or less. It is.

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and A ₁ , A ₂ , and A ₃ are each independently —O—, —CO—O—, —O—CO—, Represents a divalent substituent selected from the group of —CO—NH—, —NH—CO—, —NH—CO—O—, —O—CO—NH—, wherein X ₁ and X ₂ are each independently A single bond, an alkylene group having 1 to 12 carbon atoms, an alkenylene group having 1 to 12 carbon atoms, a divalent group selected from the group consisting of general formula (4), general formula (5), and general formula (6). Represents a substituent, and Ar represents an aromatic group.)

(In the general formula (2), R ¹ , A ₁ , A ₂ , X ₁ , X ₂ and Ar each independently represent the same as in the general formula (1).)

(In the general formula (3), R ¹ , A ₁ , A ₂ , A ₃ , X ₁ , X ₂ and Ar each independently represent the same as in the general formula (1), and A ₄ represents —O Divalent substitution selected from the group of-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -NH-CO-O-, -O-CO-NH-. And Z represents a divalent hydrocarbon group.)

(In the general formula (4), l represents an integer of 1 or more and 10 or less.)

(In the general formula (5), m represents an integer of 1 or more and 10 or less.)

(In the general formula (6), n represents an integer of 1 or more and 10 or less.)

  In the present invention, even when a recording medium having a low glossiness of the surface layer is used, the smear property is sufficiently satisfied, and the ink has excellent storage stability.

FIG. 1 is an explanatory perspective view of the recording apparatus. FIG. 2 is an explanatory perspective view of the main tank.

  Hereinafter, embodiments of the present invention will be described.

(set)
The set of the present invention includes ink, a recording medium, and the like.
<Ink>
Hereinafter, the organic solvent, water, color material, resin, additive, and the like used for the ink will be described.

<Copolymer>
The copolymer contained in the ink has a structural unit represented by any one of the general formulas (1) to (3) and a structural unit having an anionic functional group, and if necessary, And other structural units.

一般式（１）中、Ｒ^１は水素原子またはメチル基を表す。Ａ_１、Ａ_２、及びＡ_３はそれぞれ独立して−Ｏ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＮＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＮＨ−の群から選ばれる２価の置換基を表す。Ｘ_１、及びＸ_２はそれぞれ独立して単結合、炭素数１以上１２以下のアルキレン基、炭素数１以上１２以下のアルケニレン基、一般式（４）、一般式（５）、及び一般式（６）の群から選ばれる２価の置換基を表す。Ａｒは芳香族基を表し、特に制限はなく、目的に応じて適宜選択することができ、例えば、ベンゼン環、縮合ベンゼン環、非ベンゼン系芳香環、複合芳香環などが挙げられる。具体的には、例えば、フェニル基、トリル基、キシリル基、ナフチル基、メチルナフチル基、アントリル基、フェナントレニル基、ビフェニル基、ピリジニル基、トリアジニル基、フェナンスリル基、ピレニル基、フルオレニル基などが挙げられる。 -Structural unit represented by general formula (1)-

In general formula (1), R ¹ represents a hydrogen atom or a methyl group. A ₁ , A ₂ , and A ₃ are each independently —O—, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—, —NH—CO—O—, Represents a divalent substituent selected from the group of —O—CO—NH—. X ₁ and X ₂ are each independently a single bond, an alkylene group having 1 to 12 carbon atoms, an alkenylene group having 1 to 12 carbon atoms, general formula (4), general formula (5), and general formula ( 6) represents a divalent substituent selected from the group of 6). Ar represents an aromatic group and is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a benzene ring, a condensed benzene ring, a non-benzene aromatic ring, and a composite aromatic ring. Specific examples include phenyl, tolyl, xylyl, naphthyl, methylnaphthyl, anthryl, phenanthrenyl, biphenyl, pyridinyl, triazinyl, phenanthryl, pyrenyl, and fluorenyl groups. .

一般式（４）中、ｌは１以上１０以下の整数を表す。

In general formula (4), l represents an integer of 1 or more and 10 or less.

一般式（５）中、ｍは１以上１０以下の整数を表す。

In general formula (5), m represents an integer of 1 or more and 10 or less.

一般式（６）中、ｎは１以上１０以下の整数を表す。

In general formula (6), n represents an integer of 1 or more and 10 or less.

一般式（２）中、Ｒ^１、Ａ_１、Ａ_２、Ｘ_１、Ｘ_２、及びＡｒはそれぞれ独立して一般式（１）と同じものを表す。 -Structural unit represented by general formula (2)-

In general formula (2), R ¹ , A ₁ , A ₂ , X ₁ , X ₂ and Ar each independently represent the same as in general formula (1).

一般式（３）中、Ｒ^１、Ａ_１、Ａ_２、Ａ_３、Ｘ_１、Ｘ_２、及びＡｒはそれぞれ独立して一般式（１）と同じものを表す。Ａ_４は−Ｏ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＮＨ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＮＨ−の群から選ばれる２価の置換基を表す。Ｚは２価の炭化水素基を表し、例えば、脂肪族炭化水素基、環式脂肪族炭化水素基、芳香族炭化水素基などが挙げられ、炭素数２以上１５以下のアルキレン基、炭素数２以上１５以下のアルケニレン基、炭素数３以上１５以下の環式飽和炭化水素基、炭素数３以上１５以下の環式不飽和炭化水素基、炭素数６以上１５以下のアリーレン基などが好ましい。 -Structural unit represented by general formula (3)-

In General Formula (3), R ¹ , A ₁ , A ₂ , A ₃ , X ₁ , X ₂ , and Ar each independently represent the same as in General Formula (1). A ₄ is selected from the group of —O—, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—, —NH—CO—O—, —O—CO—NH—. Represents a divalent substituent. Z represents a divalent hydrocarbon group, and examples thereof include an aliphatic hydrocarbon group, a cycloaliphatic hydrocarbon group, an aromatic hydrocarbon group, and the like, an alkylene group having 2 to 15 carbon atoms, and a carbon number of 2 An alkenylene group having 15 to 15 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 15 carbon atoms, a cyclic unsaturated hydrocarbon group having 3 to 15 carbon atoms, and an arylene group having 6 to 15 carbon atoms are preferable.

  Hereinafter, structural units represented by any one of the general formulas (1) to (3) will be exemplified.

  The aromatic group represented by Ar present at the ends of the general formula (1), the general formula (2), and the general formula (3) is excellent due to π-π stacking with a pigment that is a coloring material in the ink. Has a pigment adsorption power. When the above-mentioned copolymer is used in preparing a pigment dispersion in which a pigment is dispersed in water, since the adsorptive power with the pigment is high, the dispersion stability is increased and a dispersion having high storage stability is obtained. Further, even when a hydrophilic organic solvent is added to the ink, the dispersibility is maintained and an ink having high storage stability can be obtained.

  The content of the structural unit represented by any one of the general formulas (1) to (3) is not particularly limited and may be appropriately selected depending on the intended purpose. However, with respect to the total amount of the copolymer 30 mass% or more and 80 mass% or less is preferable, and 40 mass% or more and 70 mass% or less are more preferable. When the content is within a preferable range, it is advantageous in that the image density and storage stability are improved when used in an ink.

一般式（７）中、Ｒ^２は水素原子またはメチル基を表し、Ｌは炭素数２以上１６以下のアルキレン基を表す。以下、一般式（７）の構造単位を形成するモノマーの具体例を挙げるがこれらに限定されるわけではない。

Moreover, it is preferable that the structural unit represented by any one of General formula (1) thru | or (3) has a structural unit represented by General formula (7) below.

In General Formula (7), R ² represents a hydrogen atom or a methyl group, and L represents an alkylene group having 2 to 16 carbon atoms. Hereinafter, although the specific example of the monomer which forms the structural unit of General formula (7) is given, it is not necessarily limited to these.

  In the general formula (7), polar groups such as —CO—O— group and —NH—CO— group contained in the structural unit are well-balanced in the structural unit, and the adsorbability with the pigment is sufficiently maintained. The dispersion state can be stably maintained even in the solvent used for the ink.

-Structural unit having an anionic functional group-
The structural unit having an anionic functional group is formed by copolymerizing a monomer having an anionic functional group. Examples of the monomer having an anionic functional group include an unsaturated carboxylic acid monomer, an unsaturated sulfonic acid monomer, and an unsaturated phosphoric acid monomer. These monomers having an anionic functional group may be used alone or in admixture of two or more.
Examples of the unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.
Examples of the unsaturated sulfonic acid monomer include styrene sulfonic acid and 2-acrylamido-2-methylpropane sulfonic acid.
Examples of unsaturated phosphoric acid monomers include vinylphosphonic acid, vinyl phosphate, bis (methacryloxyethyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acrylic acid. And leuoxyethyl phosphate.

The structural unit having an anionic functional group may be neutralized with a base.
Examples of the base include sodium hydroxide, potassium hydroxide, lithium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide. , Triethylmethylammonium hydroxide, tributylmethylammonium hydroxide, trioctylmethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, tris (2-hydroxyethyl) methylammonium hydroxide, propyltrimethylammonium hydroxide, hexyltrimethylammonium Hydroxide, octyltrimethylammonium hydride Xoxide, nonyltrimethylammonium hydroxide, decyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, tetradecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octadecyltrimethylammonium hydroxide, didodecyldimethylammonium hydroxide, ditetradecyl Dimethylammonium hydroxide, dihexadecyldimethylammonium hydroxide, dioctadecyldimethylammonium hydroxide, ethylhexadecyldimethylammonium hydroxide, aqueous ammonia, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, Examples include ethanolamine, methylethanolamine, methyldiethanolamine, dimethylethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, isopropanolamine, morpholine, N-methylmorphone, N-methyl-2-pyrrolidone, and 2-pyrrolidone. .
You may use the base as a neutralizing agent individually or in mixture of 2 or more types. The neutralization treatment may be performed when a monomer having an anionic functional group is copolymerized, or may be performed when the copolymer is dissolved.

  The above copolymer contains a structural unit having such an anionic functional group, thereby reacting with a cationic substance contained in the paper and increasing the cohesiveness of the pigment, thereby realizing a high image density. can do. Further, since the copolymer has reactivity with the cationic substance contained in the paper, the pigment can be strongly adsorbed on the paper surface. Therefore, it is possible to exhibit a sufficiently satisfactory smear property even on glossy paper having a large surface roughness and low gloss. The cationic substance is a substance that elutes cations into the ink when it comes into contact with the ink. For example, calcium ions are eluted.

  The content of the structural unit having an anionic functional group is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 30% by mass to 80% by mass with respect to the total amount of the copolymer. 40 mass% or more and 70 mass% or less is more preferable.

  The molar ratio between the structural unit represented by any one of the general formulas (1) to (3) and the structural unit having an anionic functional group is not particularly limited, and is appropriately determined depending on the purpose. It can be selected from the viewpoint of the balance between hydrophilicity and hydrophobicity of the copolymer, image density, storage stability, and smear properties. For example, from the viewpoint of storage stability, “1.0: 1.2 to 1.0: 2.0” is preferable. Further, from the viewpoint of image density and smear properties, “1.0: 1.5 to 1.0: 2.5” is preferable. Therefore, the molar ratio between the structural unit represented by any one of the general formulas (1) to (3) and the structural unit having an anionic functional group is “1.0: 1.5-1”. 0.0: 2.0 "is most preferred.

一般式（８）中、Ｒ^３は水素原子またはメチル基を表し、Ｘは水素原子又は陽イオンを表す。 Moreover, as a structural unit which has an anionic functional group, it is preferable to have a structural unit represented by General formula (8).

