JP2018039913A - Ink, inkjet printer, and inkjet printing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink excellent in high glossiness, ink supply stability, and discharge reliability.SOLUTION: The ink is used in an ink discharge device provided with an ink discharge head for discharging an ink, the ink discharge head having an individual liquid chamber, an inflow channel allowing the ink to flow into the individual liquid chamber, and an outflow channel allowing the ink to flow out of the individual liquid chamber. The ink contains water, a solvent comprising a dimethylpropionamide compound and/or a compound represented by general formula (2), and at least two kinds of resin particles.SELECTED DRAWING: None

Description

  The present invention relates to an ink, an inkjet printing apparatus, and an inkjet printing method.

  In industrial applications, for example, a non-permeable substrate such as a plastic film is used to improve durability such as light resistance, water resistance, and abrasion resistance, and the ink used for the non-permeable substrate Has been developed.

  As the ink, for example, a solvent-based inkjet ink using an organic solvent as a vehicle and an ultraviolet curable inkjet ink mainly composed of a polymerizable monomer are widely used. However, the solvent-based ink-jet ink has a problem that there is a concern about the environmental impact due to solvent evaporation. The UV curable ink-jet ink may have a limited choice of monomers to be used from the viewpoint of safety.

For this reason, water-based inks that have a low environmental load and can be directly recorded on a non-permeable substrate have been proposed (see, for example, Patent Document 1 and Patent Document 2).
Further, there is known an ejection head in which ink is circulated in order to avoid an increase in the size of the ejection head (see Patent Document 3).

  An object of the present invention is to provide an ink excellent in high glossiness, ink supply stability, and ejection reliability.

（ただし、前記一般式（１）中、Ｒ^１、Ｒ^２、及びＲ^３は、それぞれ、炭素数１以上５以下のアルキル基を示し、Ｒ^１、Ｒ^２、及びＲ^３は同一であっても、異なっていてもよい）

（ただし、前記一般式（２）中、Ｒ^４は、メチル基及びエチル基のいずれかを示し、Ｒ^５は、水素原子、炭素数１以上８以下のアルキル基、シクロアルキル基、及びアリール基のいずれかを示す） The ink of the present invention as means for solving the above problems is as described below.
Ink provided with an ink discharge head for discharging ink having an individual liquid chamber, an inflow channel for allowing ink to flow into the individual liquid chamber, and an outflow channel for allowing ink to flow out from the individual liquid chamber In the ink used in the ejection device,
An ink in which the ink contains water, a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2), and at least two kinds of resin particles.

(In the general formula ^(1), R 1, ^{R 2,} and ^{R 3} each represents a an alkyl group having 1 to 5 carbon ^atoms, R 1, ^{R 2,} and ^{R 3} are the same May be different)

(In the general formula (2), R ⁴ represents any of methyl and ethyl, R ⁵ is a hydrogen atom, the number 1 to 8 alkyl group carbon atoms, a cycloalkyl group and an aryl group, Indicate one of

  According to the present invention, an ink ejection apparatus capable of providing an image having high glossiness when printed on various substrates including an impermeable substrate and having ink supply stability and ejection reliability in a printing process. Can provide.

FIG. 1 is a schematic side view showing an example of a mechanism portion of the ink ejection apparatus of the present invention. FIG. 2 is an explanatory plan view of a main part of the ink ejection apparatus shown in FIG. FIG. 3 is an external perspective view showing an example of an ink discharge head in the ink discharge apparatus of the present invention. FIG. 4 is a cross-sectional explanatory diagram in a direction orthogonal to the nozzle arrangement direction of the ink discharge head of FIG. FIG. 5 is a partial cross-sectional explanatory diagram in a direction parallel to the nozzle arrangement direction of the ink discharge head of FIG. FIG. 6 is an explanatory plan view of the nozzle plate of the ink discharge head of FIG. FIG. 7A is an explanatory plan view of each member constituting the flow path member of the ink ejection head in FIG. 3. FIG. 7B is an explanatory plan view of each member constituting the flow path member of the ink discharge head of FIG. 3. FIG. 7C is an explanatory plan view of each member constituting the flow path member of the ink ejection head of FIG. 3. FIG. 7D is an explanatory plan view of each member constituting the flow path member of the ink ejection head in FIG. 3. FIG. 7E is an explanatory plan view of each member constituting the flow path member of the ink ejection head in FIG. 3. FIG. 7F is an explanatory plan view of each member constituting the flow path member of the ink ejection head in FIG. 3. FIG. 8A is an explanatory plan view of each member constituting the common liquid chamber member of the ink discharge head of FIG. 8B is an explanatory plan view of each member constituting the common liquid chamber member of the ink discharge head of FIG. FIG. 9 is a block diagram showing an example of an ink circulation system according to the present invention. FIG. 10 is a cross-sectional view taken along line A-A ′ of FIG. 4. 11 is a cross-sectional view taken along the line B-B ′ of FIG. 4. FIG. 12 is a cross-sectional explanatory view showing an example of an ink discharge head in the ink discharge apparatus of the present invention. FIG. 13 is a cross-sectional explanatory view of the ink discharge head of FIG. FIG. 14A is an explanatory diagram illustrating an example of an ink discharge head and an ink supply unit in the ink discharge apparatus of the present invention. FIG. 14B is an enlarged explanatory view of the ink discharge head shown in FIG. 14A.

