JP6973040B2 - Ink, ink container, recording device, recording method, and recorded material - Google Patents

Description

The present invention relates to ink, an ink container, a recording device, a recording method, and a recorded material.

As the ink used in the inkjet recording method, a water-based ink using a dye or a pigment is known. With such inks, it is necessary to stably disperse components such as pigments, which are difficult to dissolve in water, in water for a long period of time, so it is effective to use a dispersant in combination.

Patent Document 1 and Patent Document 2 disclose a dispersant having a structural unit having an anionic group and a structural unit having a naphthyl group at the terminal, and an ink containing these dispersants can be ejected to a recording medium by an inkjet method. Is disclosed. Further, it is disclosed that the ink using these dispersants is excellent in storage stability, image density, and beading resistance.

However, the conventional ink has a large number of coarse particles and a high rate of increase of the coarse particles when stored for a long period of time, so that there is a problem that it is difficult to stably apply the ink to the recording medium.

The invention according to claim 1 is expressed by containing a compound represented by the following formula (A-7) or the following formula (A-8), the formula (A-7) or the formula (A-8) The content of the compound is 0.0002% by mass or more and 0.08% by mass or less with respect to the total amount of the ink.

The ink of the present invention has an excellent effect that the number of coarse particles is small and the rate of increase of coarse particles when stored for a long period of time is reduced.

FIG. 1 is a perspective explanatory view showing an example of a recording device. FIG. 2 is a perspective explanatory view showing an example of the main tank.

Hereinafter, embodiments of the present invention will be described.

<< Ink >>
The ink of the present invention contains a compound represented by the general formula (1), and if necessary, contains a copolymer, water, a coloring material, an organic solvent, a surfactant, and other components.

一般式（１）で表される化合物において、Ｘは炭素数５以上９以下のアルキレン基であり、炭素数５以上７以下のアルキレン基であることが好ましく、炭素数６のアルキレン基であることがより好ましい。なお、Ｘで表されるアルキレン基は、各水素原子が置換されていないことが好ましいが、置換されていてもよく、置換されている場合はメチル基またはメトキシカルボニル基で置換されていることが好ましい。Ａｒ_１、及びＡｒ_２はそれぞれ独立してベンゼン環の１価基、又はナフタレン環の１価基であり、Ａｒ_１、及びＡｒ_２の少なくとも一方がナフタレン環の１価基であることが好ましく、Ａｒ_１、及びＡｒ_２がともにナフタレン環の１価基であることがより好ましい。なお、Ａｒ_１、及びＡｒ_２で表されるベンゼン環の１価基、又はナフタレン環の１価基は、各水素原子が置換されていないことが好ましいが、置換されていてもよい。 <Compound represented by the general formula (1)>

In the compound represented by the general formula (1), X is an alkylene group having 5 or more and 9 or less carbon atoms, preferably an alkylene group having 5 or more and 7 or less carbon atoms, and is an alkylene group having 6 carbon atoms. Is more preferable. The alkylene group represented by X is preferably not substituted with each hydrogen atom, but may be substituted, and if substituted, it may be substituted with a methyl group or a methoxycarbonyl group. preferable. It is preferable that Ar ₁ and Ar ₂ are independently monovalent groups of a benzene ring or a monovalent group of a naphthalene ring, and _{at least one of Ar 1 and Ar 2 is a monovalent group of a naphthalene ring.} It is more preferable that both Ar ₁ and Ar ₂ are monovalent groups of the naphthalene ring. The _{monovalent group of the benzene ring represented by Ar 1} and Ar ₂ or the monovalent group of the naphthalene ring is preferably not substituted with each hydrogen atom, but may be substituted.

Hereinafter, the compound represented by the general formula (1) will be exemplified, but the present application is not limited to the following specific examples.

By containing the compound represented by the general formula (1), the ink of the present invention reduces the number of coarse particles in the ink and reduces the rate of increase of coarse particles when stored for a long period of time. The mechanism by which these effects occur is not clear, but it is speculated as follows.
In general, the dispersion mechanism of particles such as pigments is to prevent reaggregation by adsorbing the dispersant to the particles when the aggregates of the particles are crushed by applying a shearing force. As a result, small particle size and stabilization of particles are achieved. At this time, if the dispersant is not sufficiently adsorbed on the particles, the crushed particles tend to reaggregate with each other, and as a result, the dispersant grows into coarse particles. The compound represented by the general formula (1) has an alkylene group having a certain length and has a benzene ring or a naphthalene ring at both ends, so that the compound is easily adsorbed on the surface of particles such as pigments. There is. In addition, since the benzene ring and naphthalene ring are hydrophobic, they also have an attractive force due to hydrophobic interaction with the hydrophobic group of the dispersant, and have a high affinity with the dispersant. Since the affinity for both particles such as pigments and the dispersant is high, coexistence with the dispersant further increases the adsorptive power between the dispersant and the particles. As a result, reaggregation of particles is prevented, the number of coarse particles in the ink is reduced, and the rate of increase of coarse particles when stored for a long period of time is reduced.

The content of the compound represented by the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose, but is 0.0001% by mass or more and 0.5% by mass or less with respect to the total amount of ink. Is preferable, and 0.001% by mass or more and 0.1% by mass or less is more preferable. When the content is 0.001% or more and 0.5% or less, the number of coarse particles in the ink is reduced, and the rate of increase of coarse particles when stored for a long period of time is reduced.

-Method for synthesizing the compound represented by the general formula (1)-
As shown in Reaction Scheme 1 below, the compound represented by the general formula (1) is subjected to an addition reaction of a diisocyanate compound (R-1) with an excess amount of phenol (R-2) or naphthol (R-3). can get.

-Analysis method of the compound represented by the general formula (1)-
The structure of the compound represented by the general formula (1) can be analyzed by separating and extracting from the ink, if necessary, and using a general analysis method such as NMR or IR.
Further, the content of the compound represented by the general formula (1) can be determined by, for example, the following method. First, as a pretreatment, the ink is placed in a container such as a beaker and concentrated to dryness on a hot plate. Next, the concentrated residue is placed in a Soxhlet extractor and extracted with tetrahydrofuran. By putting a standard substance with a known concentration in the ink to be pretreated, when the extract is measured by GC, HPLC, etc., the compound represented by the general formula (1) is calculated by the ratio with the area ratio of the standard substance. Content can be determined.

<Copolymer>
The ink of the present invention preferably contains a copolymer having a structural unit represented by the general formula (2) and a structural unit having an anionic group, if necessary. By containing the copolymer, high image density can be obtained even when recorded on plain paper, high storage stability, and ink with few coarse particles can be obtained.

一般式（２）で表される構造単位において、Ｒは水素原子又はメチル基であり、水素原子であることが好ましい。Ｙは炭素数２以上４以下のアルキレン基であり、炭素数２以上３以下のアルキレン基であることが好ましく、炭素数２のアルキレン基であることがより好ましい。なお、Ｙで表されるアルキレン基は、各水素原子が置換されていないことが好ましいが、置換されていてもよい。Ｚは炭素数５以上９以下のアルキレン基であり、炭素数５以上７以下のアルキレン基であることが好ましく、炭素数６のアルキレン基であることがより好ましい。なお、Ｚで表されるアルキレン基は、各水素原子が置換されていないことが好ましいが、置換されていてもよく、置換されている場合はメチル基またはメトキシカルボニル基で置換されていることが好ましい。 -Structural unit represented by the general formula (2)-

In the structural unit represented by the general formula (2), R is a hydrogen atom or a methyl group, and is preferably a hydrogen atom. Y is an alkylene group having 2 or more and 4 or less carbon atoms, preferably an alkylene group having 2 or more and 3 or less carbon atoms, and more preferably an alkylene group having 2 or less carbon atoms. The alkylene group represented by Y is preferably not substituted with each hydrogen atom, but may be substituted. Z is an alkylene group having 5 or more and 9 or less carbon atoms, preferably an alkylene group having 5 or more and 7 or less carbon atoms, and more preferably an alkylene group having 6 or more carbon atoms. The alkylene group represented by Z is preferably not substituted with each hydrogen atom, but may be substituted, and if substituted, it may be substituted with a methyl group or a methoxycarbonyl group. preferable.

Hereinafter, the structural unit represented by the general formula (2) will be illustrated, but the present application is not limited to the following specific examples.