In the general formula (8), R ³ represents a hydrogen atom or a methyl group, and X represents a hydrogen atom or a cation.

When X is a cation, the oxygen adjacent to the cation is present as O ⁻ . As cations, sodium ion, potassium ion, lithium ion, tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ion, tetrapentylammonium ion, tetrahexylammonium ion, triethylmethylammonium ion, tributylmethyl Ammonium ion, trioctylmethylammonium ion, 2-hydroxyethyltrimethylammonium ion, tris (2-hydroxyethyl) methylammonium ion, propyltrimethylammonium ion, hexyltrimethylammonium ion, octyltrimethylammonium ion, nonyltrimethylammonium ion, decyltrimethyl Ammonium ion Dodecyltrimethylammonium ion, tetradecyltrimethylammonium ion, hexadecyltrimethylammonium ion, octadecyltrimethylammonium ion didodecyldimethylammonium ion, ditetradecyldimethylammonium ion, dihexadecyldimethylammonium ion, dioctadecyldimethylammonium ion, ethylhexadecyl Dimethylammonium ion, ammonium ion, dimethylammonium ion, trimethylammonium ion, monoethylammonium ion, diethylammonium ion, triethylammonium ion, monoethanolammonium ion, diethanolammonium ion, triethanolammonium ion, methylethanol ammonium ion Ion, methyldiethanolammonium ion, dimethylethanolammonium ion, monopropanolammonium ion, dipropanolammonium ion, tripropanolammonium ion, isopropanolammonium ion, morpholinium ion, N-methylmorpholinium ion, N-methyl-2- Examples include pyrrolidonium ions and 2-pyrrolidonium ions. X is preferably hydrogen in terms of reactivity with cations derived from cationic substances such as calcium ions contained in paper.

  In addition, the monomer that forms the general formula (8) is preferably a monomer having a carboxyl group, and more preferably acrylic acid or methacrylic acid, from the viewpoint of storage stability of the ink.

-Other structural units-
In addition to the structural unit represented by any one of the general formulas (1) to (3) and the structural unit having an anionic functional group, the copolymer further includes other structural units as necessary. Including.
Other structural units are structural units derived from, for example, a polymerizable hydrophobic monomer, a polymerizable hydrophilic monomer, a polymerizable surfactant, and the like.

（反応式２）

また別の方法としては、先に（Ａ−１）と（Ａ−４）を反応させた後、（Ａ−２）と反応させて、一般式（１）で表される構造単位の元となるモノマーを得ることができる。
さらに別の方法としては、下記反応式３に示すように、ジイソシアネート化合物（Ａ−１）、ナフトール（Ａ−２）、ヒドロキシアルキルメタクリレート（Ａ−４）を反応させ、一般式（１）で表される構造単位の元となるモノマーを得ることもできる。
（反応式３）

-Synthesis Method of Copolymer Containing Structural Unit Represented by General Formula (1)-
The copolymer containing the structural unit represented by the general formula (1) is obtained by copolymerizing a monomer that is a base of the structural unit represented by the general formula (1), a monomer having an anionic functional group, and the like. can get.
As an example, the monomer that is the base of the structural unit represented by the general formula (1) can be synthesized and used as follows. That is, as shown in the following reaction formulas 1 and 2, first, the diisocyanate compound (A-1) and naphthol (A-2) are reacted in the presence of an acid acceptor such as an amine or pyridine, thereby producing a reaction intermediate. (A-3) is obtained. Subsequently, the monomer which becomes the origin of the structural unit represented by General formula (1) can be obtained by making hydroxyalkyl methacrylate (A-4) and (A-3) react.
(Reaction Formula 1)

(Reaction Formula 2)

As another method, (A-1) and (A-4) are reacted first, and then (A-2) is reacted with the element of the structural unit represented by the general formula (1). Can be obtained.
As another method, as shown in the following reaction formula 3, the diisocyanate compound (A-1), naphthol (A-2), and hydroxyalkyl methacrylate (A-4) are reacted, and represented by the general formula (1). It is also possible to obtain a monomer from which the structural unit is formed.
(Reaction Formula 3)

As a method for synthesizing the copolymer containing the structural unit represented by the general formula (1), a method using a radical polymerization initiator is preferable because the polymerization operation and the adjustment of the molecular weight are easy. A solution polymerization method is more preferable.
Preferred solvents for radical polymerization by the solution polymerization method include ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, acetate solvents such as ethyl acetate and butyl acetate, and aromatic carbonization such as benzene, toluene and xylene. Examples thereof include hydrogen solvents, isopropanol, ethanol, cyclohexane, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoamide, and the like, and ketone solvents, acetate solvents, and alcohol solvents are more preferable.
There is no restriction | limiting in particular as a radical polymerization initiator, According to the objective, it can select suitably. Examples thereof include peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters, cyano azobisisobutyronitriles, azobis (2-methylbutyronitrile), Examples thereof include azobis (2,2′-isovaleronitrile), non-cyano dimethyl-2,2′-azobisisobutyrate, and the like. Among these, organic peroxides and azo compounds are preferable, and azo compounds are particularly preferable because the molecular weight is easily controlled and the decomposition temperature is low.
There is no restriction | limiting in particular in content of a radical polymerization initiator, Although it can select suitably according to the objective, 1-10 mass% is preferable with respect to the total amount of a polymerizable monomer.
An appropriate amount of a chain transfer agent may be added to adjust the molecular weight of the polymer.
Examples of chain transfer agents include mercaptoacetic acid, mercaptopropionic acid, 2-propanethiol, 2-mercaptoethanol, thiophenol, dodecyl mercaptan, 1-dodecanethiol, thioglycerol, and the like.
The polymerization temperature is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 ° C to 150 ° C, more preferably 60 ° C to 100 ° C. The polymerization time is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 to 48 hours.

また別の方法としては、下記反応式５に示すように、カルボキシル基を有するナフタレン誘導体の酸塩化物（Ｂ−４）と、ジオール化合物（Ｂ−１）を、アミン又はピリジンなどの酸受容体の存在下で反応させて、反応中間体（Ｂ−３）を得ることもできる。
（反応式５）

次いで、下記反応式６に示すように、（メタ）アクリル酸クロリド（Ｂ−５）と（Ｂ−３）とを反応させて、一般式（２）で表される構造単位の元となるモノマーを得ることもできる。
（反応式６）

-Synthesis Method of Copolymer Containing Structural Unit Represented by General Formula (2)-
The copolymer containing the structural unit represented by the general formula (2) is obtained by copolymerizing a monomer that is a base of the structural unit represented by the general formula (2), a monomer having an anionic functional group, and the like. can get.
As an example, the monomer that is the base of the structural unit represented by the general formula (2) can be synthesized and used as follows. That is, as shown in the following reaction formula 4, a diol compound (B-1) and a naphthalene derivative (B-2) having a carboxyl group are reacted in the presence of an acid catalyst to produce a reaction intermediate (B-3). )
(Reaction Formula 4)

As another method, as shown in the following reaction formula 5, an acid chloride (B-4) of a naphthalene derivative having a carboxyl group and a diol compound (B-1) are converted into an acid acceptor such as an amine or pyridine. The reaction intermediate (B-3) can also be obtained by reacting in the presence of.
(Reaction Formula 5)

Next, as shown in the following reaction formula 6, (meth) acrylic acid chloride (B-5) and (B-3) are reacted to form a monomer serving as a base of the structural unit represented by the general formula (2) You can also get
(Reaction Formula 6)

  As a method for synthesizing the copolymer including the structural unit represented by the general formula (2), a method similar to the method for synthesizing the copolymer including the structural unit represented by the general formula (1) is preferable.

（反応式８）

（反応式９）

また別の方法としては、先に（Ｃ−４）と（Ｃ−６）を反応させた後、（Ｃ−１）、（Ｃ−２）と次いで反応させる方法、先に（Ｃ−１）と（Ｃ−２）を反応させて得られた中間体と、別途、（Ｃ−４）と（Ｃ−６）を反応させて得られた中間体とを反応させる方法などにより、一般式（３）で表されるモノマーを得ることができるが、（Ｃ−１）、（Ｃ−２）、（Ｃ−４）、（Ｃ−６）を反応させる順番に特に制限はない。
さらに別の方法としては、下記反応式１０に示すように、ジオール化合物（Ｃ−１）、ナフタレン酸化合物（Ｃ−２）、ジイソシアネート化合物（Ｃ−４）、ヒドロキシアルキル（メタ）アクリレート（Ｃ−６）を反応させ、一般式（３）で表されるモノマーを得ることもできる。
（反応式１０）

-Synthesis Method of Copolymer Containing Structural Unit Represented by General Formula (3)-
The copolymer containing the structural unit represented by the general formula (3) is obtained by copolymerizing a monomer that is a base of the structural unit represented by the general formula (3), a monomer having an anionic functional group, and the like. can get.
As an example, the monomer that is the base of the structural unit represented by the general formula (3) can be synthesized and used as follows. That is, as shown in the following reaction formulas 7 to 9, the diol compound (C-1) and the naphthalene acid compound (C-2) are first condensed to obtain a reaction intermediate (C-3). Next, the diisocyanate compound (C-4) and (C-3) are reacted in the presence of an acid acceptor such as amine or pyridine or in the presence of a metal catalyst such as tin or titanium, thereby producing a reaction intermediate (C -5) is obtained. Subsequently, the monomer represented by General formula (3) can be obtained by reacting hydroxyalkyl (meth) acrylate (C-6) and (C-5).
The compound represented by (C-2) is not particularly limited as long as it is a naphthalene acid compound that can be condensed with a hydroxy group, and the group represented by L is, for example, a carboxylic acid or a carboxylic acid ester such as a hydroxy group or an alkoxide group. Or a halogen-based leaving group such as chlorine, bromine and fluorine, or a leaving group such as tosyl group, mesyl group and ammonium ion, but is not limited thereto.
(Reaction Formula 7)

(Reaction Formula 8)

(Reaction Formula 9)

As another method, (C-4) and (C-6) are reacted first, and then (C-1) and (C-2) are reacted next. (C-1) And an intermediate obtained by reacting (C-2) with an intermediate obtained by reacting (C-4) and (C-6) separately, etc. Although the monomer represented by 3) can be obtained, there is no particular limitation on the order of reacting (C-1), (C-2), (C-4), and (C-6).
As another method, as shown in the following reaction formula 10, diol compound (C-1), naphthalene acid compound (C-2), diisocyanate compound (C-4), hydroxyalkyl (meth) acrylate (C- The monomer represented by the general formula (3) can also be obtained by reacting 6).
(Reaction Formula 10)

  As a method for synthesizing the copolymer containing the structural unit represented by the general formula (3), a method similar to the method for synthesizing the copolymer containing the structural unit represented by the general formula (1) is preferable.

-Physical properties of copolymer-
The weight average molecular weight of the copolymer is preferably 5000 to 50000 in terms of polystyrene. More preferably, it is 15000-40000. When the weight average molecular weight is within the preferred range, it is advantageous in that the image density and storage stability are good when used in ink.

-Amount of copolymer added-
The addition amount of the copolymer with respect to the total amount of the ink is not particularly limited and may be appropriately selected depending on the intended purpose. 3 mass% or more and 5.0 mass% or less are more preferable. When the content is 0.05% by mass or more, the effect of dispersibility and storage stability is improved, and when the content is 10.0% by mass or less, the viscosity range is suitable for discharging ink from the head. Is possible.
The copolymer is not particularly limited, and can be used as a pigment dispersant or an additive to the pigment dispersion. When used as a pigment dispersant, further improvement in storage stability is observed in an ink having a high water-soluble organic solvent content. The content of the copolymer is not particularly limited when used as a pigment dispersant, and can be appropriately selected according to the purpose. For example, 1 part by mass or more and 100 parts by mass or less is preferable with respect to 100 parts by mass of the pigment, and 5 parts by mass or more and 80 parts by mass or less are more preferable. When the content is within the above range, it is advantageous in that image density and storage stability are improved. In addition, you may use another dispersing agent together in the range which does not impair the effect as a dispersing agent of a copolymer.