（ただし、前記一般式（１）中、Ｒ^１、Ｒ^２、及びＲ^３は、それぞれ、炭素数１以上５以下のアルキル基を示し、Ｒ^１、Ｒ^２、及びＲ^３は同一であっても、異なっていてもよい）

（ただし、前記一般式（２）中、Ｒ^４は、メチル基及びエチル基のいずれかを示し、Ｒ^５は、水素原子、炭素数１以上８以下のアルキル基、シクロアルキル基、及びアリール基のいずれかを示す） (ink)
The ink of the present invention contains water, a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2), and at least two kinds of resin particles, and is further necessary. Depending on the case, it contains other components.

(In the general formula ^(1), R 1, ^{R 2,} and ^{R 3} each represents a an alkyl group having 1 to 5 carbon ^atoms, R 1, ^{R 2,} and ^{R 3} are the same May be different)

(In the general formula (2), R ⁴ represents any of methyl and ethyl, R ⁵ is a hydrogen atom, the number 1 to 8 alkyl group carbon atoms, a cycloalkyl group and an aryl group, Indicate one of

  Among the components contained in the ink, resin particles are one of the materials that greatly affect the performance of images formed by printing. Examples of the resin particles include various types such as an acrylic resin, a polyurethane resin, and a polyester resin, and the resin particles have respective characteristics. For example, an acrylic resin can obtain a suitable image hardness, There is a problem that solvent resistance is poor and it is difficult to satisfy two characteristics simultaneously with a kind of resin. In order to solve the said subject, it is possible to use two or more types of resin particles simultaneously. However, when the miscibility between resin particles and the phase solubility are poor, there is a problem that the desired effects cannot be obtained by crushing the respective properties.

  Further, when an ink discharge head having a circulation path as a flow path is used, if the flow path has a portion that comes into contact with air or has a fine path, resin aggregation tends to occur. Furthermore, the resin particles can easily form a film by drying in the vicinity of the nozzle of the discharge device, which can cause discharge failure.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. As a result, when at least two types of resin particles are used in the ink, the ink adheres by containing an organic solvent capable of dissolving the resin particles. It has been found that the miscibility of the resin particles can be enhanced in the process of drying the printed medium. Further, the use of a solvent capable of improving the resin phase solubility could suppress the problem of resin aggregation in the head having a circulation path. Furthermore, it has been found that by using the solvent within a predetermined range with respect to the total content of the resin particles in the ink, the uniformity of the resin film composed of two or more types of resin particles can be obtained and the gloss can be increased. . Further, although the reason is not clear due to the presence of two or more kinds of resins, it is considered that the formation of a film in the vicinity of the nozzle of the discharge device can be relaxed, and as a result, the discharge reliability can be improved.

（ただし、前記一般式（１）中、Ｒ^１、Ｒ^２、及びＲ^３は、それぞれ、炭素数１以上５以下のアルキル基を示し、Ｒ^１、Ｒ^２、及びＲ^３は同一であっても、異なっていてもよい）

（ただし、前記一般式（２）中、Ｒ^４は、メチル基及びエチル基のいずれかを示し、Ｒ^５は、水素原子、炭素数１以上８以下のアルキル基、シクロアルキル基、及びアリール基のいずれかを示す） <Compound represented by general formula (1) and compound represented by the following general formula (2)>
At least one of the compound represented by the following general formula (1) and the compound represented by the following general formula (2) is an ink when an image is printed using an ink containing at least two kinds of resin particles. In the drying step, a state in which at least two kinds of resins are suitably mixed can be obtained, and as a result, a synergistic effect of characteristics of at least two kinds of resin particles can be brought out.
Among these, it is preferable to use the compound represented by the general formula (1) from the viewpoint of high gloss.

(In the general formula ^(1), R 1, ^{R 2,} and ^{R 3} each represents a an alkyl group having 1 to 5 carbon ^atoms, R 1, ^{R 2,} and ^{R 3} are the same May be different)

(In the general formula (2), R ⁴ represents any of methyl and ethyl, R ⁵ is a hydrogen atom, the number 1 to 8 alkyl group carbon atoms, a cycloalkyl group and an aryl group, Indicate one of

  Among the compounds represented by the general formula (1) and the general formula (2), it is preferable to use the compound represented by the general formula (1) from the viewpoint of high gloss.