In the copolymer having the structural unit represented by the general formula (2), the naphthyl group existing at the terminal via Z is π-π stacked with the particles such as pigments in the ink, so that the particles are subjected to π-π stacking. Has excellent adsorption power. When preparing a dispersion in which particles such as pigments are dispersed in a dispersion medium such as water, if a copolymer having a structural unit represented by the general formula (2) is used, the copolymer becomes particles due to the naphthyl group. It adheres to the surface and becomes a highly dispersible and stable dispersion for a long period of time. The structural unit represented by the general formula (2) is preferably contained in the main chain of the copolymer, but a part or all of the structural unit may be contained in the side chain.
Further, as described above, since the compound represented by the general formula (1) has a benzene ring or a naphthalene ring at both ends, an attractive force acts due to a hydrophobic interaction with the hydrophobic group of the dispersant, and the compound has a high affinity with the dispersant. In other words, a hydrophobic interaction occurs between the benzene ring or naphthalene ring present at both ends of the compound represented by the general formula (1) and the structural unit represented by the general formula (2) in the copolymer. work. This prevents reaggregation of the particles, reduces the number of coarse particles in the ink, and reduces the rate of increase of coarse particles when stored for a long period of time.

-Structural unit with anionic group-
The structural unit having an anionic group is formed by copolymerizing a monomer having an anionic group. Examples of the monomer having an anionic group include an unsaturated carboxylic acid monomer, an unsaturated sulfonic acid monomer, and an unsaturated phosphoric acid monomer.
Examples of the unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like. Examples of the unsaturated sulfonic acid monomer include styrene sulfonic acid and 2-acrylamide-2-methylpropane sulfonic acid. Examples of the unsaturated phosphoric acid monomer include vinylphosphonic acid, vinyl phosphate, bis (methacryloxyethyl) phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, and dibutyl-2-acry. Examples thereof include leuroxyethyl phosphate.
Among these, a monomer having a carboxyl group is preferable, and acrylic acid or methacrylic acid is more preferable, from the viewpoint of storage stability.
Further, the monomer having an anionic group may be used alone or in combination of two or more.

Hereinafter, structural units having an anionic group will be exemplified, but the present application is not limited to the following specific examples.

Structural units with anionic groups 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, and tetrahexylammonium. Hydroxydo, Triethylmethylammonium Hydroxide, Tributylmethylammonium Hydroxide, Trioctylmethylammonium Hydroxide, 2-Hydroxyethyltrimethylammonium Hydroxide, Tris (2-Hydroxyethyl) Methylammonium Hydroxide, propyltrimethylammonium Hydroxide, Hexyl Trimethylammonium Hydroxide, Octyltrimethylammonium Hydroxide, Nonyltrimethylammonium Hydroxide, Decyltrimethylammonium Hydroxide, Dodecyltrimethylammonium Hydroxide, Tetradecyltrimethylammonium Hydroxide, Hexadecyltrimethylammonium Hydroxide, Octadecyltrimethylammonium Hydroxide, Di Dodecyldimethylammonium Hydroxide, Ditetradecyldimethylammonium Hydroxide, Dihexadecyldimethylammonium Hydroxide, Dioctadecyldimethylammonium Hydroxide, Ethylhexadecyldimethylammonium Hydroxide, Ammonia Water, Dimethylamine, trimethylamine, Monoethylamine, diethylamine, Triethylamine, monoethanolamine, diethanolamine, triethanolamine, methylethanolamine, methyldiethanolamine, dimethylethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, isopropanolamine, morpholine, N-methylmorphone, N-methyl-2- Examples thereof include pyrrolidone and 2-pyrrolidone.
The base as a neutralizing agent may be used alone or in combination of two or more.
The neutralization treatment may be performed when the monomer having an anionic group is copolymerized, or may be performed when the copolymer is dissolved.

-Composition ratio of copolymer-
The content of the structural unit represented by the general formula (2) is not particularly limited and may be appropriately selected depending on the intended purpose, but is 60% by mass or more and 90% by mass or less with respect to the total amount of the copolymer. It is preferably 75% by mass or more and 90% by mass or less, more preferably. When the content is 60% by mass or more and 90% by mass or less, it is advantageous in that the image density and storage stability are good when used in ink.

-Molecular weight of copolymer-
The weight average molecular weight of the copolymer is preferably 5,000 or more and 50,000 or less, and more preferably 15,000 or more and 40,000 or less in terms of polystyrene. When the weight average molecular weight is 5000 or more and 50,000 or less, it is advantageous in that the image density and the storage stability are good when used in ink.

-Other monomers-
The copolymer may have a structural unit represented by the general formula (2) and a structural unit composed of other polymerizable monomers in addition to the structural unit having an anionic group. The other polymerizable monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a polymerizable hydrophobic monomer, a polymerizable hydrophilic monomer and a polymerizable surfactant.

Examples of the polymerizable hydrophobic monomer include unsaturated ethylene monomers having an aromatic ring such as styrene, α-methylstyrene, 4-t-butylstyrene, and 4-chloromethylstyrene; methyl (meth) acrylate, (. Ethyl (meth) acrylate, -n-butyl (meth) acrylate, dimethyl maleate, dimethyl itacone, dimethyl fumarate, lauryl (meth) acrylate (C12), tridecyl (meth) acrylate (C13), (meth) ) Tetradecyl acrylate (C14), pentadecyl (meth) acrylate (C15), hexadecyl (meth) acrylate (C16), heptadecyl (meth) acrylate (C17), nonadecil (meth) acrylate (C19), (meth) ) Eikosyl acrylate (C20), Henicosyl (meth) acrylate (C21), Dococil (meth) acrylate (C22) and other (meth) alkyl (meth) acrylates; 1-heptene, 3,3-dimethyl-1-pentene, 4,4-dimethyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 1-octene, 3,3-dimethyl-1-hexene, 3, 4-Dimethyl-1-hexene, 4,4-dimethyl-1-hexene, 1-nonen, 3,5,5-trimethyl-1-hexene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, Examples thereof include unsaturated ethylene monomers having an alkyl group such as 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and 1-dococene. These may be used alone or in combination of two or more.
Examples of the polymerizable hydrophilic monomer include -2-hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, and polyethylene glycol mono. (Meta) acrylate, (meth) acrylamide, N-methylol (meth) acrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, acrylamide, N, N-dimethylacrylamide, N-t-butylacrylamide, N Examples thereof include nonionic unsaturated ethylene monomers such as −octylacrylamide and Nt-octylacrylamide. These may be used alone or in combination of two or more.
One or more of the polymerizable hydrophobic monomer and the polymerizable hydrophilic monomer are mixed to form a structural unit represented by the general formula (2) and a structural unit having an anionic group. It can be used in an amount of 5% by mass or more and 100% by mass or less with respect to the total amount of the monomers.

一般式（３）で表されるモノマーにおいて、Ｒ、Ｙ、及びＺは、それぞれ一般式（２）で表される構造単位におけるＲ、Ｙ、及びＺと同様である。 -Synthesis of copolymer-
The copolymer is obtained by copolymerizing the monomer represented by the general formula (3) with a monomer having an anionic group in the presence of a radical polymerization initiator.

In the monomer represented by the general formula (3), R, Y, and Z are the same as R, Y, and Z in the structural unit represented by the general formula (2), respectively.

Hereinafter, the monomer represented by the general formula (3) will be exemplified, but the present application is not limited to the following specific examples.

The monomer represented by the general formula (3) can be synthesized and used as follows. That is, as shown in the following reaction formulas 2 to 3, first, the diisocyanate compound (R-1) and naphthol (R-3) are reacted in the presence of an acid receptor such as amine or pyridine to form a reaction intermediate. (R-4) is obtained. Next, the hydroxyalkyl methacrylate (R-5) and (R-4) can be reacted to obtain a monomer represented by the general formula (3).

Alternatively, as another method, first react with (R-1) and (R-5) and then react with (R-3) to obtain a monomer represented by the general formula (3). Can be done.
As yet another method, as shown in the following reaction formula 4, the general formula (3) is obtained by reacting the diisocyanate compound (R-1), naphthol (R-3), and hydroxyalkyl methacrylate (R-5). ) Can also be obtained.