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

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

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

The ink used in the set of the present invention preferably uses an organic solvent having a solubility parameter of 9.00 or more and 11.80 or less for the purpose of improving image quality. By using such an organic solvent, defective images such as beading and bleeding are generated even when ink is applied to a recording medium having a surface layer used in the present invention, such as a recording medium having low ink absorption. Without this, high-quality image formation is possible. On the other hand, when such an organic solvent is used, in the ink, the adsorptive power of the copolymer with respect to the pigment may be reduced, and the dispersion stability of the pigment may be reduced and ejection failure may occur, but the general formula ( By using the copolymer having the structural unit represented by any one of 1) to (3), it is possible to achieve both high image quality, dispersion stability, and good dispersion stability.
The solubility parameter is obtained by quantifying each other's solubility, and is expressed by a square root of an attraction force between molecules, that is, a cohesive energy density CED (Cohesive Energy Density). CED is the amount of energy required to evaporate 1 mL.
The solubility parameter (SP value) is defined by the regular solution theory introduced by Hildebrand and is a measure of the solubility of the binary solution. Although there are various theories on the calculation method of the solubility parameter, the SP value can be calculated by the following formula (A) by the method of Fedors generally used in the present invention.
Solubility parameter (SP value) = (CED value) ^1/2 = (E / V) ^1/2 Formula (A)
In the formula (A), E is the molecular cohesive energy (cal / mol), V is the molecular volume (cm ³ / mol), and when the atom group evaporation energy is Δei and the molar volume is Δvi, the following formula (B ) And the formula (C).
E = ΣΔei Expression (B)
V = ΣΔvi Expression (C)
In addition, as various data of said calculation method, evaporation energy (DELTA) ei of each atomic group, and molar volume (DELTA) vi, the data as described in "Fundamental theory of adhesion | attachment" (Akira Imoto, the publication of a polymer publication, Chapter 5) are used. Can be used. For those in which values such as -CF ₃ group are not shown, Robert F. et al. Fedors, Polymer Engineering and Science, 1974, Vol14, No. 2,147-154. Note that. The unit of the solubility parameter is (cal / cm ³ ) ^1/2 .
Specific examples of the organic solvent having a solubility parameter of 9.00 or more and 11.80 or less are listed below together with the solubility parameter.
3-butoxy-N, N-dimethylpropanamide (9.03), N, N-dimethyl-3-propanamide (9.08), 3-ethoxy-N, N-dimethylpropanamide (9.13), 3-methoxy-N, N-dimethylpropanamide (9.19), 3-methoxy-3-methylbutanol (9.64), diethylene glycol monohexyl ether (9.66), triethylene glycol monobutyl ether (9.77) ), 3-methyl-1-butanol (9.79), 1-propoxy-2-propanol (9.82), diethylene glycol monobutyl ether (9.86), 3-methoxy-1-butanol (9.98), 2-butanol (9.98), ethylene glycol monobutyl ether (9.99), 1-pentanol (9.99) Diethylene glycol monoethyl ether (10.14), 1-methoxy-2-propanol (10.19), 1-butanol (10.21), 2-propanol (10.24), 1-propanol (10.52), 1-methyl-2-pyrrolidone (10.84), ethanol (10.96), δ-valerolactone (11.06), 3-ethyl-3-oxetanemethanol (11.31), hexylene glycol (11. 49), tetraethylene glycol (11.58), γ-butyrolactone (11.62), menothal (11.68), 3-methyl-3-oxetanemethanol (11.79) and the like.
Among these organic solvents, 3-butoxy-N, N-dimethylpropanamide, N, N-dimethyl-3-propanamide, and 3-ethoxy-N are preferred in terms of both storage stability and high-quality image formation. , N-dimethylpropanamide, 3-methoxy-N, N-dimethylpropanamide, 3-ethyl-3-oxetanemethanol and 3-methyl-3-oxetanemethanol are preferred. Any of these may be used alone or in combination of two or more. The content of the organic solvent having a solubility parameter of 9.00 or more and 11.80 or less is 10% by mass or more and 60% by mass or less, and more preferably 20% by mass or more and 50% by mass or less with respect to the total amount of the ink.

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

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

<Color material>
The color material is not particularly limited, and pigments and dyes can be used.
An inorganic pigment or an organic pigment can be used as the pigment. These may be used alone or in combination of two or more. A mixed crystal may be used.
As the pigment, for example, a black pigment, a yellow pigment, a magenta pigment, a cyan pigment, a white pigment, a green pigment, an orange pigment, a glossy pigment such as gold or silver, a metallic pigment, or the like can be used.
Carbon black produced by known methods such as contact method, furnace method, thermal method in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow as inorganic pigments Can be used.
Organic pigments include azo pigments, polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.) Dye chelates (for example, basic dye type chelates, acidic dye type chelates), nitro pigments, nitroso pigments, aniline black, and the like can be used. Of these pigments, those having good affinity with the solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used.
Specific examples of pigments include black for carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, or copper, iron (CI pigment black 11). And metal pigments such as titanium oxide and organic pigments such as aniline black (CI Pigment Black 1).
Further, for color use, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104 , 108, 109, 110, 117, 120, 138, 150, 153, 155, 180, 185, 213, C.I. I. Pigment orange 5, 13, 16, 17, 36, 43, 51, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48: 2, 48: 2 (Permanent Red 2B (Ca)), 48: 3, 48: 4, 49: 1, 52: 2, 53: 1, 57: 1 (Brilliant Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (Bengara), 104, 105, 106, 108 ( Cadmium red), 112, 114, 122 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 184, 185, 190, 193, 202, 207, 208, 209, 213, 219, 224, 254, 264, C.I. I. Pigment violet 1 (rhodamine lake), 3, 5: 1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15: 1, 15: 2, 15: 3, 15: 4 (phthalocyanine blue), 16, 17: 1, 56, 60, 63, C.I. I. Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, etc.
The dye is not particularly limited, and an acid dye, a direct dye, a reactive dye, and a basic dye can be used. One kind may be used alone, or two or more kinds may be used in combination.
Examples of the dye include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142, C.I. I. Acid Red 52, 80, 82, 249, 254, 289, C.I. I. Acid Blue 9, 45, 249, C.I. I. Acid Black 1, 2, 24, 94, C.I. I. Food Black 1, 2, C.I. I. Direct Yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 142, 144, 173, C.I. I. Direct Red 1, 4, 9, 80, 81, 225, 227, C.I. I. Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202, C.I. I. Directed Black 19, 38, 51, 71, 154, 168, 171, 195, C.I. I. Reactive Red 14, 32, 55, 79, 249, C.I. I. Reactive black 3, 4, and 35 are mentioned.

  The content of the color material in the ink is preferably 0.1% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass from the viewpoints of improvement in image density, good fixability and ejection stability. It is as follows.

In order to disperse the pigment in the ink, a method of introducing a hydrophilic functional group into the pigment to form a self-dispersing pigment, a method of dispersing the pigment surface by coating with a resin, a method of dispersing using a dispersant, Etc.
Examples of a method for introducing a hydrophilic functional group into a pigment to form a self-dispersing pigment include a self-dispersing pigment that can be dispersed in water by adding a functional group such as a sulfone group or a carboxyl group to the pigment (for example, carbon). Can be used.
As a method for coating the surface of the pigment with a resin and dispersing it, a method in which the pigment is included in microcapsules and can be dispersed in water can be used. This can be paraphrased as a resin-coated pigment. In this case, it is not necessary that all pigments blended in the ink are coated with a resin, and within a range where the effects of the present invention are not impaired, uncoated pigments and partially coated pigments are dispersed in the ink. It may be.
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low-molecular type dispersant or high-molecular type dispersant represented by a surfactant.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or the like can be used depending on the pigment.
RT-100 (nonionic surfactant) manufactured by Takemoto Yushi Co., Ltd. and naphthalenesulfonic acid Na formalin condensate can also be suitably used as a dispersant.
A dispersing agent may be used individually by 1 type, or may use 2 or more types together.

<Pigment dispersion>
An ink can be obtained by mixing a material such as water or an organic solvent with a color material. Further, it is also possible to produce an ink by mixing a pigment, other water, a dispersant, and the like into a pigment dispersion and mixing a material such as water or an organic solvent.
The pigment dispersion is obtained by dispersing water, a pigment, a pigment dispersant, and other components as required, and adjusting the particle size. For dispersion, a disperser is preferably used.
The particle size of the pigment in the pigment dispersion is not particularly limited, but the maximum frequency is 20 nm or more in terms of maximum number because the pigment dispersion stability is good and the image quality such as ejection stability and image density is also high. 500 nm or less is preferable and 20 nm or more and 150 nm or less are more preferable. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).
The content of the pigment in the pigment dispersion is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of obtaining good ejection stability and increasing the image density, 0.1% by mass. % To 50% by mass is preferable, and 0.1% to 30% by mass is more preferable.
The pigment dispersion is preferably degassed by filtering coarse particles with a filter, a centrifugal separator or the like, if necessary.

<Resin>
The type of resin contained in the ink is not particularly limited and can be appropriately selected according to the purpose. For example, urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene type Examples thereof include resins, styrene-butadiene resins, vinyl chloride resins, acrylic styrene resins, and acrylic silicone resins.
Resin particles made of these resins may be used. An ink can be obtained by mixing resin particles with a material such as a colorant or an organic solvent in a resin emulsion state in which water is dispersed as a dispersion medium. As said resin particle, what was synthesize | combined suitably may be used and a commercial item may be used. Moreover, these may be used individually by 1 type, or may be used in combination of 2 or more types of resin particles.

The volume average particle diameter of the resin particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 nm or more and 1,000 nm or less from the viewpoint of obtaining good fixability and high image hardness. It is more preferably 200 nm or less and particularly preferably 10 nm or more and 100 nm or less.
The volume average particle diameter can be measured using, for example, a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

  The resin content is not particularly limited and may be appropriately selected according to the purpose. However, from the viewpoint of fixability and ink storage stability, the content of the resin is 1% by mass or more and 30% by mass or less. Is preferable, and 5 mass% or more and 20 mass% or less are more preferable.

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

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

<Surfactant>
As the surfactant, any of silicone surfactants, fluorine surfactants, amphoteric surfactants, nonionic surfactants and anionic surfactants can be used.
There is no restriction | limiting in particular in silicone type surfactant, According to the objective, it can select suitably. Among them, those that do not decompose even at high pH are preferable, and examples thereof include side chain modified polydimethylsiloxane, both terminal modified polydimethylsiloxane, one terminal modified polydimethylsiloxane, and side chain both terminal modified polydimethylsiloxane. Those having an oxyethylene group or a polyoxyethylene polyoxypropylene group are particularly preferred because they exhibit good properties as an aqueous surfactant. In addition, as the silicone surfactant, a polyether-modified silicone surfactant can be used, and examples thereof include a compound in which a polyalkylene oxide structure is introduced into the side chain of the Si portion of dimethylsiloxane.
Examples of the fluorosurfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. Polyoxyalkylene ether polymer compounds are particularly preferred because of their low foaming properties. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid, perfluoroalkyl sulfonate, and the like. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylate. Examples of the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain include a sulfate ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in the side chain and a perfluoroalkyl ether group in the side chain. Examples thereof include salts of polyoxyalkylene ether polymers. As counter ions of salts in these fluorosurfactants, Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , NH (CH ₂ CH ₂ OH) ₃ etc. are mentioned.
Examples of amphoteric surfactants include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.
Nonionic surfactants include, for example, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, polyoxyethylene sorbitan Examples include fatty acid esters and ethylene oxide adducts of acetylene alcohol.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, laurate, polyoxyethylene alkyl ether sulfate salt, and the like.
These may be used alone or in combination of two or more.