（ただし、前記一般式（１）中、Ｒ^１、Ｒ^２、及びＲ^３は、それぞれ、炭素数１以上５以下のアルキル基を示し、Ｒ^１、Ｒ^２、及びＲ^３は同一であっても、異なっていてもよい） << Compound Represented by Formula (1) >>
The compound represented by the general formula (1) is as follows.

(In the general formula ^(1), R 1, ^{R 2,} and ^{R 3} each represents a an alkyl group having 1 to 5 carbon ^atoms, R 1, ^{R 2,} and ^{R 3} are the same May be different)

  Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a pentyl group.

  Examples of the compound represented by the general formula (1) include 3-methoxy-N, N-dimethylpropionamide represented by the following structural formula (1-1); represented by the following structural formula (1-2). 3-butoxy-N, N-dimethylpropionamide; 3-methoxy-N, N-diethylpropionamide and the like. These may be used alone or in combination of two or more. Among these, 3-methoxy-N, N-dimethylpropionamide represented by the following structural formula (1-1) is preferable from the viewpoints of adhesion, scratch resistance, non-transferability, and high gloss.

  By containing the compound represented by the general formula (1), the compatibility between the organic solvent and the resin particles can be increased, and the dispersibility can be improved. Moreover, since the compound represented by the general formula (1) has high permeability to various non-permeable substrates, sufficient wettability to the ink substrate can be secured. As a result, an image having further excellent gloss can be obtained.

  The compound represented by the general formula (1) includes resin particles and 1,2-propanediol, 1,3-propanediol, 1,2 having a certain degree of affinity and a relatively low boiling point. -By using an organic solvent such as butanediol, 1,3-butanediol, or 2,3-butanediol in combination, the dispersion stability of the resin particles in the ink can be secured, and the uniformity of the solid image portion after recording Can be improved, and an image having excellent gloss can be obtained.

  The ink used in the present invention is excellent in dispersion stability of resin particles, and when circulated in a head having a circulation path having a fine path, the dispersibility is maintained without aggregation of the resin particles. . As a result, even when used for a long time, it is possible to circulate the ink without the resin particles adhering to the flow path, the ink flow rate is stabilized, and the ejection stability can be achieved.

As a commercial item of the compound represented by the general formula (1), for example, trade name “Examide M-100” (manufactured by Idemitsu Kosan Co., Ltd., 3-methoxy-N, N-dimethylpropionamide, , R ¹ : methyl group, R ² : methyl group, R ³ : methyl group), trade name “Ecamide B100” (produced by Idemitsu Kosan Co., Ltd., 3-butoxy-N, N-dimethylpropionamide, in the above general formula, R ¹ : methyl group, R ² : methyl group, R ³ : butyl group) and the like. These may be used alone or in combination of two or more.

（ただし、前記一般式（２）中、Ｒ^４は、メチル基及びエチル基のいずれかを示し、Ｒ^５は、水素原子、炭素数１以上８以下のアルキル基、シクロアルキル基、及びアリール基のいずれかを示す） << Compound Represented by Formula (2) >>
The compound represented by the general formula (2) is as follows.

(In the general formula (2), R ⁴ represents any of methyl and ethyl, R ⁵ is a hydrogen atom, the number 1 to 8 alkyl group carbon atoms, a cycloalkyl group and an aryl group, Indicate one of

R ⁴ in the general formula (2) is preferably a hydrogen atom.
Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.

  Examples of the compound represented by the general formula (2) include 3-methyl-3-oxetanemethanol represented by the following structural formula (2-1) and 3 represented by the following structural formula (2-2). -Ethyl-3-oxetanemethanol and the like. These may be used alone or in combination of two or more.

  The total content of the compound represented by the general formula (1) and the compound represented by the general formula (2) is preferably 5% by mass or more and 55% by mass or less, and preferably 10% by mass with respect to the total amount of the ink. % To 45% by mass is more preferable. When the content is 5% by mass or more and 55% by mass or less, the effect of uniform mixing is enhanced, and good dischargeability can be obtained when used in an inkjet printing method. Moreover, it becomes easy to produce an ink having excellent wettability to a non-permeable substrate.

  The content of at least one of the compound represented by the general formula (1) and the compound represented by the general formula (2) in the ink can be confirmed by a gas chromatograph mass spectrometry (GCMS) method. Specifically, the entire ink is subjected to GCMS, and a qualitative analysis of the contained solvent is performed. Once the type of solvent can be identified, a calibration curve for the concentration of each solvent can be created to quantify each solvent contained in the ink.