The compound represented by the above general formula (1) can also be obtained as a by-product when synthesizing the monomer represented by the general formula (3). Therefore, a crude product of the monomer represented by the general formula (3) containing the compound represented by the general formula (1) as a by-product is used for producing a copolymer, and the obtained copolymer is used as an ink. When added, an ink containing the compound represented by the general formula (1) is obtained.
However, in general, the compound represented by the general formula (1) generated as a by-product is purified and removed by silica gel column chromatography or the like in the process of synthesizing the monomer represented by the general formula (3). .. Therefore, when a purified product of the monomer represented by the general formula (3) is used for producing a copolymer and the obtained copolymer is added to the ink, substantially the general formula (1) is contained in the ink. Does not contain the compound represented by. Specifically, the content of the compound represented by the general formula (1) does not exceed 0.0001% by mass with respect to the total amount of ink. The present invention substantially reduces the number of coarse particles in the ink and reduces the rate of increase of coarse particles when stored for a long period of time when an ink containing no compound represented by the general formula (1) is used. You cannot get the effect of.
The compound represented by the general formula (1) in the present application may be contained in the ink as a by-product when synthesizing the monomer represented by the general formula (3) as described above, and is separately synthesized. The compound represented by the general formula (1) may be added to the ink. When the compound represented by the general formula (1) is contained in the ink as a by-product, the content of the compound represented by the general formula (1) in the ink is, for example, the diisocyanate compound (R-1) at the time of synthesis. ) And naphthol (R-3) can be adjusted by changing the ratio.

As a method for synthesizing the copolymer, a method using a radical polymerization initiator is preferable because the polymerization operation and the molecular weight can be easily adjusted, and a solution polymerization method in which the polymerization reaction is carried out in a solution is more preferable.

Preferred solvents for radical polymerization by the solution polymerization method are 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 a hydrogen-based solvent, isopropanol, ethanol, cyclohexane, tetrahydrofuran, dimethylformamide, dimethylsulfoxide and hexamethylphosphoamide, and more preferably, a ketone-based solvent, an acetate ester-based solvent and an alcohol-based solvent.

The radical polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxyester, cyano-based azobisisobutyronitrile, and 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 can be easily controlled and the decomposition temperature is low.
The content of the radical polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1% by mass or more and 10% by mass or less with respect to the total amount of the polymerizable monomer.

Further, in order to adjust the molecular weight of the polymer, an appropriate amount of the chain transfer agent may be added. 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. or higher and 150 ° C. or lower, and more preferably 60 ° C. or higher and 100 ° C. or lower. The polymerization time is also not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 hours or more and 48 hours or less.

-Amount of copolymer added-
The content of the copolymer with respect to the total amount of ink is not particularly limited and may be appropriately selected depending on the intended purpose, but the solid content is preferably 0.05% by mass or more and 10% by mass or less, preferably 0.3% by mass. More preferably, it is 5% by mass or less.
When the content is 0.05% by mass or more, the dispersibility of the particles in the ink and the storage stability of the ink are improved, and when it is 10% by mass or less, the ink viscosity at the time of ejecting the ink from the inkjet head is appropriate. Can be a range.

-Use of copolymer-
The copolymer is not particularly limited and can be used as a dispersant for particles such as pigments or as an additive to the dispersion. When used as a particle dispersant, storage stability is improved in inks having a high content of water-soluble organic solvents.

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

<Color material>
The coloring material is not particularly limited, and pigments and dyes can be used.
As the pigment, an inorganic pigment or an organic pigment can be used. These may be used alone or in combination of two or more. Further, a mixed crystal may be used as the pigment.
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 color pigment such as gold or silver, a metallic pigment, or the like can be used.
As inorganic pigments, 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, and chrome yellow. Can be used.
Examples of organic pigments include azo pigments and polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.). , Dye chelate (for example, basic dye type chelate, acid dye type chelate, etc.), nitro pigment, nitroso pigment, aniline black and the like can be used. Among these pigments, those having a good affinity with a solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used.
As a specific example of the pigment, for black, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, or copper, iron (CI pigment black 11) , Metals such as titanium oxide, and organic pigments such as aniline black (CI pigment black 1).
Further, for color, 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 Calcium 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 Greens 1, 4, 7, 8, 10, 17, 18, 36, etc.
The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used, and one type may be used alone or two or more types may be used in combination.
As a dye, for example, 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. Dilekdo 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, 35 can be mentioned.

The content of the coloring 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 viewpoint of improving the image density, good fixing property and ejection stability. It is as follows.

As a method of dispersing the pigment to obtain an ink, a method of introducing a hydrophilic functional group into the pigment to obtain a self-dispersible pigment, a method of coating the surface of the pigment with a resin and dispersing it, and a method of dispersing using a dispersant are used. The method, etc. can be mentioned.
As a method of introducing a hydrophilic functional group into a pigment to obtain a self-dispersing pigment, for example, a method of adding a functional group such as a sulfone group or a carboxyl group to a pigment (for example, carbon) so that the pigment can be dispersed in water. Can be mentioned.
Examples of the method of coating the surface of the pigment with a resin and dispersing the pigment include a method of encapsulating the pigment in microcapsules so that the pigment can be dispersed in water. This can be rephrased as a resin-coated pigment. In this case, it is not necessary that all the pigments blended in the ink are coated with the resin, and the uncoated pigments and the partially coated pigments are dispersed in the ink as long as the effect of the present invention is not impaired. May be.
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low-molecular-weight dispersant and high-molecular-weight dispersant represented by a surfactant.
As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant and the like can be used depending on the pigment.
As the dispersant, RT-100 (nonionic surfactant) manufactured by Takemoto Oil & Fat Co., Ltd. and a naphthalene sulfonic acid Na formalin condensate can also be suitably used as the dispersant.
The dispersant may be used alone or in combination of two or more.

<Pigment dispersion>
It is possible to obtain an ink by mixing a material such as water or an organic solvent with a pigment. It is also possible to produce an ink by mixing a material such as water or an organic solvent with a pigment dispersion obtained by mixing a pigment and other water or a dispersant.
The pigment dispersion is obtained by mixing and dispersing water, a pigment, a pigment dispersant, and other components as necessary, and adjusting the particle size. It is good to use a disperser for dispersion.
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 the maximum number because the dispersion stability of the pigment is good and the image quality such as ejection stability and image density is also high. It is preferably 500 nm or less, and more preferably 20 nm or more and 150 nm or less. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrac 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, but is 0.1% by mass from the viewpoint of obtaining good ejection stability and increasing the image density. 50% by mass or more is preferable, and 0.1% by mass or more and 30% by mass or less is more preferable.
It is preferable to degas the pigment dispersion by filtering the coarse particles with a filter, a centrifuge, or the like, if necessary.

<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 polyhydric alcohols 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, Glycolin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl- Examples thereof include 1,3-pentanediol and petriol.
Examples of the polyhydric alcohol alkyl ethers include 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 the polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.
Examples of the nitrogen-containing heterocyclic compound include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, and γ-butyrolactone. Can be mentioned.
Examples of the amides include formamide, N-methylformamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide and the like.
Examples of amines include monoethanolamine, diethanolamine, triethylamine and the like.
Examples of sulfur-containing compounds include dimethyl sulfoxide, sulfolane, and thiodiethanol.
Examples of other organic solvents include propylene carbonate and ethylene carbonate.
It is preferable to use an organic solvent having a boiling point of 250 ° C. or lower because it not only functions as a wetting agent but also has good drying properties.

As the organic solvent, 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 and 2,2,4-trimethyl-1,3-pentanediol.
Specific examples of the glycol ether compound 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. Ethers; Examples thereof 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 the permeability of ink when paper is used as a recording medium.

The content of the organic solvent 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 60% by mass or less from the viewpoint of ink drying property and ejection reliability. More preferably, it is 20% by mass or more and 60% by mass or less.

<Surfactant>
As the surfactant, any of a silicone-based surfactant, a fluorine-based surfactant, an amphoteric surfactant, a nonionic surfactant, and an anionic surfactant can be used.
The silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Of these, those that do not decompose even at high pH are preferable. Examples of the silicone-based surfactant include side chain modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, single-ended modified polydimethylsiloxane, and side chain double-ended modified polydimethylsiloxane. Those having a polyoxyethylene group and a polyoxyethylene polyoxypropylene group as the modifying group are particularly preferable because they exhibit good properties as an aqueous surfactant. Further, as the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include compounds in which a polyalkylene oxide structure is introduced into the Si portion side chain of dimethylsiloxane.
Examples of the fluorine-based surfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate ester compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. Polyoxyalkylene ether polymer compounds are particularly preferred because they have low foaming properties. Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid and perfluoroalkyl sulfonic acid salt. Examples of the perfluoroalkylcarboxylic acid compound include perfluoroalkylcarboxylic acid and perfluoroalkylcarboxylic acid salt. 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 poly having a perfluoroalkyl ether group in the side chain. Examples thereof include salts of oxyalkylene ether polymers. The counter ions of the salts in these fluorine-based surfactants include Li, Na, K, NH ₄ , NH ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ , and NH (CH ₂ CH ₂ OH). ₃ etc. can be mentioned.
Examples of the amphoteric tenside include laurylaminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.
Examples of the nonionic surfactant include polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl amine, polyoxyethylene alkyl amide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan. Examples thereof include a fatty acid ester and an ethylene oxide adduct of acetylene alcohol.
Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl salt, polyoxyethylene alkyl ether sulfate salt and the like.
These may be used alone or in combination of two or more.