一般式（Ｓ−１）
（但し、一般式（Ｓ−１）式中、ｍ、ｎ、ａ、及びｂは整数を表わす。Ｒ及びＲ’はアルキル基、アルキレン基を表わす。）
上記のポリエーテル変性シリコーン系界面活性剤としては、市販品を用いることができ、例えば、ＫＦ−６１８、ＫＦ−６４２、ＫＦ−６４３（信越化学工業株式会社）、ＥＭＡＬＥＸ−ＳＳ−５６０２、ＳＳ−１９０６ＥＸ（日本エマルジョン株式会社）、ＦＺ−２１０５、ＦＺ−２１１８、ＦＺ−２１５４、ＦＺ−２１６１、ＦＺ−２１６２、ＦＺ−２１６３、ＦＺ−２１６４（東レ・ダウコーニング・シリコーン株式会社）、ＢＹＫ−３３、ＢＹＫ−３８７（ビックケミー株式会社）、ＴＳＦ４４４０、ＴＳＦ４４５２、ＴＳＦ４４５３（東芝シリコン株式会社）などが挙げられる。 The silicone surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, side chain modified polydimethylsiloxane, both terminal modified polydimethylsiloxane, one terminal modified polydimethylsiloxane, side Since both ends of the chain are modified with polydimethylsiloxane, a polyether-modified silicone surfactant having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group exhibits good properties as an aqueous surfactant. preferable.
As such a surfactant, an appropriately synthesized product or a commercially available product may be used. Commercially available products can be obtained from, for example, Big Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., and Kyoeisha Chemical Co., Ltd.
There is no restriction | limiting in particular as said polyether modified silicone surfactant, According to the objective, it can select suitably, For example, the polyalkylene oxide structure represented by a general formula (S-1) type | formula is dimethylpolyethylene. Examples thereof include those introduced into the side chain of Si part of siloxane.

Formula (S-1)
(In the general formula (S-1), m, n, a, and b represent integers. R and R ′ represent an alkyl group and an alkylene group.)
A commercial item can be used as said polyether modified silicone type surfactant, For example, KF-618, KF-642, KF-643 (Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5602, SS- 1906EX (Japan Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (Toray Dow Corning Silicone Co., Ltd.), BYK-33, BYK-387 (Bic Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.), etc. are mentioned.

一般式（Ｆ−１）
上記一般式（Ｆ−１）で表される化合物において、水溶性を付与するためにｍは０〜１０の整数が好ましく、ｎは０〜４０の整数が好ましい。

上記一般式（Ｆ−２）で表される化合物において、ＹはＨ、又はＣｎＦ_２ｎ＋１でｎは１〜６の整数、又はＣＨ_２ＣＨ（ＯＨ）ＣＨ_２−ＣｎＦ_２ｎ＋１でｎは４〜６の整数、又はＣｐＨ_２ｐ＋１でｐは１〜１９の整数である。ａは４〜１４の整数である。
上記のフッ素系界面活性剤としては市販品を使用してもよい。この市販品としては、例えば、サーフロンＳ−１１１、Ｓ−１１２、Ｓ−１１３、Ｓ−１２１、Ｓ−１３１、Ｓ−１３２、Ｓ−１４１、Ｓ−１４５（いずれも、旭硝子株式会社製）；フルラードＦＣ−９３、ＦＣ−９５、ＦＣ−９８、ＦＣ−１２９、ＦＣ−１３５、ＦＣ−１７０Ｃ、ＦＣ−４３０、ＦＣ−４３１（いずれも、住友スリーエム株式会社製）；メガファックＦ−４７０、Ｆ−１４０５、Ｆ−４７４（いずれも、大日本インキ化学工業株式会社製）；ゾニール（Ｚｏｎｙｌ）ＴＢＳ、ＦＳＰ、ＦＳＡ、ＦＳＮ−１００、ＦＳＮ、ＦＳＯ−１００、ＦＳＯ、ＦＳ−３００、ＵＲ（いずれも、ＤｕＰｏｎｔ社製）；ＦＴ−１１０、ＦＴ−２５０、ＦＴ−２５１、ＦＴ−４００Ｓ、ＦＴ−１５０、ＦＴ−４００ＳＷ（いずれも、株式会社ネオス社製）、ポリフォックスＰＦ−１３６Ａ，ＰＦ−１５６Ａ、ＰＦ−１５１Ｎ、ＰＦ−１５４、ＰＦ−１５９（オムノバ社製）、ユニダインＤＳＮ−４０３Ｎ（ダイキン工業株式会社製）などが挙げられ、これらの中でも、良好な印字品質、特に発色性、紙に対する浸透性、濡れ性、均染性が著しく向上する点から、Ｄｕ Ｐｏｎｔ社製のＦＳ−３００、株式会社ネオス製のＦＴ−１１０、ＦＴ−２５０、ＦＴ−２５１、ＦＴ−４００Ｓ、ＦＴ−１５０、ＦＴ−４００ＳＷ、オムノバ社製のポリフォックスＰＦ−１５１Ｎ及びダイキン工業株式会社製のユニダインＤＳＮ−４０３Ｎが特に好ましい。 As the fluorine-based surfactant, a fluorine-substituted compound having 2 to 16 carbon atoms is preferable, and a fluorine-substituted compound having 4 to 16 carbon atoms is more preferable.
Examples of the fluorosurfactant include perfluoroalkyl phosphate compounds, perfluoroalkylethylene oxide adducts, and polyoxyalkylene ether polymer compounds having a perfluoroalkyl ether group in the side chain. Among these, a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain is preferable because of its low foaming property, and in particular, fluorine-based compounds represented by the general formulas (F-1) and (F-2) A surfactant is preferred.

Formula (F-1)
In the compound represented by the general formula (F-1), m is preferably an integer of 0 to 10 and n is preferably an integer of 0 to 40 in order to impart water solubility.

In the compound represented by the general formula (F-2), Y is H, or CnF _{2n + 1} , n is an integer of 1 to 6, or CH ₂ CH (OH) CH ₂ —CnF _{2n + 1,} where n is 4 to 6. An integer, or CpH _{2p + 1} , p is an integer of 1-19. a is an integer of 4-14.
A commercial item may be used as said fluorosurfactant. As this commercial item, for example, Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, S-145 (all manufactured by Asahi Glass Co., Ltd.); Fullrad FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Limited); Megafac F-470, F -1405, F-474 (all manufactured by Dainippon Ink & Chemicals, Inc.); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR (all FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW (all are corporations) (Manufactured by Male), Polyfox PF-136A, PF-156A, PF-151N, PF-154, PF-159 (Omnova), Unidyne DSN-403N (Daikin Industries, Ltd.), and the like. Among these, FS-300 manufactured by Du Pont, FT-110, FT-250 manufactured by Neos Co., Ltd., and the like, have excellent print quality, particularly color developability, paper permeability, wettability, and leveling. FT-251, FT-400S, FT-150, FT-400SW, Polyfox PF-151N manufactured by Omninova, and Unidyne DSN-403N manufactured by Daikin Industries, Ltd. are particularly preferable.

  There is no restriction | limiting in particular as content of surfactant in an ink, Although it can select suitably according to the objective, From the point which is excellent in wettability and discharge stability, and image quality improves, it is 0.001 mass. % To 5% by mass is preferable, and 0.05% to 5% by mass is more preferable.

<Antifoaming agent>
There is no restriction | limiting in particular as an antifoamer, For example, a silicone type antifoamer, a polyether type | system | group antifoamer, a fatty-acid ester type | system | group antifoamer etc. are mentioned. These may be used alone or in combination of two or more. Among these, a silicone type antifoaming agent is preferable from the viewpoint of excellent foam breaking effect.

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

<Rust preventive>
There is no restriction | limiting in particular as a rust preventive agent, For example, acidic sulfite, sodium thiosulfate, etc. are mentioned.

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

There is no restriction | limiting in particular as a physical property of an ink, According to the objective, it can select suitably, For example, it is preferable that a viscosity, surface tension, pH, etc. are the following ranges.
The viscosity at 25 ° C. of the ink is preferably 5 mPa · s or more and 30 mPa · s or less, preferably 5 mPa · s or more and 25 mPa · s or less from the viewpoint of improving the printing density and character quality and obtaining good discharge properties. More preferred. Here, for the viscosity, for example, a rotary viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.) can be used. Measurement conditions are 25 ° C., standard cone rotor (1 ° 34 ′ × R24), sample liquid amount 1.2 mL, rotation speed 50 rpm, and measurement is possible for 3 minutes.
The surface tension of the ink is preferably 35 mN / m or less and more preferably 32 mN / m or less at 25 ° C. from the viewpoint that the ink is suitably leveled on the recording medium and the drying time of the ink is shortened.
The pH of the ink is preferably 7 to 12 and more preferably 8 to 11 from the viewpoint of preventing corrosion of the metal member in contact with the liquid.

<Recording medium>
The recording medium used in the set of the present invention has a support and a surface layer to which ink is applied. Such a recording medium is also called coated paper or coated paper, and the surface layer is also called a coated layer.

-Support-
There is no restriction | limiting in particular as a support body, According to the objective, it can select suitably, For example, the sheet-like substance like the nonwoven fabric mainly composed of paper, wood fiber, and synthetic fiber, etc. are mentioned.
There is no restriction | limiting in particular in the thickness of a support body, Although it can select suitably according to the objective, 50 micrometers-300 micrometers are preferable. The basis weight of the ^{support, 45g / m 2 ~290g / m} 2 is preferred.

-Surface layer-
The surface layer contains a pigment and a binder (binder), and further contains a surfactant and other components as necessary.
As the pigment, an inorganic pigment or a combination of an inorganic pigment and an organic pigment can be used. Examples of inorganic pigments include kaolin, talc, heavy calcium carbonate, light calcium carbonate, calcium sulfite, amorphous silica, titanium white, magnesium carbonate, titanium dioxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, and water. Examples include zinc oxide and chlorite. The amount of the inorganic pigment added is preferably 50 parts by mass or more with respect to 100 parts by mass of the binder.
Examples of the organic pigment include water-soluble dispersions such as styrene-acrylic copolymer particles, styrene-butadiene copolymer particles, polystyrene particles, and polyethylene particles. The addition amount of the organic pigment is preferably 2 parts by mass to 20 parts by mass with respect to 100 parts by mass of the total pigment in the surface layer.
As the binder, it is preferable to use an aqueous resin. As the aqueous resin, at least one of a water-soluble resin and a water-dispersible resin can be suitably used. There is no restriction | limiting in particular as water-soluble resin, According to the objective, it can select suitably, For example, polyvinyl alcohol, cation modified polyvinyl alcohol, acetal modified polyvinyl alcohol, polyester, polyurethane, polyester, polyurethane, etc. are mentioned.
The surfactant contained as necessary in the surface layer is not particularly limited and may be appropriately selected depending on the intended purpose. However, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants can be selected. Either can be used.
There is no restriction | limiting in particular as a formation method of a surface layer, According to the objective, it can select suitably, It can carry out by the method of impregnating or apply | coating the liquid which comprises a surface layer on a support body. Adhesion amount of the liquid constituting the surface layer is not particularly limited and may be appropriately selected depending on the purpose, the solid content ^is preferably ^{0.5g / m 2 ~20g / m 2} , 1g / m 2 ~ 15 g / m ² is more preferable.