<Resin particles>
As the resin particles, at least two kinds are used.
The resin particles are not particularly limited, and examples thereof include polyester resin particles; polyurethane resin particles; epoxy resin particles; polyamide resin particles; polyether resin particles; acrylic resin particles; acrylic-silicone resin particles; Condensation-based synthetic resin particles; polyolefin resin particles, polystyrene-based resin particles, polyvinyl alcohol-based resin particles, polyvinyl ester-based resin particles, polyacrylic acid-based resin particles, unsaturated carboxylic acid-based resin-added synthetic resin particles; celluloses And natural polymers such as rosins and natural rubber. These are used in combination of two or more.

  Among these resin particles, one of the at least two types of resin particles is preferably polyurethane resin particles from the viewpoint of ink dispersion stability and high gloss. Due to excellent dispersion stability of ink, ejection reliability is further improved.

  In addition, it is preferable to use polyurethane resin particles and polyvinyl chloride resin particles in combination from the viewpoint of excellent ink supply stability as at least two kinds of resin particles.

  As the resin fine particles, those appropriately synthesized may be used, or commercially available products may be used.

<< Polyurethane resin particles >>
There is no restriction | limiting in particular as said polyurethane resin particle, For example, the polyurethane resin particle etc. which are obtained by making a polyol and polyisocyanate react are mentioned.
Examples of the polyol include polyether polyol, polycarbonate polyol, and polyester polyol. These may be used alone or in combination of two or more.

-Polyether polyol-
Examples of the polyether polyol include those obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as starting materials.

  Examples of the starting material include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, and trimethylolethane. And trimethylolpropane. These may be used alone or in combination of two or more.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran. These may be used alone or in combination of two or more.

  Examples of the polyether polyol include polyoxytetramethylene glycol, polyoxypropylene glycol and the like from the viewpoint of obtaining an ink binder capable of imparting very excellent scratch resistance. These may be used alone or in combination of two or more.

-Polycarbonate polyol-
Examples of the polycarbonate polyol that can be used for the production of the polyurethane resin particles include those obtained by reacting a carbonate with a polyol, and those obtained by reacting phosgene with bisphenol A and the like. These may be used alone or in combination of two or more.

  Examples of the carbonate ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, and diphenyl carbonate. These may be used alone or in combination of two or more.

  Examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1, 2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 -Octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydroquinone, resorcinol , Bisphenol-A, bisphe Relatively low molecular weight dihydroxy compounds such as polyol-F, 4,4′-biphenol, polyether polyols such as polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, polyhexamethylene adipate, polyhexamethylene succinate, poly Examples thereof include polyester polyols such as caprolactone. These may be used alone or in combination of two or more.

-Polyester polyol-
Examples of the polyester polyol include those obtained by esterifying low molecular weight polyols and polycarboxylic acids, polyesters obtained by ring-opening polymerization reaction of cyclic ester compounds such as ε-caprolactone, and copolymers thereof. Examples include polyester. These may be used alone or in combination of two or more.

Examples of the low molecular weight polyol include ethylene glycol and propylene glycol. These may be used alone or in combination of two or more.
Examples of the polycarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, anhydrides or ester-forming derivatives thereof. These may be used alone or in combination of two or more.

-Polyisocyanate-
Examples of the polyisocyanate include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate and naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene Examples thereof include aliphatic or alicyclic diisocyanates such as diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate. These may be used alone or in combination of two or more. Among these, since the ink of the present invention is also used for outdoor applications such as posters and signboards, it requires a coating film having very high long-term weather resistance. From the viewpoint of the long-term weather resistance, aliphatic Or alicyclic diisocyanate is preferable.

Furthermore, it is preferable to use at least one alicyclic diisocyanate because the coating strength and scratch resistance can be obtained when an image is formed.
Examples of the alicyclic diisocyanate include isophorone diisocyanate and dicyclohexylmethane diisocyanate.
As content of the said alicyclic diisocyanate, 60 mass% or more is preferable with respect to the isocyanate compound whole quantity.

<< Method for Producing Polyurethane Resin Particles >>
The polyurethane resin particles used in the ink of the present invention can be obtained by a conventionally used production method, and examples thereof include the following methods.
First, an isocyanate-terminated urethane prepolymer is produced by reacting the polyol and the polyisocyanate in an equivalent ratio in which an isocyanate group becomes excessive in the absence of a solvent or in the presence of an organic solvent.
Next, the anionic group in the isocyanate-terminated urethane prepolymer is neutralized with a neutralizing agent as necessary, and then reacted with a chain extender, and finally the organic solvent in the system is removed as necessary. Can be obtained.