（但し、一般式（Ｓ−１）式中、ｍ、ｎ、ａ、及びｂは、それぞれ独立に、整数を表わし、Ｒは、アルキレン基を表し、Ｒ’は、アルキル基を表す。）
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-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, side-chain modified polydimethylsiloxane, double-ended modified polydimethylsiloxane, one-ended modified polydimethylsiloxane, side chain. Examples thereof include both-terminal modified polydimethylsiloxane, and a polyether-modified silicone-based surfactant having a polyoxyethylene group and a polyoxyethylene polyoxypropylene group as modifying groups is particularly preferable because it exhibits good properties as an aqueous surfactant. ..
As such a surfactant, an appropriately synthesized one may be used, or a commercially available product may be used. As commercially available products, for example, they can be obtained from Big Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., Kyoeisha Chemical Co., Ltd. and the like.
The above-mentioned polyether-modified silicone-based surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polyalkylene oxide structure represented by the general formula (S-1) may be dimethylpoly. Examples thereof include those introduced into the Si part side chain of siloxane.

(However, in the general formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R'represents an alkyl group.)
Commercially available products can be used as the above-mentioned polyether-modified silicone-based surfactant, for example, KF-618, KF-642, KF-643 (Shinetsu Chemical Industry Co., Ltd.), EMALEX-SS-5602, SS-. 1906EX (Nippon 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 (Big Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.) and the like can be mentioned.

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ＣｍＦ_２ｍ＋１でｍは１〜６の整数、又はＣＨ_２ＣＨ（ＯＨ）ＣＨ_２−ＣｍＦ_２ｍ＋１でｍは４〜６の整数、又はＣｐＨ_２ｐ＋１でｐは１〜１９の整数である。ｎは１〜６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、キャプストーンＦＳ−３０、ＦＳ−３１、ＦＳ−３１００、ＦＳ−３４、ＦＳ−３５（いずれも、Ｃｈｅｍｏｕｒｓ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、Ｃｈｅｍｏｕｒｓ社製のＦＳ−３１００、ＦＳ−３４、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 compound having 2 to 16 carbon atoms substituted with fluorine is preferable, and a compound having 4 to 16 carbon atoms substituted with fluorine is more preferable.
Examples of the fluorosurfactant include a perfluoroalkyl phosphate ester compound, a perfluoroalkylethylene oxide adduct, and a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain. Among these, the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in the side chain is preferable because it has less foaming property, and is particularly a fluorine-based compound represented by the general formula (F-1) and the general formula (F-2). Surfactants are preferred.

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 above general formula (F-2), Y is H or CmF _{2m + 1} and m is an integer of 1 to 6, or CH ₂ CH (OH) CH _2- CmF _{2m + 1} and m is 4 to 6. It is an integer, or CpH _{2p + 1} and p is an integer of 1-19. n is an integer of 1 to 6. a is an integer of 4 to 14.
Commercially available products may be used as the above-mentioned fluorine-based surfactant. Examples of this commercially available product include Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, and S-145 (all manufactured by Asahi Glass Co., Ltd.); Full Lard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M Co., Ltd.); Megafuck F-470, F -1405, F-474 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR, Capstone FS-30, FS-31, FS-3100, FS-34, FS-35 (all manufactured by The Chemours Company); FT-110, FT-250, FT-251, FT-400S, FT-150, FT- 400SW (all manufactured by Neos Co., Ltd.), Polyfox PF-136A, PF-156A, PF-151N, PF-154, PF-159 (manufactured by Omniova), Unidyne DSN-403N (manufactured by Daikin Industries Co., Ltd.) Among these, the FS-3100, FS-34, and FS- 300, FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW manufactured by Neos Co., Ltd., Polyfox PF-151N manufactured by Omninova, and Unidyne DSN-manufactured by Daikin Industries Co., Ltd. 403N is particularly preferable.

The content of the surfactant in the ink is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of excellent wettability and ejection stability and improvement in image quality, 0.001 mass is used. % Or more and 5% by mass or less are preferable, and 0.05% by mass or more and 5% by mass or less are more preferable.

<Defoamer>
The defoaming agent is not particularly limited, and examples thereof include a silicone-based defoaming agent, a polyether-based defoaming agent, and a fatty acid ester-based defoaming agent. These may be used alone or in combination of two or more. Among these, a silicone-based defoaming agent is preferable because it has an excellent defoaming effect.

<Preservatives and fungicides>
The antiseptic and antifungal agent is not particularly limited, and examples thereof include 1,2-benzisothiazolin-3-one and the like.

<Rust inhibitor>
The rust preventive is not particularly limited, and examples thereof include acidic sulfite and sodium thiosulfate.

<pH adjuster>
The pH adjusting agent 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.

<< Ink manufacturing method >>
As a method for producing ink, for example, water, a coloring material, a compound represented by the general formula (1), a copolymer, and other components are dispersed or dissolved in an aqueous medium, and the ink is produced by stirring and mixing. Can be mentioned. Further, the copolymer may be used as a color material dispersion resin used when producing a color material dispersion.
Dispersion can be performed by, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, ultrasonic dispersion, or the like. The stirring and mixing can be performed by, for example, a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser, or the like.

<< Recording medium >>
The recording medium used for recording is not particularly limited, and examples thereof include plain paper, glossy paper, special paper, cloth, film, transparency sheet, and general-purpose printing paper.

<< Recorded material >>
The recording material has a recording medium and a print layer formed by the ink of the present invention applied on the recording medium. Since the print layer is a layer formed by applying the ink of the present invention and drying it, it contains the general formula (1).
When the ink of the present invention is applied to a recording medium with a general amount of ink applied to form a solid image, the content of the general formula (1) per ^{unit area (1 cm 2) in the region where the solid image is formed is formed.} Is 5.6 × 10 ^-7 mg or more and 2.8 × 10 ^-3 mg or less. The solid image means an image having at least a part of a region formed by a single ink. That is, the solid image does not need to be formed by a single ink on the entire surface of the image formed by the ink. The content of the general formula (1) is determined from the content of the general formula (1) contained in the solid image area of the unit area (1 cm ^2), a solid having a larger area than the unit area (1 cm ²⁾ The unit area (1 cm) is derived from the content of the general formula (1) contained in the image region or the total content of the general formula (1) contained in a plurality of solid image regions having a total area larger than the ^{unit area (1 cm 2).} The content of the general formula (1) included in the solid image area around ^{2) may be obtained by calculation.}

<< Ink container >>
The ink container may include an ink container for accommodating the ink of the present invention, and may further have other members appropriately selected as necessary.
The shape, structure, size, material, etc. of the ink container can be appropriately selected according to the purpose. For example, an ink container having an ink container made of an aluminum laminate film, a resin film, or the like, or having a large capacity. An ink tank or the like is suitable.