  The recording medium used in the set of the present invention has a surface layer formed at least on the surface to which ink is applied, and the 60-degree glossiness of the surface layer is 13 or less, preferably 2 or more. By setting the gloss level within such a range, the gloss of the unprinted portion can be suppressed, so that the glossy range can be used for high-quality art books, photo books, posters, calendars, catalogs and the like that require a high-class feeling. The surface layer of such a recording medium includes a surface layer in which a pigment having a large average particle diameter is used, a surface layer having a high pigment content, and the like. For this reason, the smoothness and adhesive strength of the surface layer are inferior, and smearing may be a problem. The copolymer used in the set of the present invention contains a structural unit having an anionic functional group that reacts and aggregates with a cation derived from a cationic substance contained in the pigment of the surface layer. Therefore, a sufficiently satisfactory smear property can be exhibited in a recording medium having a large surface roughness and provided with a surface layer containing a cationic substance. The cations derived from the cationic substance contained in the pigment of the surface layer include, for example, calcium ion, sodium ion, potassium ion, titanium ion, aluminum ion, magnesium ion, iron ion, manganese ion, nickel ion, and zinc ion. Etc. On the other hand, in a recording medium with a high glossiness of the surface layer, the smoothness of the surface layer is high, so that there are not many cases where smearing is a problem. Therefore, even if an ink containing a copolymer having a structural unit that reacts with a cation is disclosed, when the glossiness of the surface layer on the recording medium to which the ink is applied is high, the purpose is to improve the image density. It is difficult to stay and grasp the above smear problem. The 60 degree glossiness of the present invention can be measured using a gloss meter (BYK Gardener, 4501) according to JIS-Z-8741. As the recording medium used in the present invention, dull or matte coated paper can be used. Specific examples are shown below with glossiness, but are not limited thereto.

  The recording medium used in the set of the present invention may be dull or matte coated paper, such as New Age W (manufactured by Oji Paper Co., Ltd., glossiness: 3.6), POD mat (Oji). Glossy: 3.8), OK Top Coat Dal (A720) (Oji Paper Co., Ltd., glossiness: 4.4), OK Royal Coat (Oji Paper Co., Ltd., glossiness: 4. 4), New Age (A720) (Oji Paper Co., Ltd., glossiness: 4.4), New Age (Oji Paper Co., Ltd., glossiness: 4.6), OK Top Coat Dal (Oji Paper Co., Ltd.) Glossiness: 5.1), OK top coat mat N (A720) (Oji Paper Co., Ltd., glossiness: 5.3), OK Kouou (Oji Paper Co., Ltd., glossiness: 5.4), OK Top Coat Mat N (Oji Paper Co., Ltd.) Manufactured, glossiness: 5.5), OK white L (manufactured by Oji Paper Co., Ltd., glossiness: 5.5), royal coat L (manufactured by Oji Paper Co., Ltd., glossiness: 5.9), OK Astro Matte (Oji Paper Co., Ltd., gloss: 6.3), OK Neo Top Coat Mat (A720) (Oji Paper Co., Ltd., gloss: 6.7), OK Neo Top Coat Mat (Oji Paper Co., Ltd.) Gloss: 7.5), OK Evergreen Dal (Oji Paper Co., Ltd., gloss: 8.6), OK Marnosdal (Oji Paper Co., Ltd., gloss: 8.6), Z Coat (Oji Paper Co., Ltd.) Company-made, glossiness: 9.4), OK Trinity Navi (A720 127.9 gsm) (Oji Paper Co., Ltd., glossiness: 9.9), OK Trinity Navi (A720) (Oji Paper Co., Ltd., glossiness) : 10.3 ), OK Trinity Navi (manufactured by Oji Paper Co., Ltd., glossiness 10.6), OK Astro Dal (manufactured by Oji Paper Co., Ltd., glossiness 12.1), super fine paper (manufactured by Seiko Epson Corporation, glossiness) Degree: 2.5), Canto Excelbar (Daio Paper Co., Ltd., glossiness: 3.4), Green Utrillo mat 100 (Daio Paper Co., Ltd., glossiness: 4.2), Utrilogros mat (Dao Paper) Co., Ltd., glossiness: 4.3), Utrillo L mat W (Daio Paper Co., Ltd., glossiness: 4.8), Kant Excel (Dao Paper Co., Ltd., glossiness: 5.2), Utrillo Excel (Daio Paper Co., Ltd., gloss: 6.1), FS Utrillo Avance L mat (Dao Paper Co., Ltd., gloss: 7.9), Easter DX (Nippon Paper Industries Co., Ltd., gloss: 3. ), Silver diamond (made by Nippon Paper Industries Co., Ltd., glossiness: 4.4), Ulite (made by Nippon Paper Industries Co., Ltd., glossiness: 4.4), Ulite (A720) (made by Nippon Paper Industries Co., Ltd., glossiness) : 4.4), Shiraoi mat (manufactured by Nippon Paper Industries Co., Ltd., glossiness: 6.6), Neptune (manufactured by Nippon Paper Industries Co., Ltd., glossiness: 11.2), swing mat (manufactured by Mitsubishi Paper Industries Co., Ltd., gloss) Degree: 4.9), Broad mat (Mitsubishi Paper Co., Ltd., glossiness: 5.3), New V mat (Mitsubishi Paper Co., Ltd., glossiness: 6.5), White New V mat (Mitsubishi Paper stock) Company-made, glossiness: 7.6).

<Recorded material>
Using the set of the present invention, it is possible to form a recorded matter provided with ink on a recording medium. The recorded matter can be produced by an ink jet recording apparatus and an ink jet recording method.

<Recording apparatus and recording method>
The ink used in the set of the present invention can be suitably used in various recording apparatuses using an ink jet recording method, such as a printer, a facsimile apparatus, a copying apparatus, a printer / fax / copier multifunction machine, and a three-dimensional modeling apparatus. The recording apparatus and the recording method are an apparatus that can eject ink, various processing liquids, and the like to a recording medium, and a method that performs recording using the apparatus. The recording medium means a medium on which ink or various processing liquids can be temporarily attached.
The recording apparatus can include not only a head portion that ejects ink but also means for feeding, transporting, and discharging a recording medium, and other devices called pre-processing devices and post-processing devices. . The recording apparatus and the recording method may include a heating unit used in the heating step and a drying unit used in the drying step. The heating means and the drying means include, for example, a means for heating and drying the printing surface and the back surface of the recording medium. Although it does not specifically limit as a heating means and a drying means, For example, a warm air heater and an infrared heater can be used. Heating and drying can be performed before printing, during printing, after printing, and the like.
Further, the recording apparatus and the recording method are not limited to those in which significant images such as characters and figures are visualized by ink. For example, what forms patterns, such as a geometric pattern, etc. includes what forms a three-dimensional image.
Further, the recording apparatus includes both a serial type apparatus that moves the ejection head and a line type apparatus that does not move the ejection head, unless otherwise specified.
Furthermore, this recording apparatus can use not only a desktop type but also a wide recording apparatus that can print on an A0 size recording medium, for example, a continuous paper wound up in a roll shape as a recording medium. Also included are continuous paper printers. An example of the recording apparatus will be described with reference to FIGS. FIG. 1 is a perspective view of the apparatus. FIG. 2 is an explanatory perspective view of the main tank. An image forming apparatus 400 as an example of a recording apparatus is a serial type image forming apparatus. A mechanism unit 420 is provided in the exterior 401 of the image forming apparatus 400. Each ink storage portion 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), yellow (Y) is packaged, for example, an aluminum laminate film It is formed by a member. The ink storage unit 411 is stored in, for example, a plastic container case 414. As a result, the main tank 410 is used as an ink cartridge for each color.
On the other hand, a cartridge holder 404 is provided on the inner side of the opening when the cover 401c of the apparatus main body is opened. A main tank 410 is detachably attached to the cartridge holder 404. Thus, the ink discharge ports 413 of the main tank 410 and the discharge heads 434 for the respective colors communicate with each other via the supply tubes 436 for the respective colors, and ink can be discharged from the discharge heads 434 to the recording medium.

The recording apparatus can include not only a portion that ejects ink but also a device called a pre-processing device or a post-processing device.
As one mode of the pretreatment device and the posttreatment device, as in the case of inks such as black (K), cyan (C), magenta (M), and yellow (Y), a pretreatment liquid and a posttreatment liquid are included. There is a mode in which a liquid container and a liquid discharge head are added, and a pretreatment liquid and a posttreatment liquid are discharged by an ink jet recording method.
As another aspect of the pretreatment apparatus and the posttreatment apparatus, there is an aspect in which, for example, a pretreatment apparatus or a posttreatment apparatus other than the ink jet recording method is provided by a blade coating method, a roll coating method, or a spray coating method.

<Application>
The use of the ink used in the set of the present invention is not particularly limited and can be appropriately selected depending on the purpose. For example, it can be applied to printed matter, paints, coating materials, foundations and the like. Furthermore, it can be used not only to form two-dimensional characters and images using ink, but also as a three-dimensional modeling material for forming a three-dimensional three-dimensional image (three-dimensional modeled object).
A known three-dimensional modeling apparatus for modeling a three-dimensional model can be used, and is not particularly limited. For example, a three-dimensional modeling apparatus including an ink storage unit, a supply unit, a discharge unit, a drying unit, or the like is used. be able to. The three-dimensional structure includes a three-dimensional structure obtained by repeatedly applying ink. Further, a molded product obtained by processing a structure provided with ink on a substrate such as a recording medium is also included. The molded product is obtained by subjecting a recorded matter or a structure formed in a sheet shape or a film shape to a molding process such as heat stretching or punching, for example, an automobile, OA equipment, It is suitably used for applications in which the surface is molded after decorating, such as meters for electronic devices and cameras, and panels for operation units.

Examples of the present invention will be described below, but the present invention is not limited to these examples. In the examples, “parts” is “parts by mass” unless otherwise specified.
Moreover, the average molecular weight of the copolymer used by the Example and the comparative example was calculated | required as follows.

<Measurement of weight average molecular weight of copolymer>
The measurement was performed by GPC (Gel Permeation Chromatography) under the following conditions.
・ Device: GPC-8020 (manufactured by Tosoh Corporation)
Column: TSK G2000HXL and G4000HXL (manufactured by Tosoh Corporation)
・ Temperature: 40 ℃
・ Solvent: THF (tetrahydrofuran)
・ Flow rate: 1.0 mL / min 1 mL of a copolymer having a concentration of 0.5% by mass was injected, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample from the molecular weight distribution of the copolymer measured under the above conditions was used. The number average molecular weight Mn and the weight average molecular weight Mw of the copolymer were calculated.