Examples of organic solvents that can be used for the production of polyurethane resin particles include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetates such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; dimethylformamide Amides such as N-methylpyrrolidone and N-ethylpyrrolidone. These may be used alone or in combination of two or more.
Examples of the chain extender include polyamines and other active hydrogen group-containing compounds. These may be used alone or in combination of two or more.

  Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 1,4-cyclohexane. Diamines such as diamines; Polyamines such as diethylenetriamine, dipropylenetriamine and triethylenetetramine; Hydrazines such as hydrazine, N, N′-dimethylhydrazine and 1,6-hexamethylenebishydrazine; Succinic dihydrazide, Adipic dihydrazide And dihydrazides such as glutaric acid dihydrazide, sebacic acid dihydrazide, and isophthalic acid dihydrazide. These may be used alone or in combination of two or more.

  Examples of the other active hydrogen group-containing compounds include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, Glycols such as saccharose, methylene glycol, glycerin, sorbitol; phenols such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone Kind; water etc. are mentioned. These may be used singly or in combination of two or more as long as the storage stability of the ink is not lowered.

  The polyurethane resin particles are preferably polycarbonate urethane resin particles from the viewpoint of high gloss. In the case of the polycarbonate-based urethane resin particles, it is possible to obtain an ink that maintains high gloss even for a recorded matter used in a harsh environment such as an outdoor use.

  As the polyurethane resin particles, commercially available products may be used. For example, U-coat UX-485 (polycarbonate urethane resin particles), U-coat UWS-145 (polyester urethane resin particles), Permarin UA-368T (polycarbonate urethane). Resin particles), permarine UA-200 (polyether urethane resin particles) (manufactured by Sanyo Chemical Industries, Ltd.), and the like. These may be used alone or in combination of two or more.

<< Polyvinyl chloride resin particles >>
The polyvinyl chloride resin particles are preferably vinyl chloride-ethylene copolymers and vinyl chloride-acrylic copolymers, from the viewpoint of ensuring miscibility with pigments and other resin particles contained in the ink. A vinyl chloride-ethylene copolymer is more preferable because it is particularly excellent in adhesion to a polar substrate.

  The polyvinyl chloride resin particles are not particularly limited, and commercially available products can be used. Commercially available polyvinyl chloride resin emulsions, commercially available polyvinyl chloride-acrylic copolymer emulsions, commercially available vinyl chlorides— Examples thereof include emulsions of ethylene copolymers. These may be used alone or in combination of two or more.

As said commercially available polyvinyl chloride resin emulsion, product number 985 (solid content concentration: 40 mass%, anionic property) is mentioned, for example among Nishin Chemical Industry Co., Ltd. Vinibrand (trademark) series. These may be used alone or in combination of two or more.
Examples of the commercially available vinyl chloride-acrylic copolymer emulsion include product number 278 (solid content concentration: 43% by mass, anionic) in the Vinyblan (registered trademark) series manufactured by Nissin Chemical Industry Co., Ltd., 700 ( Solid content concentration: 30% by mass, anionic), 701 (solid content concentration: 30% by mass, anionic), 711 (solid content concentration: 50% by mass, anionic), 721 (solid content concentration: 30% by mass, Anionic), 700FS (solid content concentration: 30% by mass, anionic), 701RL35 (solid content concentration: 30% by mass, anionic), 701RL (solid content concentration: 30% by mass, anionic), 701RL65 (solid content) (Concentration: 30% by mass, anionic). These may be used alone or in combination of two or more.
As the emulsion of the commercially available vinyl chloride-ethylene copolymer, for example, product number 1010 (Smell content concentration: 50 ± 1% by mass, anionic) of Sumierite (registered trademark) series manufactured by Sumika Chemtex Co., Ltd. , 1210 (solid content concentration: 50 ± 1 mass%, anionic), 1320 (solid content concentration: 50 ± 1 mass%, anionic), and the like. These may be used alone or in combination of two or more.
Other commercially available products include the product numbers E15 / 48A (solid content concentration: 50% by mass, anionic), E22 / 48A (solid content) of the VINNOL series manufactured by Wacker Chemie AG in which a hydroxyl component is introduced into a polyvinyl chloride resin. (Concentration: 30% by mass, anionic). These may be used alone or in combination of two or more.

<< Polyester resin particles >>
The polyester resin particles preferably do not contain a hydrophilic component remaining in the dried film such as an emulsifier and a sulfonate in order to obtain water resistance of the image.

  There is no restriction | limiting in particular as said polyester resin particle | grains, A commercial item can be used, For example, as a polyester resin emulsion of the said commercial item, it is product number KZA among emulsion Eritel (trademark) series made from Unitika Co., Ltd. -1449 (solid content concentration: 30% by mass, anionic), KZA-3556 (solid content concentration: 30% by mass, anionic), KZA-0134 (solid content concentration: 30% by mass, anionic), Takamatsu Yushi Co., Ltd. Among the pesresin A series manufactured by the company, product numbers A-124GP (solid content concentration: 30% by mass), A-125S (solid content concentration: 30% by mass), A-160P (solid content concentration: 25% by mass), and the like are listed. It is done. These may be used alone or in combination of two or more.