<< Recording device, recording method >>
The ink of the present invention can be suitably used for various recording devices by an inkjet recording method, for example, a printer, a facsimile device, a copying device, a printer / fax / copier multifunction device, a three-dimensional modeling device, and the like.
In the present invention, the recording device and the recording method are devices capable of ejecting ink, various processing liquids, and the like to a recording medium, and a method for recording using the device. The recording medium means a medium to which ink and various treatment liquids can adhere even temporarily.
This recording device can include not only a head portion for ejecting ink, but also means related to feeding, transporting, and discharging paper of a recording medium, a pretreatment device, a device called a posttreatment device, and the like. ..
The recording device and the recording method may have a heating means used in the heating step and a drying means used in the drying step. The heating means and the drying means include, for example, means for heating and drying the printed surface and the back surface of the recording medium. The heating means and the drying means are not particularly limited, but for example, a hot 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 device and the recording method are not limited to those in which significant images such as characters and figures are visualized by ink. For example, those that form patterns such as geometric patterns and those that form three-dimensional images are also included.
Further, the recording device includes both a serial type device that moves the discharge head and a line type device that does not move the discharge head, unless otherwise specified.
Further, as this recording device, it is possible to use not only a desktop type but also a wide recording device capable of printing on an A0 size recording medium, or, for example, continuous paper wound in a roll shape as a recording medium. A continuous book printer is also included.
An example of the recording device will be described with reference to FIGS. 1 and 2. FIG. 1 is a perspective explanatory view of the device. FIG. 2 is a perspective explanatory view of the main tank. The image forming apparatus 400 as an example of the recording apparatus is a serial type image forming apparatus. A mechanism portion 420 is provided in the exterior 401 of the image forming apparatus 400. Each ink storage section 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is, for example, packaged in an aluminum laminated film or the like. It is formed of members. The ink storage unit 411 is housed in, for example, a plastic storage 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 behind the opening when the cover 401c of the main body of the apparatus is opened. A main tank 410 is detachably attached to the cartridge holder 404. As a result, each ink ejection port 413 of the main tank 410 and the ejection head 434 for each color communicate with each other via the supply tube 436 for each color, and ink can be ejected from the ejection head 434 to the recording medium.

The method of using the ink is not limited to the inkjet recording method, and can be widely used. In addition to the inkjet recording method, examples thereof include a blade coating method, a gravure coating method, a bar coating method, a roll coating method, a dip coating method, a curtain coating method, a slide coating method, a die coating method, and a spray coating method.

<< Use >>
The use of the ink of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose, and can be applied to, for example, printed matter, paints, coating materials, base materials and the like. Further, it can be used not only as an ink to form two-dimensional characters and images, but also as a three-dimensional modeling material for forming a three-dimensional stereoscopic image (three-dimensional model).
As the three-dimensional modeling apparatus for modeling the three-dimensional object, a known one can be used, and is not particularly limited, but for example, one provided with ink accommodating means, supply means, ejection means, drying means and the like is used. be able to. The three-dimensional model includes a three-dimensional model obtained by overcoating with ink. Further, a molded product obtained by processing a structure in which ink is applied on a base material such as a recording medium is also included. The molded product is, for example, a sheet-shaped or film-shaped recorded material or structure that has been subjected to molding processing such as heat stretching or punching, and is, for example, an automobile, OA equipment, electricity, or. It is suitably used for molding after decorating the surface of electronic devices, meters of cameras, panels of operation parts, and the like.

Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples. In addition, "part" in an example represents "mass part".

The average molecular weight of the copolymers used in Examples and Comparative Examples was determined as follows.
[Measurement of average molecular weight of copolymer]
It was measured by GPC (Gel Permeation Chromatography) under the following conditions.
・ Equipment: GPC-8020 (manufactured by Tosoh Corporation)
-Column: TSK G2000HXL and G4000HXL (manufactured by Tosoh Corporation)
・ Temperature: 40 ℃
-Solvent: THF (tetrahydrofuran)
-Flow flow rate: 1.0 mL / min Inject 1 mL of a copolymer with a concentration of 0.5% by mass, and use 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. The number average molecular weight Mn and the weight average molecular weight Mw of the copolymer were calculated.

<Example of synthesis of compound represented by general formula (1)>
-Synthesis of compound A-7-
50.5 g (300 mmol) of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30.4 g (300 mmol) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) are dissolved in 500 ml of dry toluene and stirred under an argon stream. While heating to 105 ° C. A solution prepared by dissolving 86.6 g (600 mmol) of 2-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) in 3000 ml of dry toluene was slowly added dropwise thereto. After the dropping, the mixture was stirred at 105 ° C. for 4 hours. After cooling to room temperature, the precipitated white solid was filtered, washed with toluene and hexane, and dried to obtain 119 g of compound A-7 of the general formula (1).

-Synthesis of compound A-8-
50.5 g (300 mmol) of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30.4 g (300 mmol) of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) are dissolved in 500 ml of dry toluene and stirred under an argon stream. While heating to 105 ° C. A solution prepared by dissolving 86.6 g (600 mmol) of 1-naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.) in 3000 ml of dry toluene was slowly added dropwise thereto. After the dropping, the mixture was stirred at 105 ° C. for 4 hours. After cooling to room temperature, the precipitated white solid was filtered, washed with toluene and hexane, and dried to obtain 106 g of compound A-8 of the general formula (1).

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の構造式（１）の反応中間体を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Ｍ−２を得た。

１２．４ｇ（１７２ｍｍｏｌ）のアクリル酸（東京化成工業社製）、４７．６ｇ（１０８ｍｍｏｌ）のモノマーＭ−２を、４２０ｍｌの乾燥メチルエチルケトンに溶解してモノマー溶液を調製した。モノマー溶液の１０質量％をアルゴン気流下で７５℃まで加熱した後、残りのモノマー溶液に２．３０ｇの２，２’−アゾビス（イソブチロニトリル）（ＡＩＢＮ、東京化成工業社製）、０．２０ｇのα−チオグリセロール（東京化成工業社製）を溶解した溶液を２．５時間かけて滴下し、７５℃で６時間撹拌した。室温まで冷却し、得られた反応溶液をヘキサンに投下した。析出物した共重合体をろ別し、減圧乾燥して、５８．５ｇの共重合体ＣＰ−１（重量平均分子量（Ｍｗ）：２２０００）を得た。 <Example of synthesis of copolymer>
-Synthesis of copolymer CP-1-
50.5 g (300 mmol) of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 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. While heating 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 the 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 the mixture was stirred at room temperature for 1 hour. The white solid was filtered off to obtain 53.0 g of the reaction intermediate of the following structural formula (1).

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 the mixture was stirred at room temperature under an argon air flow. 0.03 g of dibutyl tin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto, and the mixture was heated to 50 ° C. with stirring. A solution prepared by dissolving 50.0 g of the reaction intermediate of the structural formula (1) in 120 ml of methyl ethyl ketone was slowly added dropwise thereto. After the dropping, the mixture was stirred at 50 ° C. for 2 hours. After cooling to room temperature, the insoluble material was filtered off, and the solvent was distilled off from the filtrate to obtain a paste-like crude product. This was purified by silica gel column chromatography (methylene chloride / ethyl acetate = 6/1) to obtain 48.0 g of the target monomer M-2.

A monomer solution was prepared by dissolving 12.4 g (172 mmol) of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 47.6 g (108 mmol) of monomer M-2 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 in the remaining monomer solution. 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 the mixture was stirred at 75 ° C. for 6 hours. The mixture was cooled to room temperature, and the obtained reaction solution was dropped onto hexane. The precipitated copolymer was separated by filtration and dried under reduced pressure to obtain 58.5 g of the copolymer CP-1 (weight average molecular weight (Mw): 22000).

-Synthesis of copolymer CP-2-
A monomer solution was prepared by dissolving 14.9 g (173 mmol) of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 45.1 g (102 mmol) of monomer M-2 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 in the remaining monomer solution. A solution in which 30 g of α-thioglycerol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved was added dropwise over 2.5 hours, and the mixture was stirred at 75 ° C. for 6 hours. The mixture was cooled to room temperature, and the obtained reaction solution was dropped onto hexane. The precipitated copolymer was separated by filtration and dried under reduced pressure to obtain 58.1 g of the copolymer CP-2 (weight average molecular weight (Mw): 19500).

１４．６ｇ（１７０ｍｍｏｌ）のメタクリル酸（東京化成工業社製）、４５．４ｇ（１０２ｍｍｏｌ）のモノマーＭ−１１を、４２０ｍｌの乾燥メチルエチルケトンに溶解してモノマー溶液を調製した。モノマー溶液の１０質量％をアルゴン気流下で７５℃まで加熱した後、残りのモノマー溶液に１．９０ｇの２，２’−アゾビス（イソブチロニトリル）（ＡＩＢＮ、東京化成工業社製）、０．１０ｇのα−チオグリセロール（東京化成工業社製）を溶解した溶液を２．５時間かけて滴下し、７５℃で６時間撹拌した。室温まで冷却し、得られた反応溶液をヘキサンに投下した。析出物した共重合体をろ別し、減圧乾燥して、５７．８ｇの共重合体ＣＰ−３（重量平均分子量（Ｍｗ）：２９０００）を得た。 -Synthesis of copolymer CP-3-
18.6 g (160 mmol) of 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80 ml of methyl ethyl ketone, and the mixture was stirred under an argon stream at room temperature. 0.03 g of dibutyl tin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto, and the mixture was heated to 50 ° C. with stirring. A solution prepared by dissolving 50.0 g of the reaction intermediate of the structural formula (1) in 120 ml of methyl ethyl ketone was slowly added dropwise thereto. After the dropping, the mixture was stirred at 50 ° C. for 2 hours. After cooling to room temperature, the insoluble material was filtered off, and the solvent was distilled off from the filtrate to obtain a paste-like crude product. This was purified by silica gel column chromatography (methylene chloride / ethyl acetate = 6/1) to obtain 45.9 g of the target monomer M-11.