２０．８ｇ（１６０ｍｍｏｌ）の２−ヒドロキシエチルメタクリレート（東京化成工業社製）を８０ｍｌのメチルエチルケトンに溶解させ、アルゴン気流下、室温で撹拌した。ここに０．０３ｇのジブチル錫ジラウレート（東京化成工業社製）を滴下し、撹拌しながら５０℃へ加熱した。ここに５０．０ｇの上記構造の反応中間体１を１２０ｍｌのメチルエチルケトンに溶解させた溶液をゆっくり滴下した。滴下後、５０℃で２時間撹拌した。室温まで冷却した後、不溶物をろ別し、ろ液から溶媒を留去してペースト状の粗収物を得た。これをシリカゲルカラムクロマトグラフィー（塩化メチレン／酢酸エチル＝６／１）により精製し、目的物となる４８．０ｇのモノマー１を得た。 <Preparation Example 1>
-Synthesis of monomers that are the basis of the structural unit represented by the general formula (1)-
50.5 g (300 mmol) of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), 30.4 g (300 mmol) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) are dissolved in 300 ml of dry toluene and stirred under an argon stream. The mixture was heated to 105 ° C. A solution prepared by dissolving 43.3 g (300 mmol) of 2-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) in 1500 ml of dry toluene was slowly added dropwise thereto. After dropping, the mixture was stirred at 105 ° C. for 2 hours. After cooling to room temperature, the precipitate was filtered off and the filtrate was collected. The solvent was distilled off from the filtrate to obtain a white solid. 200 ml of hexane was added thereto and stirred at room temperature for 1 hour. The white solid was filtered off to obtain 53.0 g of a reaction intermediate 1 having the following structural formula.

20.8 g (160 mmol) of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80 ml of methyl ethyl ketone, and stirred at room temperature under an argon stream. 0.03 g of dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto and heated to 50 ° C. with stirring. A solution prepared by dissolving 50.0 g of the reaction intermediate 1 having the above structure in 120 ml of methyl ethyl ketone was slowly added dropwise thereto. After dropping, the mixture was stirred at 50 ° C. for 2 hours. After cooling to room temperature, insoluble matters were filtered off, and the solvent was distilled off from the filtrate to obtain a pasty crude product. This was purified by silica gel column chromatography (methylene chloride / ethyl acetate = 6/1) to obtain 48.0 g of monomer 1 as a target product.

-Synthesis of a copolymer having a structural unit represented by the general formula (1)-
A monomer solution was prepared by dissolving 18.0 g (155 mmol) of maleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 42.7 g (97 mmol) of monomer 1 in 420 ml of dry methyl ethyl ketone. After heating 10% by mass of the monomer solution to 75 ° C. under an argon stream, 2.30 g of 2,2′-azobis (isobutyronitrile) (AIBN, manufactured by Tokyo Chemical Industry Co., Ltd.), 0 A solution in which 20 g of α-thioglycerol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved was added dropwise over 2.5 hours and stirred at 75 ° C. for 6 hours. After cooling to room temperature, the resulting reaction solution was dropped into hexane. The precipitated copolymer was filtered off and dried under reduced pressure to obtain 56.9 g of copolymer 1 (weight average molecular weight (Mw): 22000).

-Preparation of pigment dispersion-
The copolymer 1 having 4.0 parts of the structural unit represented by the general formula (1) was dissolved in 80.0 parts of tetraethylammonium hydroxide aqueous solution so that the pH was 8.0. 16.0 parts of carbon black (NIPEX150, manufactured by Degussa) was added to 84.0 parts of the resulting aqueous copolymer solution and stirred for 12 hours. The obtained mixture was circulated and dispersed for 1 hour at a peripheral speed of 10 m / s using a disk-type bead mill (Shinmaru Enterprises Co., Ltd., KDL type, media: using zirconia balls with a diameter of 0.1 mm), and then the pore size was 1 The mixture was filtered through a 2 μm membrane filter, and an adjusted amount of ion-exchanged water was added to obtain 97.0 parts of pigment dispersion 1.

-Preparation of ink-
40.0 parts pigment dispersion 1, 5.0 parts glycerin, 20 parts 3-butoxy-N, N-dimethylpropanamide (solubility parameter: 9.03), 10.0 parts 1,3-butane Diol, 1.0 part 2-ethyl-1,3-hexanediol, 1.0 part 2,2,4-trimethyl-1,3-pentanediol, 1.0 part Unidyne DSN-403N (Daikin Industries) And 22.0 parts of ion-exchanged water were mixed and stirred for 1 hour, and then filtered through a membrane filter having a pore size of 1.2 μm to obtain ink 1.

次に、４１．０ｇ（１５１ｍｍｏｌ）の上記構造式の反応中間体２を２５０ｍＬの塩化メチレンに溶解させ、２０．０ｇ（１９８ｍｍｏｌ）のトリエチルアミン（東京化成工業社製）を加えた。この溶液を氷浴下で冷却し、２０．０ｇ（１９１ｍｍｏｌ）のメタクリル酸クロリド（東京化成工業製）を、３０分かけて滴下した後、氷浴下で１時間撹拌、室温で３時間撹拌した。沈殿物をろ別し、ろ液を水、飽和炭酸水素ナトリウム水溶液、飽和食塩水で洗った後、有機相を単離し、硫酸マグネシウムで乾燥し、溶媒を留去した。残留物を、溶離液としてｎ−ヘキサン／酢酸エチル（体積比６／１）混合溶媒を用いて、シリカゲルカラムクロマトグラフィーにより精製し、３９．４ｇの目的物となるモノマー２を得た。 <Preparation Example 2>
-Synthesis of monomers that are the basis of the structural unit represented by the general formula (2)-
62.0 g (525 mmol) of 1,6-hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 700 mL of methylene chloride, and 20.7 g (262 mmol) of pyridine was added.
A solution prepared by dissolving 50.0 g (262 mmol) of 2-naphthalenecarbonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of methylene chloride was added dropwise to this solution with stirring over 2 hours, followed by stirring at room temperature for 6 hours. did. After the obtained reaction solution was washed with water, the organic phase was isolated and dried over magnesium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of methylene chloride / methanol (volume ratio 98/2) as an eluent to obtain 52.5 g of a reaction intermediate 2 having the following structural formula.

Next, 41.0 g (151 mmol) of the reaction intermediate 2 having the above structural formula was dissolved in 250 mL of methylene chloride, and 20.0 g (198 mmol) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. This solution was cooled in an ice bath, and 20.0 g (191 mmol) of methacrylic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 30 minutes, followed by stirring in an ice bath for 1 hour and stirring at room temperature for 3 hours. . The precipitate was filtered off and the filtrate was washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then the organic phase was isolated and dried over magnesium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of n-hexane / ethyl acetate (volume ratio 6/1) as an eluent to obtain 39.4 g of monomer 2 as a target product.

-Synthesis of a copolymer having a structural unit represented by the general formula (2)-
A monomer solution was prepared by dissolving 18.0 g (155 mmol) of maleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 33.0 g (97 mmol) of monomer 2 in 500 ml of dry methyl ethyl ketone. After heating 10% by mass of the monomer solution to 75 ° C. under an argon stream, 5.0 g of 2,2′-azobis (isobutyronitrile) (AIBN, manufactured by Tokyo Chemical Industry Co., Ltd.) is dissolved in the remaining monomer solution. The solution was added dropwise over 2 hours and stirred at 75 ° C. for 6 hours. After cooling to room temperature, the resulting reaction solution was dropped into hexane. The precipitated copolymer was filtered off and dried under reduced pressure to obtain 59.7 g of copolymer 2 (weight average molecular weight (Mw): 22500).

-Preparation of pigment dispersion-
97.0 parts of Pigment Dispersion 2 were obtained in the same manner as in the preparation of the pigment dispersion of Ink Preparation Example 1 except that Copolymer 2 was used instead of Copolymer 1.

-Preparation of ink-
40.0 parts Pigment Dispersion 2, 5.0 parts glycerin, 20 parts diethylene glycol monoethyl ether (solubility parameter: 10.14), 10.0 parts 1,3-butanediol, 1.0 part 2-ethyl-1,3-hexanediol, 1.0 part 2,2,4-trimethyl-1,3-pentanediol, 1.0 part Unidyne DSN-403N (Daikin Industries), and 22.0 Part of ion-exchanged water was mixed and stirred for 1 hour, and then filtered through a membrane filter having a pore size of 1.2 μm to obtain ink 2.

<Preparation Example 3>
-Synthesis of monomers that are the basis of the structural unit represented by the general formula (3)-
62.0 parts 1,6-hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 900 parts methylene chloride, and 20.7 parts pyridine was added. A solution prepared by dissolving 50.0 parts of 2-naphthalenecarbonyl chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) in 130 parts of methylene chloride was added dropwise to this solution with stirring over 2 hours, and then stirred at room temperature for 6 hours. After the obtained reaction solution was washed with water, the organic layer was isolated and dried over magnesium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of methylene chloride / methanol (volume ratio 92/2) as an eluent to obtain 52.5 parts of 2-naphthoic acid-6-hydroxyhexyl ester. .
Next, 38.3 parts of 4,4′-diphenylmethane diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.), 19.9 parts of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 41.7 parts of 2-naphthoic acid. The 6-hydroxyhexyl ester was dissolved in 50 parts toluene and 10 parts methyl ethyl ketone. 0.04 part of dibutyltin laurate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto and stirred at 60 ° C. for 8 hours. The solvent was distilled off, and the residue was purified by silica gel column chromatography using toluene / ethyl acetate (volume ratio 85/15) mixed solvent as an eluent to obtain 43.5 parts of the following structural formula. Monomer 3 was obtained.

-Synthesis of a copolymer having a structural unit represented by the general formula (3)-
A monomer solution was prepared by dissolving 18.0 g (155 mmol) of maleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 63.2 g (97 mmol) of the monomer 3 in 600 parts of methyl ethyl ketone. After heating 10 mass% of the monomer solution to 75 ° C. under an argon stream, 4.0 parts of 2,2′-azobis (isobutyronitrile) (AIBN, manufactured by Tokyo Chemical Industry Co., Ltd.) A solution in which 0.5 part of α-thioglycerol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved was added dropwise over 2.5 hours and stirred at 75 ° C. for 6 hours. After cooling to room temperature, the resulting reaction solution was dropped into hexane. The precipitated copolymer was separated by filtration and dried under reduced pressure to obtain 79.6 g of copolymer 3 (weight average molecular weight (Mw): 23000).

-Preparation of pigment dispersion-
97.0 parts of Pigment Dispersion 3 was obtained in the same manner as in the preparation of the pigment dispersion of Ink Preparation Example 1 except that the copolymer 3 was used instead of the copolymer 1.

-Preparation of ink-
40.0 parts pigment dispersion 3, 5.0 parts glycerin, 20 parts 3-ethoxy-N, N-dimethylpropanamide (solubility parameter: 9.13), 10.0 parts 1,3-butane Diol, 1.0 part 2-ethyl-1,3-hexanediol, 1.0 part 2,2,4-trimethyl-1,3-pentanediol, 1.0 part Unidyne DSN-403N (Daikin Industries) And 22.0 parts of ion exchange water were mixed and stirred for 1 hour, followed by filtration with a membrane filter having a pore size of 1.2 μm to obtain ink 3.

<Preparation Example 4>
-Synthesis of a monomer as a base of the structural unit represented by the general formula (7)-
106.2 g (525 mmol) of 1,12-dodecanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 700 mL of methylene chloride, and 20.7 g (262 mmol) of pyridine was added.
To this solution, a solution prepared by dissolving 50.0 g (262 mmol) of 2-naphthalenecarbonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of methylene chloride was dropped with stirring over 2 hours, and then stirred at room temperature for 6 hours. . After the obtained reaction solution was washed with water, the organic phase was isolated and dried over magnesium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of methylene chloride / methanol (volume ratio 98/2) as an eluent to obtain 52.5 g of 2-naphthoic acid-2-hydroxyethyl ester.
Next, 42.1 g (155 mmol) of 2-naphthoic acid-2-hydroxyethyl ester was dissolved in 80 mL of dry methyl ethyl ketone and heated to 60 ° C. To this solution, a solution of 24.0 g (155 mmol) of 2-methacryloyloxyethyl isocyanate (produced by Showa Denko KK, Karenz MOI) dissolved in 20 mL of dry methyl ethyl ketone was added dropwise with stirring over 1 hour, and then 70 ° C. For 12 hours. After cooling to room temperature, the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of methylene chloride / methanol (volume ratio 99/1) as an eluent to obtain 65.7 g of monomer 4 having the following structural formula as the target product.