<< Acrylic resin particles >>
The acrylic resin particles are preferably used as a copolymer with other monomers or a modified acrylic resin in consideration of the affinity with the pigment particles in the ink and the recording material.

  There is no restriction | limiting in particular as said acrylic resin particle | grains, A commercial item can be used, As said acrylic resin particle | grains of the said commercial item, for example, microgel E-1002, E-5002 (styrene-acrylic resin fine particle, Nippon Paint Co., Ltd., Boncoat 4001 (acrylic resin fine particles, manufactured by Dainippon Ink & Chemicals, Inc.), Boncoat 5454 (styrene-acrylic resin fine particles, manufactured by Dainippon Ink & Chemicals, Inc.), SAE-1014 (styrene) -Acrylic resin fine particles, manufactured by Nippon Zeon Co., Ltd., Cybinol SK-200 (acrylic resin fine particles, manufactured by Seiden Chemical Co., Ltd.), Primal AC-22, AC-61 (acrylic resin fine particles, Rohm and Haas Company) Manufactured), NANOCRYL SBCX-2821, 3689 (acrylic resin) Corn-based resin particles, manufactured by Toyo Ink Mfg. Co., Ltd.), # 3070 (methyl polymer resin particles methacrylate, manufactured by Mikuni Color Ltd.). These may be used alone or in combination of two or more.

  In the present invention, the resin particles are not particularly limited, and those supplied in the form of an aqueous emulsion are preferably used. Considering the ease of work of preparing a water-based ink by blending with a solvent, a colorant, and water, and the dispersion in the ink as uniformly as possible, the resin particles were stably dispersed using water as a dispersion medium. It is preferable to add to the ink in the state of a resin emulsion.

  As the resin particles, film formation is facilitated by a water-soluble organic solvent that is added at the time of ink use in actual use, and the film formation of the resin particles is promoted with evaporation of the solvent and water. When the ink of the present invention is used, a heating step is not necessarily required. However, by providing the heating step, a further high-speed printing effect can be obtained.

In dispersing the resin particles in an aqueous medium, a forced emulsification type using a dispersant can also be used. So-called self-emulsifying resin particles having an anionic group are suitable.
The acid value of the anionic group of the self-emulsifying resin particles is preferably 5 mgKOH / g or more and 100 mgKOH / g or less from the viewpoint of water dispersibility, abrasion resistance, and chemical resistance, and 5 mgKOH / mg or more and 50 mgKOH / g. mg or less is preferred.

  Examples of the anionic group include a carboxyl group, a carboxylate group, a sulfonic acid group, and a sulfonate group. Among these, a carboxylate group or a sulfonate group partially or wholly neutralized with a basic compound or the like is preferable from the viewpoint of maintaining good water dispersion stability. In order to introduce the anionic group into the resin, a monomer having the anionic group may be used.

Examples of the method for producing an aqueous dispersion of resin particles having an anionic group include adding a basic compound that can be used for neutralization of an anionic group to the aqueous dispersion.
Examples of the basic compound include organic amines such as ammonia, triethylamine, pyridine, and morpholine; alkanolamines such as monoethanolamine; metal base compounds including Na, K, Li, Ca, and the like. These may be used alone or in combination of two or more.
As a method for producing an aqueous dispersion using the forced emulsification type resin particles, for example, a surfactant such as a nonionic surfactant or an anionic surfactant can be used. These may be used alone or in combination of two or more. Among these, nonionic surfactants are preferable from the viewpoint of water resistance.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene derivative, polyoxyethylene fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene propylene polyol, Examples include sorbitan fatty acid ester, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polycyclic phenyl ether, polyoxyethylene alkylamine, alkylalkanolamide, and polyalkylene glycol (meth) acrylate. Among these, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene alkylamine are preferable. These may be used alone or in combination of two or more.

  Examples of the anionic surfactant include alkyl sulfate salts, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, α-olefin sulfonates, methyl taurates, sulfosuccinates, ether sulfonates, ethers. Examples thereof include carboxylate, fatty acid salt, naphthalenesulfonic acid formalin condensate, alkylamine salt, quaternary ammonium salt, alkylbetaine, and alkylamine oxide. Among these, polyoxyethylene alkyl ether sulfate and sulfosuccinate are preferable.