A monomer solution was prepared by dissolving 14.6 g (170 mmol) of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 45.4 g (102 mmol) of monomer M-11 in 420 ml of dry methyl ethyl ketone. After heating 10% by mass of the monomer solution to 75 ° C. under an argon stream, 1.90 g of 2,2'-azobis (isobutyronitrile) (AIBN, manufactured by Tokyo Chemical Industry Co., Ltd.), 0 in the remaining monomer solution. A solution in which 10 g of α-thioglycerol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved was added dropwise over 2.5 hours, and the mixture was stirred at 75 ° C. for 6 hours. The mixture was cooled to room temperature, and the obtained reaction solution was dropped onto hexane. The precipitated copolymer was separated by filtration and dried under reduced pressure to obtain 57.8 g of the copolymer CP-3 (weight average molecular weight (Mw): 29000).

<Example of adjusting pigment dispersion>
-Adjustment of pigment dispersion PD-1-
After dissolving 1.0 part of compound A-7 of the general formula (1) and 6.0 parts of the copolymer CP-1 in 20.0 parts of tetrahydrofuran, the solvent is removed under reduced pressure. As a result, a mixture of compound A-7 of the general formula (1) and the copolymer CP-1 was obtained.
This mixture was dissolved in 50.0 parts of a diethanolamine aqueous solution so that the pH was 8.0. Further, ion-exchanged water was added to make the total amount of the aqueous solution 80.0 parts. To 80.0 parts of the obtained aqueous solution, 20.0 parts of Pigment Red 122 (Toner Magenta EO02, manufactured by Clariant) was added 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 (KDL type, media: using zirconia balls having a diameter of 0.1 mm) manufactured by Simmal Enterprises, and then the average pore size was averaged. The mixture was filtered through a 1.2 μm membrane filter, and an adjusted amount of ion-exchanged water was added to obtain 97.0 parts by mass of a pigment dispersion PD-1 (pigment solid content concentration: 20% by mass).

-Adjustment of pigment dispersion PD-2-
0.2 parts of compound A-8 of the general formula (1) and 6.0 parts of the copolymer CP-2 are dissolved in 20.0 parts of tetrahydrofuran, and then the solvent is removed under reduced pressure. As a result, a mixture of compound A-8 of the general formula (1) and the copolymer CP-2 was obtained.
This mixture was dissolved in 50.0 parts of a tetraethylammonium hydroxide aqueous solution so that the pH was 8.0. Further, ion-exchanged water was added to make the total amount of the aqueous solution 80.0 parts. To 80.0 parts of the obtained aqueous solution, 20.0 parts of Pigment Red 122 (Toner Magenta EO02, manufactured by Clariant) was added 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 (KDL type, media: using zirconia balls having a diameter of 0.1 mm) manufactured by Simmal Enterprises, and then the average pore size was averaged. The mixture was filtered through a 1.2 μm membrane filter, and an adjusted amount of ion-exchanged water was added to obtain 97.0 parts by mass of a pigment dispersion PD-2 (pigment solid content concentration: 20% by mass).

-Adjustment of pigment dispersion PD-3-
0.1 parts of compound A-7 of the general formula (1) and 5.0 parts of the copolymer CP-3 are dissolved in 20.0 parts of tetrahydrofuran, and then the solvent is removed under reduced pressure. As a result, a mixture of compound A-7 of the general formula (1) and the copolymer CP-3 was obtained.
This mixture was dissolved in 50.0 parts of a tetraethylammonium hydroxide aqueous solution so that the pH was 8.0. Further, ion-exchanged water was added to make the total amount of the aqueous solution 80.0 parts. To 80.0 parts of the obtained aqueous solution, 20.0 parts of Pigment Red 122 (Toner Magenta EO02, manufactured by Clariant) was added 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 (KDL type, media: using zirconia balls having a diameter of 0.1 mm) manufactured by Simmal Enterprises, and then the average pore size was averaged. The mixture was filtered through a 1.2 μm membrane filter, and an adjusted amount of ion-exchanged water was added to obtain 97.0 parts by mass of a pigment dispersion PD-3 (pigment solid content concentration: 20% by mass).

-Adjustment of pigment dispersion PD-4-
After dissolving 0.005 parts of compound A-7 of the general formula (1) and 7.5 parts of the copolymer CP-1 in 20.0 parts of tetrahydrofuran, the solvent is removed under reduced pressure. As a result, a mixture of compound A-7 of the general formula (1) and the copolymer CP-1 was obtained.
This mixture was dissolved in 50.0 parts of a diethanolamine aqueous solution so that the pH was 8.0. Further, ion-exchanged water was added to make the total amount of the aqueous solution 80.0 parts. To 80.0 parts of the obtained aqueous solution, 20.0 parts of Pigment Red 122 (Toner Magenta EO02, manufactured by Clariant) was added 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 (KDL type, media: using zirconia balls having a diameter of 0.1 mm) manufactured by Simmal Enterprises, and then the average pore size was averaged. The mixture was filtered through a 1.2 μm membrane filter, and an adjusted amount of ion-exchanged water was added to obtain 97.0 parts by mass of a pigment dispersion PD-4 (pigment solid content concentration: 20% by mass).

-Adjustment of pigment dispersion PD-5-
0.05 parts of compound A-7 of the general formula (1) was dissolved in tetrahydrofuran to make the total amount of the solution 100 parts. 1.0 part of a solution of compound A-7 of the general formula (1) in tetrahydrofuran (0.005% by mass) and 2.5 parts of the copolymer CP-1 were dissolved in 20.0 parts of tetrahydrofuran. Then, the solvent was removed under reduced pressure to obtain a mixture of compound A-7 of the general formula (1) and the copolymer CP-1.
This mixture was dissolved in 50.0 parts of a diethanolamine aqueous solution so that the pH was 8.0. Further, ion-exchanged water was added to make the total amount of the aqueous solution 80.0 parts. To 80.0 parts of the obtained aqueous solution, 20.0 parts of Pigment Red 122 (Toner Magenta EO02, manufactured by Clariant) was added 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 (KDL type, media: using zirconia balls having a diameter of 0.1 mm) manufactured by Simmal Enterprises, and then the average pore size was averaged. The mixture was filtered through a 1.2 μm membrane filter, and an adjusted amount of ion-exchanged water was added to obtain 97.0 parts by mass of a pigment dispersion PD-5 (pigment solid content concentration: 20% by mass).

-Adjustment of pigment dispersion PD-6-
After dissolving 0.075 parts of compound A-7 of the general formula (1) and 4.0 parts of the copolymer CP-1 in 20.0 parts of tetrahydrofuran, the solvent is removed under reduced pressure. As a result, a mixture of compound A-7 of the general formula (1) and the copolymer CP-1 was obtained.
This mixture was dissolved in 50.0 parts of sodium hydroxide aqueous solution so that the pH was 8.0. Further, ion-exchanged water was added to make the total amount of the aqueous solution 84.0 parts. To 84.0 parts of the obtained aqueous solution, 16.0 parts of carbon black (NIPEX150, manufactured by Degussa) was added 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 (KDL type, media: using zirconia balls having a diameter of 0.1 mm) manufactured by Simmal Enterprises, and then the average pore size was averaged. The mixture was filtered through a 1.2 μm membrane filter, and an adjusted amount of ion-exchanged water was added to obtain 97.0 parts by mass of a pigment dispersion PD-6 (pigment solid content concentration: 16% by mass).