-Synthesis of a copolymer having a structural unit represented by the general formula (7)-
A monomer solution was prepared by dissolving 18.0 g (155 mmol) of maleic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 49.6 g (97 mmol) of monomer 4 in 600 parts of methyl ethyl ketone. After heating 10 mass% of the monomer solution to 75 ° C. under an argon stream, 4.0 parts of 2,2′-azobis (isobutyronitrile) (AIBN, manufactured by Tokyo Chemical Industry Co., Ltd.) A solution in which 0.5 part of α-thioglycerol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved was added dropwise over 2.5 hours and stirred at 75 ° C. for 6 hours. After cooling to room temperature, the resulting reaction solution was dropped into hexane. The precipitated copolymer was filtered off and dried under reduced pressure to obtain 63.6 g of copolymer 4 (weight average molecular weight (Mw): 23500).

-Preparation of pigment dispersion-
97.0 parts of Pigment Dispersion 4 were obtained in the same manner as in the preparation of the pigment dispersion of Ink Preparation Example 1 except that Copolymer 4 was used instead of Copolymer 1.

-Preparation of ink-
40.0 parts pigment dispersion 4, 5.0 parts glycerin, 20 parts 3-ethyl-3-oxetanemethanol (solubility parameter: 11.31), 10.0 parts 1,3-butanediol, 0.0 part 2-ethyl-1,3-hexanediol, 1.0 part 2,2,4-trimethyl-1,3-pentanediol, 1.0 part Unidyne DSN-403N (manufactured by Daikin Industries), And 22.0 parts of ion exchange water were mixed and stirred for 1 hour, and then filtered through a membrane filter having a pore size of 1.2 μm to obtain ink 4.

<Preparation Example 5>
-Synthesis of a monomer as a base of the structural unit represented by the general formula (7)-
62.0 g (525 mmol) of 1,6-hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 700 mL of methylene chloride, and 20.7 g (262 mmol) of pyridine was added.
To this solution, a solution prepared by dissolving 50.0 g (262 mmol) of 2-naphthalenecarbonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of methylene chloride was dropped with stirring over 2 hours, and then stirred at room temperature for 6 hours. . After the obtained reaction solution was washed with water, the organic phase was isolated and dried over magnesium sulfate, and the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of methylene chloride / methanol (volume ratio 98/2) as an eluent to obtain 52.5 g of 2-naphthoic acid-2-hydroxyethyl ester.
Next, 42.1 g (155 mmol) of 2-naphthoic acid-2-hydroxyethyl ester was dissolved in 80 mL of dry methyl ethyl ketone and heated to 60 ° C. To this solution, a solution of 24.0 g (155 mmol) of 2-methacryloyloxyethyl isocyanate (produced by Showa Denko KK, Karenz MOI) dissolved in 20 mL of dry methyl ethyl ketone was added dropwise with stirring over 1 hour, and then 70 ° C. For 12 hours. After cooling to room temperature, the solvent was distilled off. The residue was purified by silica gel column chromatography using a mixed solvent of methylene chloride / methanol (volume ratio 99/1) as an eluent to obtain 57.0 parts of monomer 5 having the following structural formula as the target product. .

-Synthesis of a copolymer having a structural unit represented by the general formula (7)-
A monomer solution was prepared by dissolving 11.2 g (155 mmol) of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 41.4 g (97 mmol) of the monomer 5 in 600 parts of methyl ethyl ketone. After heating 10 mass% of the monomer solution to 75 ° C. under an argon stream, 4.0 parts of 2,2′-azobis (isobutyronitrile) (AIBN, manufactured by Tokyo Chemical Industry Co., Ltd.) A solution in which 0.5 part of α-thioglycerol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved was added dropwise over 2.5 hours and stirred at 75 ° C. for 6 hours. After cooling to room temperature, the resulting reaction solution was dropped into hexane. The precipitated copolymer was filtered off and dried under reduced pressure to obtain 49.6 g of copolymer 5 (weight average molecular weight (Mw): 23000).

-Preparation of pigment dispersion-
97.0 parts of Pigment Dispersion 5 were obtained in the same manner as in Preparation of Pigment Dispersion in Ink Preparation Example 1 except that Copolymer 5 was used instead of Copolymer 1.

-Preparation of ink-
40.0 parts pigment dispersion 5, 5.0 parts glycerin, 20 parts diethylene glycol monohexyl ether (solubility parameter: 9.66), 10.0 parts 1,3-butanediol, 1.0 part 2-ethyl-1,3-hexanediol, 1.0 part 2,2,4-trimethyl-1,3-pentanediol, 1.0 part Unidyne DSN-403N (Daikin Industries), and 22.0 A portion of ion-exchanged water was mixed and stirred for 1 hour, and then filtered through a membrane filter having a pore size of 1.2 μm to obtain ink 5.

<Preparation Example 6>
Ink 6 was produced in the same manner as in Ink Preparation Example 5, except that the synthesis of the copolymer having the structural unit represented by Formula (7) in Ink Preparation Example 5 was changed as follows.
-Synthesis of a copolymer having a structural unit represented by the general formula (7)-
A monomer solution was prepared by dissolving 11.2 g (155 mmol) of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60.3 g (141 mmol) of the monomer 5 in 600 parts of methyl ethyl ketone. After heating 10 mass% of the monomer solution to 75 ° C. under an argon stream, 4.0 parts of 2,2′-azobis (isobutyronitrile) (AIBN, manufactured by Tokyo Chemical Industry Co., Ltd.) A solution in which 0.5 part of α-thioglycerol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved was added dropwise over 2.5 hours and stirred at 75 ° C. for 6 hours. After cooling to room temperature, the resulting reaction solution was dropped into hexane. The precipitated copolymer was separated by filtration and dried under reduced pressure to obtain 66.5 g of copolymer 6 (weight average molecular weight (Mw): 22500).

<Preparation Example 7>
Ink 7 was produced in the same manner as in Ink Preparation Example 5, except that the synthesis of the copolymer having the structural unit represented by Formula (7) in Ink Preparation Example 5 was changed as follows.
-Synthesis of a copolymer having a structural unit represented by the general formula (7)-
A monomer solution was prepared by dissolving 11.2 g (155 mmol) of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 55.2 g (129 mmol) of the monomer 5 in 600 parts of methyl ethyl ketone. After heating 10 mass% of the monomer solution to 75 ° C. under an argon stream, 4.0 parts of 2,2′-azobis (isobutyronitrile) (AIBN, manufactured by Tokyo Chemical Industry Co., Ltd.) A solution in which 0.5 part of α-thioglycerol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved was added dropwise over 2.5 hours and stirred at 75 ° C. for 6 hours. After cooling to room temperature, the resulting reaction solution was dropped into hexane. The precipitated copolymer was separated by filtration and dried under reduced pressure to obtain 66.5 g of copolymer 7 (weight average molecular weight (Mw): 22000).

<Preparation Example 8>
Ink 8 was produced in the same manner as in Ink Preparation Example 5, except that the synthesis of the copolymer having the structural unit represented by Formula (7) in Ink Preparation Example 5 was changed as follows.
-Synthesis of a copolymer having a structural unit represented by the general formula (7)-
A monomer solution was prepared by dissolving 11.2 g (155 mmol) of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 33.1 g (78 mmol) of the monomer 5 in 600 parts of methyl ethyl ketone. After heating 10 mass% of the monomer solution to 75 ° C. under an argon stream, 4.0 parts of 2,2′-azobis (isobutyronitrile) (AIBN, manufactured by Tokyo Chemical Industry Co., Ltd.) A solution in which 0.5 part of α-thioglycerol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved was added dropwise over 2.5 hours and stirred at 75 ° C. for 6 hours. After cooling to room temperature, the resulting reaction solution was dropped into hexane. The precipitated copolymer was separated by filtration and dried under reduced pressure to obtain 40.5 g of copolymer 8 (weight average molecular weight (Mw): 23000).

<Preparation Example 9>
Ink 9 was produced in the same manner as in Ink Preparation Example 5, except that the synthesis of the copolymer having the structural unit represented by Formula (7) in Ink Preparation Example 5 was changed as follows.
-Synthesis of a copolymer having a structural unit represented by the general formula (7)-
A monomer solution was prepared by dissolving 11.2 g (155 mmol) of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 31.6 g (74 mmol) of the monomer 5 in 600 parts of methyl ethyl ketone. After heating 10 mass% of the monomer solution to 75 ° C. under an argon stream, 4.0 parts of 2,2′-azobis (isobutyronitrile) (AIBN, manufactured by Tokyo Chemical Industry Co., Ltd.) A solution in which 0.5 part of α-thioglycerol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved was added dropwise over 2.5 hours and stirred at 75 ° C. for 6 hours. After cooling to room temperature, the resulting reaction solution was dropped into hexane. The precipitated copolymer was separated by filtration and dried under reduced pressure to obtain 38.5 g of copolymer 9 (weight average molecular weight (Mw): 23500).

<Comparative Preparation Example 10>
In Preparation Example 1 of the ink, the synthesis of the copolymer having the structural unit represented by the general formula (1) was performed without synthesizing the monomer as the base of the structural unit represented by the general formula (1). Ink 10 was produced in the same manner as Ink Preparation Example 1 except that the above was changed.
-Synthesis of copolymer-
Acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 g, styrene (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 g, benzyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 g and butyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 g are dissolved in 150 mL of dry methyl ethyl ketone. A monomer solution was prepared. After heating 10% of the monomer solution to 75 ° C. under an argon stream, 0.82 g of 2,2′-azoiso (butyronitrile) dissolved in the remaining monomer solution was added dropwise over 1.5 hours. Stir at 6 ° C. for 6 hours. After cooling to room temperature, the resulting reaction solution was dropped into hexane. The supernatant was discarded, and a precipitated copolymer was obtained. The obtained copolymer was dissolved in tetrahydrofuran, evaporated, and dried under reduced pressure to obtain 38.8 g of copolymer 10 (weight average molecular weight Mw: 165000).

<Comparative Preparation Example 11>
In ink preparation example 1, ink 11 was prepared in the same manner as ink preparation example 1, except that the synthesis of the copolymer having the structural unit represented by formula (1) was changed as follows. did. However, this copolymer is unnecessary for water, and a pigment dispersion and an ink could not be prepared.
-Synthesis of copolymer-
42.7 g (97 mmol) of the monomer 1 was dissolved in 420 ml of dry methyl ethyl ketone to prepare a monomer solution. After heating 10% by mass of the monomer solution to 75 ° C. under an argon stream, 2.30 g of 2,2′-azobis (isobutyronitrile) (AIBN, manufactured by Tokyo Chemical Industry Co., Ltd.), 0 A solution in which 20 g of α-thioglycerol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved was added dropwise over 2.5 hours and stirred at 75 ° C. for 6 hours. After cooling to room temperature, the resulting reaction solution was dropped into hexane. The precipitated copolymer was filtered off and dried under reduced pressure to obtain 39.4 g of copolymer 11 (weight average molecular weight (Mw): 22000).