  There is no restriction | limiting in particular as content of the said surfactant, 0.1 mass% or more and 30 mass% or less are preferable with respect to the resin particle whole quantity, and 5 mass% or more and 20 mass% or less are more preferable. When the content is in the range of 0.1% by mass or more and 30% by mass or less, the resin particles are preferably formed into a film, and an ink excellent in adhesion and water resistance is obtained, and the recorded matter is blocked. It is suitably used.

Further, the volume average particle diameter of the resin particles is preferably 10 nm or more and 1,000 nm or less, more preferably 10 nm or more and 200 nm or less, and particularly preferably 10 nm or more and 100 nm or less, particularly considering use in an ink jet printing apparatus. .
By using resin particles having a volume average particle size of 10 nm or more and 1,000 nm or less, excellent ink supply properties and ejection reliability can be obtained when used in an ink ejection apparatus having a circulation means for circulating ink. In the process of drying the ink on the printing material such as a printing medium, the resin particles are easily dissolved in the organic solvent, and the effect of spreading the resin is easily obtained, so that it is easy to form a high gloss image.
The volume average particle diameter can be measured using, for example, a particle size analyzer (Microtrac Model UPA9340, manufactured by Nikkiso Co., Ltd.).

  In the present invention, the ink contains at least two kinds of resin particles. The total content of the resin particles is 1% by mass or more and 15% by mass with respect to the total amount of the ink from the viewpoint of dispersion stability of the ink. % Or less, and more preferably 5% by mass or more and 12% by mass or less from the viewpoint that the smoothness of the ink layer is further improved, high glossiness can be obtained, and the fixability to the substrate is also improved.

  In the present invention, the ink contains at least two kinds of resins, but the at least two kinds of resins in the present invention means that the components of the resin are different, and the resins having the same components differ only in the weight average molecular weight. The resin particles are the same resin particles. However, even if the components forming the main skeleton are the same, if the side chains are different or other components are included by copolymerization, different types of resins are used.

The qualitative and quantitative determination of the resin particles can be confirmed by, for example, a procedure detailed in Reference Document 1 below. Specifically, it can be confirmed by analysis using a measurement apparatus as shown below.
[Reference 1]
"Testing method and evaluation results of each dynamic characteristic of plastic materials (22); Takeo Yasuda, Plastics: Journal of Japan Plastic Industry Federation /" Plastics "Editorial Board"

<< Infrared Spectroscopic Analysis (IR) >>
Qualitative analysis of resin particles can be performed by measuring absorption wavelengths of various functional groups possessed by the resin particles and comparing them with the IR spectra of known resin particles. Moreover, the relative amount of several types of monomers and resin particles can be compared by comparing the absorbance of the functional group absorption of each resin particle.

<< Thermal analysis (DS / A, TG / DTA) >>
The polymer can be identified by measuring the melting point, glass transition point, etc. of the resin particles using differential scanning calorimetry (DS / A) or differential thermal analysis (DTA).

<< Pyrolysis Gas Chromatography (PyGC) >>
Thermal decomposition products can be separated by gas chromatography, and composition analysis and structural analysis can be performed.
In addition, if a mass spectrometer is directly connected to PyGC, and a decomposition product generated by thermal decomposition is identified, a more accurate analysis can be performed.

<< Nuclear Magnetic Resonance (NMR) >>
Compared with the spectrum of known resin particles, the resin particles can be identified and confirmed. In the case of unknown resin particles, the molecular structure can be estimated. Furthermore, quantitative analysis of the composition ratio and blend ratio of a copolymer and a blend of a plurality of polymers can be performed.

  Before analyzing the resin particles using the measuring device, the colorant component in the ink is precipitated by centrifugation as a pretreatment, and the supernatant containing the resin particles is collected, or the resin is recovered using an appropriate organic solvent. Extracting particles is also effective as a means for improving analysis accuracy.

  When the ink of the present invention is heated after recording, the residual solvent is reduced and the adhesiveness is improved. In particular, when the minimum film-forming temperature of the resin particles (hereinafter sometimes referred to as “MFT”) exceeds 80 ° C., heating can be performed from the viewpoint of eliminating resin film-forming defects and improving image fastness. preferable.

When adjusting the minimum film-forming temperature of the resin emulsion in order to obtain the ink of the present invention, for example, it can be adjusted by controlling the glass transition point of the resin (hereinafter also referred to as “Tg”). In the case where the resin particles are a copolymer, it can be adjusted by changing the ratio of the monomers forming the copolymer. In the present invention, the minimum film-forming temperature refers to the minimum temperature at which a transparent continuous film is formed when the emulsion is thinly cast on a metal plate such as aluminum and the temperature is raised. In the temperature range below the membrane temperature, the emulsion is in the form of a white powder. Specifically, the “film-forming temperature test device” (manufactured by Imoto Seisakusho Co., Ltd.), “TP-801 MFT Tester” (Tester Sangyo Co., Ltd.) A value measured by a commercially available minimum film-forming temperature measuring device such as a company).
Moreover, since it changes also by control of the particle diameter of resin, it is possible to make the minimum film forming temperature of resin into the target value by these control factors.