-Adjustment of pigment dispersion PD-7-
After dissolving 0.075 parts of compound A-7 of the general formula (1) and 7.5 parts of the copolymer CP-2 in 20.0 parts of tetrahydrofuran, the solvent is removed under reduced pressure. As a result, a mixture of compound A-7 of the general formula (1) and the copolymer CP-2 was obtained.
This mixture was dissolved in 50.0 parts of a diethanolamine aqueous solution so that the pH was 8.0. Further, ion-exchanged water was added to make the total amount of the aqueous solution 80.0 parts. To 80.0 parts of the obtained aqueous solution, 20.0 parts of Pigment Blue 15: 3 (Chromofine Blue A-220JC, manufactured by Dainichiseika Co., Ltd.) was added 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 (KDL type, media: using zirconia balls having a diameter of 0.1 mm) manufactured by Simmal Enterprises, and then the average pore size was averaged. The mixture was filtered through a 1.2 μm membrane filter, and an adjusted amount of ion-exchanged water was added to obtain 97.0 parts by mass of a pigment dispersion PD-7 (pigment solid content concentration: 20% by mass).

-Adjustment of pigment dispersion PD-8-
After dissolving 0.075 parts of compound A-8 of the general formula (1) and 8.0 parts of the copolymer CP-1 in 20.0 parts of tetrahydrofuran, the solvent is removed under reduced pressure. As a result, a mixture of compound A-8 of the general formula (1) and the copolymer CP-1 was obtained.
This mixture was dissolved in 50.0 parts of a diethanolamine aqueous solution so that the pH was 8.0. Further, ion-exchanged water was added to make the total amount of the aqueous solution 80.0 parts. To 80.0 parts of the obtained aqueous solution, 20.0 parts of Pigment Yellow 74 (First Yellow 531 manufactured by Dainichiseika Co., Ltd.) was added 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 (KDL type, media: using zirconia balls having a diameter of 0.1 mm) manufactured by Simmal Enterprises, and then the average pore size was averaged. The mixture was filtered through a 1.2 μm membrane filter, and an adjusted amount of ion-exchanged water was added to obtain 97.0 parts by mass of a pigment dispersion PD-8 (pigment solid content concentration: 20% by mass).

<Example 1>
-Making ink GJ-1-
40.0 parts by mass of pigment dispersion PD-1, 20.0 parts by mass of glycerin, 5.0 parts by mass of 1,3-butanediol, 10.0 parts by mass of 3-methoxy-N, N-dimethylpropion Amid, 5.0 parts by mass 3-ethyl-3-hydroxymethyloxetane, 1.0 part by mass 2-ethyl-1,3-hexanediol, 1.0 part by mass 2,2,4-trimethyl-1 , 3-Pentanediol, 1.0 part by mass of Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.), and 17.0 parts by mass of ion-exchanged water were mixed and stirred for 1 hour, and then the average pore size was 1.2 μm. The ink GJ-1 of Example 1 was prepared by filtering with a membrane filter.

<Examples 2 to 8>
Inks GJ-2 to 8 of Examples 2 to 8 were prepared in the same manner as in Example 1 except that the composition of Example 1 was changed as shown in Table 1 below. The unit of each number in Table 1 is "part by mass".

<Comparative Example 1>
-Adjustment of pigment dispersion PRD-1-
4.0 parts of the copolymer CP-1 was dissolved in 50.0 parts of a diethanolamine aqueous solution so that the pH was 8.0. Further, ion-exchanged water was added to make the total amount of the aqueous solution 80.0 parts. To 80.0 parts of the obtained aqueous solution, 20.0 parts of Pigment Red 122 (Toner Magenta EO02, manufactured by Clariant) was added 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 (KDL type, media: using zirconia balls having a diameter of 0.1 mm) manufactured by Simmal Enterprises, and then the average pore size was averaged. The mixture was filtered through a 1.2 μm membrane filter, and an adjusted amount of ion-exchanged water was added to obtain 97.0 parts by mass of a pigment dispersion RPD-1 (pigment solid content concentration: 20% by mass).
-Preparation of ink RGJ-1-
Next, a comparative ink RGJ-1 was obtained in the same manner as in Example 1 except that the pigment dispersion RPD-1 was used instead of the pigment dispersion PD-1 in the ink production of Example 1.

<Comparative Example 2>
-Adjustment of pigment dispersion PRD-2-
2.25 parts of compound A-7 of the general formula (1) and 6.0 parts of the copolymer CP-1 are dissolved in 20.0 parts of tetrahydrofuran, and then the solvent is removed under reduced pressure. As a result, a mixture of compound A-7 of the general formula (1) and the copolymer CP-1 was obtained.
This mixture was dissolved in 50.0 parts of a diethanolamine aqueous solution so that the pH was 8.0. Further, ion-exchanged water was added to make the total amount of the aqueous solution 80.0 parts. To 80.0 parts of the obtained aqueous solution, 20.0 parts of Pigment Red 122 (Toner Magenta EO02, manufactured by Clariant) was added 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 (KDL type, media: using zirconia balls having a diameter of 0.1 mm) manufactured by Symmulenterprises, and then the average pore size was averaged. The mixture was filtered through a 1.2 μm membrane filter, and an adjusted amount of ion-exchanged water was added to obtain 97.0 parts by mass of a pigment dispersion RPD-2 (pigment solid content concentration: 20% by mass).
-Preparation of ink RGJ-2-
Next, a comparative ink RGJ-2 was obtained in the same manner as in Example 1 except that the pigment dispersion RPD-2 was used instead of the pigment dispersion PD-1 in the preparation of the ink of Example 1.

次いで、３．２０ｇ（４４．４ｍｍｏｌ）のアクリル酸（アルドリッチ社製）、及び１５．８２ｇ（３７．０ｍｍｏｌ）のモノマーＲＭ−１、及び０．６６８ｇ（４．０７ｍｍｏｌ）の２，２’−アゾビスイソ（ブチロニトリル）（東京化成社製）を１２８ｍＬのメチルエチルケトン（関東化学社製）に溶解して、モノマー溶液を調製した。反応容器に３２ｍＬのメチルエチルケトン（関東化学社製）を加え、アルゴン気流下で７５℃まで加熱した後、モノマー溶液を１時間かけて滴下し還流下で５時間撹拌した。室温まで冷却し、得られた反応溶液をヘキサンに投下した。析出物した共重合体をろ別し、減圧乾燥して、１９．９２ｇの共重合体ＲＣＰ−１（重量平均分子量（Ｍｗ）：２０，１００、数平均分子量（Ｍｎ）９８００）を得た。
−顔料分散体ＲＰＤ−３の調製−
４．０部の共重合体ＲＣＰ−１を、ｐＨが８．０となるように、５０．０部のジエタノールアミン水溶液に溶解した。さらにイオン交換水を加え、水溶液の全量を８０．０部とした。得られた水溶液８０．０部に対し、２０．０部のピグメントレッド１２２（トナーマゼンタＥＯ０２、クラリアント社製）を加えて１２時間攪拌した。
得られた混合物をディスクタイプのビーズミル（シンマルエンタープライゼス社製、ＫＤＬ型、メディア：直径０．１ｍｍのジルコニアボール使用）を用いて、周速１０ｍ／ｓで１時間循環分散した後、平均孔径１．２μｍのメンブレンフィルターでろ過し、調整量のイオン交換水を加えて、９７．０質量部の顔料分散体ＲＰＤ−３（顔料固形分濃度：２０質量％）を得た。
−インクＲＧＪ−３の調製−
次に、実施例１のインクの作製における顔料分散体ＰＤ−１の代わりに、顔料分散体ＲＰＤ−３を用いた以外は、実施例１と同様にして、比較インクＲＧＪ−３を得た。 <Comparative Example 3>
-Synthesis of copolymer RCP-1-
62.0 g (525 mmol) of 1,6-hexanediol (manufactured by Tokyo Kasei 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-naphthalene carbonyl chloride (manufactured by Tokyo Kasei Co., Ltd.) in 100 mL of methylene chloride was added dropwise to this solution with stirring over 2 hours, and then the mixture was stirred at room temperature for 6 hours. .. After washing the obtained reaction solution with water, the organic phase was isolated, 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-6-hydroxyhexyl ester.
Next, 42.1 g (155 mmol) of 2-naphthoic acid-2-hydroxyhexyl ester was dissolved in 80 mL of ultra-dehydrated dichloromethane (manufactured by Wako Pure Chemical Industries, Ltd.). To this solution, 24.0 g (155 mmol) of 2-methacryloyloxyethyl isocyanate (Kalens MOI, manufactured by Showa Denko KK) was added dropwise over 1 hour with stirring, and then the mixture was stirred at 40 ° C. for 12 hours. 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, and 57.0 g of the monomer RM represented by the following structural formula was used. I got -1.