粘度の測定には、粘度計（ＲＥ８０Ｌ、東機産業株式会社製）を使用し、２５℃における粘度を、５０回転で測定した。
−評価基準−
Ａ：粘度の変化率が±５％以内
Ｂ：粘度の変化率が±５％を超え、±８％以内
Ｃ：粘度の変化率が±８％を超え、±１０％以内
Ｄ：粘度の変化率が±１０％を超え、±３０％以内
Ｅ：粘度の変化率が±３０％を超える [Storage stability of pigment dispersion]
Each pigment dispersion was filled into a glass container with a lid with a capacity of 30 mL, and stored at 70 ° C. for 2 weeks. The change rate of the viscosity after storage with respect to the viscosity before storage was obtained from the following formula, and the following criteria were used. It was evaluated with. The results are shown in Table 1. C and above are practical.

For measurement of the viscosity, a viscometer (RE80L, manufactured by Toki Sangyo Co., Ltd.) was used, and the viscosity at 25 ° C. was measured at 50 revolutions.
-Evaluation criteria-
A: Change rate of viscosity is within ± 5% B: Change rate of viscosity exceeds ± 5% and within ± 8% C: Change rate of viscosity exceeds ± 8% and within ± 10% D: Change in viscosity The rate exceeds ± 10% and within ± 30% E: The rate of change in viscosity exceeds ± 30%

粘度の測定には、粘度計（ＲＥ８０Ｌ、東機産業株式会社製）を使用し、２５℃における粘度を、５０回転で測定した。
−評価基準−
Ａ：粘度の変化率が±５％以内
Ｂ：粘度の変化率が±５％を超え、±８％以内
Ｃ：粘度の変化率が±８％を超え、±１０％以内
Ｄ：粘度の変化率が±１０％を超え、±３０％以内
Ｅ：粘度の変化率が±３０％を超える [Ink storage stability]
Each ink was filled in an ink container and stored at 70 ° C. for 2 weeks. The change rate of the viscosity after storage with respect to the viscosity before storage was obtained from the following formula and evaluated according to the following criteria. The results are shown in Tables 2-5. C and above are practical.

For measurement of the viscosity, a viscometer (RE80L, manufactured by Toki Sangyo Co., Ltd.) was used, and the viscosity at 25 ° C. was measured at 50 revolutions.
-Evaluation criteria-
A: Change rate of viscosity is within ± 5% B: Change rate of viscosity exceeds ± 5% and within ± 8% C: Change rate of viscosity exceeds ± 8% and within ± 10% D: Change in viscosity The rate exceeds ± 10% and within ± 30% E: The rate of change in viscosity exceeds ± 30%

[Image density]
In a 23 point, 50% RH environment, an ink jet printer (Ricoh Co., Ltd., IPSiO GX5000) was filled with each ink, and 64 points of JIS X 0208 (1997), 2223 made by Microsoft Word 2000 (manufactured by Microsoft). The chart on which the general symbols are described is printed on an OK top coat mat N (coated paper made from Oji Paper Co., Ltd., 60 ° glossiness: 5.5), and the symbol part on the printed surface is X-Rite 938 (manufactured by X-Rite). The color was measured according to the following criteria. The results are shown in Tables 2-5. C and above are practical. In addition, "-" in a table | surface shows that evaluation is not performed.
As the print mode, a mode in which the “plain paper-standard fast” mode is changed to “no color correction” from the user setting of plain paper by a driver attached to the printer.
The general symbols of JIS X 0208 (1997) and 2223 are symbols whose outer shape is a regular square and the entire surface of the symbol is filled with ink.
-Evaluation criteria-
A: 2.20 or more B: 2.10 or more and less than 2.20 C: 2.00 or more and less than 2.10 D: Less than 2.00

[Smear property]
Under an environment of 23 ° C. and 50% RH, an ink jet printer (IPCO GX5000, manufactured by Ricoh Co., Ltd.) is filled with each ink, and a solid image of 5 cm × 5 cm is printed on the following nine types of paper, and the surface of the print image is printed The sample was reciprocated 15 times with a cotton cloth set on a clock meter (manufactured by Atlas Co., Ltd.), and the image density of the ink transferred to the cotton cloth was measured with X-Rite 938 (manufactured by X-Rite Co., Ltd.) and evaluated according to the following criteria. Any cation eluted from the following paper by contact with ink is calcium ion. In addition, smear property is so favorable that a numerical value is small, and C or more is practical. The results are shown in Tables 2-5.
-Paper type-
Paper type 1: Super fine paper (Seiko Epson coated paper, 60 degree gloss: 2.5)
Paper type 2: POD mat (coated paper made by Oji Paper Co., 60 degree gloss: 3.8)
Paper Type 3: OK Top Coat Mat N (Oji Paper Coated Paper, 60 Degree Gloss: 5.5)
Paper type 4: FS Utrilo Avance L mat (Coated paper made by Daio Paper, 60 degree gloss: 7.9)
Paper type 5: OK Trinity Navi (Oji Paper Coated Paper, 60 degree gloss: 10.6)
Paper type 6: OK Astro Dal (Oji Paper Coated Paper, 60 degree gloss: 12.1)
Paper type 7: LumiArt Gloss 90GSM (coated paper manufactured by STORA ENSO, 60 degree gloss: 29.1)
Paper type 8: OK top coat + (Oji Paper Coated Paper, 60 degree gloss: 26.2)
Paper type 9: POD gloss coat (coated paper manufactured by Oji Paper Co., Ltd., 60 degree gloss: 39.6)
-Evaluation criteria-
A: Less than 0.05 B: 0.05 or more and less than 0.075 C: 0.075 or more and less than 0.10 D: 0.10 or more

400 Image forming apparatus 401 Exterior of image forming apparatus 401c Cover of apparatus main body 404 Cartridge holder 410 Main tank 410k, 410c, 410m, 410y For each color of black (K), cyan (C), magenta (M), yellow (Y) Main tank 411 Ink storage section 413 Ink discharge port 414 Storage container case 420 Mechanism section 434 Discharge head 436 Supply tube

JP-A-2016-196621

Claims (9)

A set comprising an ink containing a copolymer and a recording medium having a surface layer containing a cationic substance,
The copolymer has a structural unit represented by any one of the following general formulas (1) to (3), and a structural unit having an anionic functional group,
A set in which the 60-degree glossiness in the surface layer of the recording medium is 13 or less.

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and A ₁ , A ₂ , and A ₃ are each independently —O—, —CO—O—, —O—CO—, Represents a divalent substituent selected from the group of —CO—NH—, —NH—CO—, —NH—CO—O—, —O—CO—NH—, wherein X ₁ and X ₂ are each independently A single bond, an alkylene group having 1 to 12 carbon atoms, an alkenylene group having 1 to 12 carbon atoms, a divalent group selected from the group consisting of general formula (4), general formula (5), and general formula (6). Represents a substituent, and Ar represents an aromatic group.)

(In the general formula (2), R ¹ , A ₁ , A ₂ , X ₁ , X ₂ and Ar each independently represent the same as in the general formula (1).)

(In the general formula (3), R ¹ , A ₁ , A ₂ , A ₃ , X ₁ , X ₂ and Ar each independently represent the same as in the general formula (1), and A ₄ represents —O Divalent substitution selected from the group of-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -NH-CO-O-, -O-CO-NH-. And Z represents a divalent hydrocarbon group.)

(In the general formula (4), l represents an integer of 1 or more and 10 or less.)

(In the general formula (5), m represents an integer of 1 or more and 10 or less.)

(In the general formula (6), n represents an integer of 1 or more and 10 or less.)   The set according to claim 1, wherein Ar in the general formulas (1), (2), and (3) has a naphthyl group. The set according to claim 1 or 2, wherein the structural unit represented by any one of the general formulas (1) to (3) includes a structural unit represented by the following general formula (7).

(In the general formula (7), R ² represents a hydrogen atom or a methyl group, and L represents an alkylene group having 2 to 16 carbon atoms.) The set according to any one of claims 1 to 3, wherein the structural unit having an anionic functional group has a structural unit represented by the following general formula (8).

(In the general formula (8), R ³ represents a hydrogen atom or a methyl group, and X represents a hydrogen atom or a cation.)   The molar ratio between the structural unit represented by any one of the general formulas (1) to (3) and the structural unit having the anionic functional group is 1.0: 1.2-1. The set according to any one of claims 1 to 4, which is 0: 2.0.   The set according to any one of claims 1 to 5, wherein the ink contains an organic solvent having a solubility parameter of 9.00 or more and 11.80 or less. The recording medium has a surface layer on the surface to which the ink is applied,
The set according to any one of claims 1 to 6, wherein the cationic substance elutes calcium ions in the ink by contact with the ink. A recording method for applying an ink containing a copolymer to a recording medium having a surface layer containing a cationic substance,
The copolymer has a structural unit represented by any one of the following general formulas (1) to (3), and a structural unit having an anionic functional group,
A recording method in which the 60 ° glossiness in the surface layer of the recording medium is 13 or less.

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and A ₁ , A ₂ , and A ₃ are each independently —O—, —CO—O—, —O—CO—, Represents a divalent substituent selected from the group of —CO—NH—, —NH—CO—, —NH—CO—O—, —O—CO—NH—, wherein X ₁ and X ₂ are each independently A single bond, an alkylene group having 1 to 12 carbon atoms, an alkenylene group having 1 to 12 carbon atoms, and a divalent group selected from the group consisting of general formula (4), general formula (5), and general formula (6). And Ar represents an aromatic group.)

(In the general formula (2), R ¹ , A ₁ , A ₂ , X ₁ , X ₂ and Ar each independently represent the same as in the general formula (1).)

(In the general formula (3), R ¹ , A ₁ , A ₂ , A ₃ , X ₁ , X ₂ and Ar each independently represent the same as in the general formula (1), and A ₄ represents —O Divalent substitution selected from the group of-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -NH-CO-O-, -O-CO-NH-. And Z represents a divalent hydrocarbon group.)

(In the general formula (4), l represents an integer of 1 or more and 10 or less.)

(In the general formula (5), m represents an integer of 1 or more and 10 or less.)

(In the general formula (6), n represents an integer of 1 or more and 10 or less.) A recording apparatus for applying an ink containing a copolymer to a recording medium having a surface layer containing a cationic substance,
The recording apparatus includes an ejection unit that ejects the ink.
The copolymer has a structural unit represented by any one of the following general formulas (1) to (3), and a structural unit having an anionic functional group,
A recording apparatus having a 60 degree glossiness of 13 or less in the surface layer of the recording medium.

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and A ₁ , A ₂ , and A ₃ are each independently —O—, —CO—O—, —O—CO—, Represents a divalent substituent selected from the group of —CO—NH—, —NH—CO—, —NH—CO—O—, —O—CO—NH—, wherein X ₁ and X ₂ are each independently A single bond, an alkylene group having 1 to 12 carbon atoms, an alkenylene group having 1 to 12 carbon atoms, and a divalent group selected from the group consisting of general formula (4), general formula (5), and general formula (6). And Ar represents an aromatic group.)

(In the general formula (2), R ¹ , A ₁ , A ₂ , X ₁ , X ₂ and Ar each independently represent the same as in the general formula (1).)

(In the general formula (3), R ¹ , A ₁ , A ₂ , A ₃ , X ₁ , X ₂ and Ar each independently represent the same as in the general formula (1), and A ₄ represents —O Divalent substitution selected from the group of-, -CO-O-, -O-CO-, -CO-NH-, -NH-CO-, -NH-CO-O-, -O-CO-NH-. And Z represents a divalent hydrocarbon group.)

(In the general formula (4), l represents an integer of 1 or more and 10 or less.)

(In the general formula (5), m represents an integer of 1 or more and 10 or less.)

(In the general formula (6), n represents an integer of 1 or more and 10 or less.)

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