Then 3.20 g (44.4 mmol) of acrylic acid (manufactured by Aldrich), 15.82 g (37.0 mmol) of monomer RM-1, and 0.668 g (4.07 mmol) of 2,2'-azobisisobuty. (Butyronitrile) (manufactured by Tokyo Kasei Co., Ltd.) was dissolved in 128 mL of methyl ethyl ketone (manufactured by Kanto Chemical Co., Inc.) to prepare a monomer solution. 32 mL of methyl ethyl ketone (manufactured by Kanto Chemical Co., Inc.) was added to the reaction vessel, heated to 75 ° C. under an argon stream, and then the monomer solution was added dropwise over 1 hour and stirred under reflux for 5 hours. The mixture was cooled to room temperature, and the obtained reaction solution was dropped onto hexane. The precipitated copolymer was separated by filtration and dried under reduced pressure to obtain 19.92 g of the copolymer RCP-1 (weight average molecular weight (Mw): 20,100, number average molecular weight (Mn) 9800).
-Preparation of pigment dispersion RPD-3-
4.0 parts of the copolymer RCP-1 was dissolved in 50.0 parts of a diethanolamine aqueous solution so that the pH was 8.0. Further, ion-exchanged water was added to make the total amount of the aqueous solution 80.0 parts. To 80.0 parts of the obtained aqueous solution, 20.0 parts of Pigment Red 122 (Toner Magenta EO02, manufactured by Clariant) was added 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 (KDL type, media: using a zirconia ball having a diameter of 0.1 mm) manufactured by Symmulenterprises, and then the average pore diameter was averaged. The mixture was filtered through a 1.2 μm membrane filter, and an adjusted amount of ion-exchanged water was added to obtain 97.0 parts by mass of a pigment dispersion RPD-3 (pigment solid content concentration: 20% by mass).
-Preparation of ink RGJ-3-
Next, a comparative ink RGJ-3 was obtained in the same manner as in Example 1 except that the pigment dispersion RPD-3 was used instead of the pigment dispersion PD-1 in the preparation of the ink of Example 1.

<Comparative Example 4>
-Preparation of pigment dispersion RPD-4-
4.0 parts of the copolymer RCP-1 was dissolved in 50.0 parts of a diethanolamine aqueous solution so that the pH was 8.0. Further, ion-exchanged water was added to make the total amount of the aqueous solution 84.0 parts. To 84.0 parts of the obtained aqueous solution, 16.0 parts of carbon black (NIPEX150, manufactured by Degussa) was added 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 (KDL type, media: using zirconia balls having a diameter of 0.1 mm) manufactured by Simmal Enterprises, and then the average pore size was averaged. The mixture was filtered through a 1.2 μm membrane filter, and an adjusted amount of ion-exchanged water was added to obtain 97.0 parts by mass of a pigment dispersion RPD-4 (pigment solid content concentration: 20% by mass).
-Preparation of ink RGJ-4-
Next, a comparative ink RGJ-4 was obtained in the same manner as in Example 1 except that the pigment dispersion RPD-4 was used instead of the pigment dispersion PD-1 in the preparation of the ink of Example 1.

<Comparative Example 5>
-Preparation of pigment dispersion RPD-5-
6.0 parts of the copolymer RCP-1 was dissolved in 50.0 parts of a diethanolamine aqueous solution so that the pH became 8.0. Further, ion-exchanged water was added to make the total amount of the aqueous solution 80.0 parts. To 80.0 parts of the obtained aqueous solution, 20.0 parts of Pigment Blue 15: 3 (Chromofine Blue A-220JC, manufactured by Dainichiseika Co., Ltd.) was added 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 (KDL type, media: using zirconia balls having a diameter of 0.1 mm) manufactured by Simmal Enterprises, and then the average pore size was averaged. The mixture was filtered through a 1.2 μm membrane filter, and an adjusted amount of ion-exchanged water was added to obtain 97.0 parts by mass of a pigment dispersion RPD-5 (pigment solid content concentration: 20% by mass).
-Preparation of ink RGJ-5-
Next, a comparative ink RGJ-5 was obtained in the same manner as in Example 1 except that the pigment dispersion RPD-5 was used instead of the pigment dispersion PD-1 in the preparation of the ink of Example 1.

<Comparative Example 6>
-Preparation of pigment dispersion RPD-6-
6.0 parts of the copolymer RCP-1 was dissolved in 50.0 parts of a diethanolamine aqueous solution so that the pH became 8.0. Further, ion-exchanged water was added to make the total amount of the aqueous solution 80.0 parts. To 80.0 parts of the obtained aqueous solution, 20.0 parts of Pigment Yellow 74 (First Yellow 531 manufactured by Dainichiseika Co., Ltd.) was added 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 (KDL type, media: using zirconia balls having a diameter of 0.1 mm) manufactured by Simmal Enterprises, and then the average pore size was averaged. The mixture was filtered through a 1.2 μm membrane filter, and an adjusted amount of ion-exchanged water was added to obtain 97.0 parts by mass of a pigment dispersion RPD-6 (pigment solid content concentration: 20% by mass).
-Preparation of ink RGJ-6-
Next, a comparative ink RGJ-6 was obtained in the same manner as in Example 1 except that the pigment dispersion RPD-6 was used instead of the pigment dispersion PD-1 in the preparation of the ink of Example 1.

Next, the characteristics of the inks produced in Examples 1 to 8 and Comparative Examples 1 to 6 were evaluated according to the following methods and evaluation criteria. The results are shown in Table 2.

[Number of coarse particles]
Using AccuSizer780 (manufactured by Particle Sigmaning Systems), the number of coarse particles having a particle size of 0.5 μm or more and the number of coarse particles having a particle size of 1.0 μm or more present in 5 μL of ink were measured. It is practical that the number of coarse particles having a particle size of 0.5 μm or more is 3,000,000 or less and the number of coarse particles having a particle size of 1.0 μm or more is 10,000 or less. I decided.

[Increase in the number of coarse particles]
Each ink is filled in an ink container and stored at 70 ° C. for one week, and the rate of change in the number of coarse particles of 1.0 μm or more after storage is calculated from the following formula with respect to the number of coarse particles of 1.0 μm or more before storage. Evaluated by criteria. It was judged that it was practical when the rate of change in the number of coarse particles was within 25%.
Increase rate of the number of coarse particles (%) = (number of coarse particles of 1.0 μm or more after storage-number of coarse particles of 1.0 μm or more before storage / number of coarse particles before storage) × 100
[Evaluation criteria]
A: The rate of change in the number of coarse particles is within ± 10% B: The rate of change in the number of coarse particles exceeds ± 10% and is within ± 15% C: The rate of change in the number of coarse particles exceeds ± 15% and is ± 25% Within D: The rate of change in the number of coarse particles exceeds ± 25% and within ± 40% E: The rate of change in the number of coarse particles exceeds ± 40%

From the results in Table 2, the ink containing the compound represented by the general formula (1) of Examples 1 to 8 is compared with the ink containing no compound represented by the general formula (1) of Comparative Examples 1 to 6. It was found that the number of coarse particles was small and the rate of increase in the number of coarse particles after storage was small.
In addition, "-" in Table 2 indicates that the compound represented by the general formula (1) is not substantially contained in the ink.

400 Image forming device 401 Image forming device exterior 401c Device body cover 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 unit 413 Ink discharge port 414 Storage container case 420 Mechanical unit 434 Discharge head 436 Supply tube

Japanese Unexamined Patent Publication No. 2016-196621 Japanese Unexamined Patent Publication No. 2017-082085

Claims (8)

It contains a compound represented by the following chemical formula (A-7) or the following chemical formula (A-8).
An ink in which the content of the compound represented by the chemical formula (A-7) or the chemical formula (A-8) is 0.0002% by mass or more and 0.08% by mass or less with respect to the total amount of the ink.

Further, water, and ink of claim 1 containing a coloring material. The ink according to claim 2 , wherein the coloring material is a pigment. The ink according to claim 3, wherein the pigment is a magenta pigment. An ink container for containing the ink according to any one of claims 1 to 4. A recording device comprising the ink container according to claim 5 and a ejection means for ejecting the contained ink to a recording medium. A recording method comprising a ejection step of ejecting the ink according to any one of claims 1 to 4 onto a recording medium. A recording material having a recording medium and a printing layer formed on the recording medium.
The printed layer contains a compound represented by the following chemical formula (A-7) or the following chemical formula (A-8).
In the region having the printed layer of the recorded material, the content of the chemical formula (A-7) or the chemical formula (A-8) per ^{unit area (1 cm 2} ) is 5.6 × ^10-7 mg or more 2 Records of .8 x 10 ^-3 mg or less.

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