<Mass ratio (S / A)>
The total content S (mass%) of the compound represented by the general formula (1) and the compound represented by the general formula (2) in the ink, and the total solid content concentration A (mass%) of the resin particles. ) And the mass ratio (S / A) is preferably 0.5 or more and 5 or less, and more preferably 1.0 or more and 4.0 or less. When the mass ratio (S / A) is 0.5 or more and 5 or less, a plurality of resin particles used in image formation can be mixed well, and ink supply is stable in an ejection head device having a circulation path. The discharge stability can be secured.

<Organic solvent>
There is no restriction | limiting in particular as said organic solvent, For example, a water-soluble organic solvent etc. are mentioned.
Examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, 2-methyl-2,4-pentanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol, glycerin, 1, Polyhydric alcohols such as 2,6-hexanetriol, 2-ethyl-1,3-hexanediol, 1,2,4-butanetriol, 1,2,3-butanetriol, and petriol; ethylene glycol monoethyl ether , Ethylene glycol monobutyl ether, diethylene glycol Polyhydric alcohol alkyl ethers such as coal monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether; ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether Polyhydric alcohol aryl ethers such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, γ-butyrolactone, etc. Heterocyclic compounds; Amides such as formamide, N-methylformamide, N, N-dimethylformamide; monoethanolamine, di Ethanolamine, an amine such as triethylamine; dimethyl sulfoxide, sulfolane, sulfur-containing compounds such as thiodiethanol; propylene carbonate; ethylene carbonate. These may be used alone or in combination of two or more.
Among these, from the viewpoint of high gloss and prevention of particle aggregation, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3- Butanediol, 2-methyl-2,4-pentanediol, and dipropylene glycol monomethyl ether are preferred. In addition, 1,2-propanediol and 1,2-butanediol having a boiling point of less than 200 ° C. are preferable from the viewpoint of promoting high scratch resistance, solvent resistance, and resin film formation.

  There is no restriction | limiting in particular as content of the said organic solvent, 20 mass% or more and 70 mass% or less are preferable with respect to the ink whole quantity, and 30 mass% or more and 60 mass% or less are more preferable. When the content is 20% by mass or more and 70% by mass or less, the drying property is excellent and good ejection stability is obtained.

<Water>
There is no restriction | limiting in particular as said water, According to the objective, it can select suitably, For example, pure water, such as ion-exchange water, ultrafiltration water, reverse osmosis water, distilled water; Ultrapure water etc. are mentioned. . These may be used individually by 1 type and may use 2 or more types together.

  The water content is preferably 15% by mass or more and 60% by mass or less based on the total amount of ink. When the content is 15% by mass or more, it is possible to prevent high viscosity and improve the discharge stability. When the content is 60% by mass or less, the wettability to the non-permeable substrate is preferable. Image quality can be improved.

<Other ingredients>
Examples of the other components include pigments, surfactants, antiseptic / antifungal agents, rust preventives, pH adjusters, colorless anti-aging agents for rubbers and plastics such as hindered phenols and hindered phenol amines, and the like. Can be mentioned.

<< Pigment >>
Examples of the pigment include inorganic pigments and organic pigments. These may be used alone or in combination of two or more.

Examples of the inorganic pigment include titanium oxide and iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow, as well as a known method such as a contact method, a furnace method, and a thermal method. And carbon black. These may be used alone or in combination of two or more.
Examples of the organic pigment include azo pigments (for example, azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments, etc.), 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 (eg basic dye chelates, acidic dye chelates), nitro pigments, nitroso pigments, aniline black, etc. Is mentioned. These may be used alone or in combination of two or more.
In addition, resin hollow particles and inorganic hollow particles can also be used.
Of these pigments, those having good affinity with the solvent are preferably used.

  As content of the said pigment, 0.1 to 10 mass% is preferable, and 1 to 10 mass% is preferable. When the content is 0.1% by mass or more and 10% by mass or less, image density, fixability, and ejection stability can be improved.

As specific examples of the pigment, for black, for example, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, or copper, iron (C.I. Pigment black 11), metals such as titanium oxide, and organic pigments such as aniline black (CI pigment black 1). These may be used alone or in combination of two or more.
For color, for example, 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; 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, 185, 190, 193, 209, 219; 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 (phthalocyanine blue), 16, 17: 1, 56, 60, 63; I. Pigment green 1, 4, 7, 8, 10, 17, 18, 36, and the like. These may be used alone or in combination of two or more.

In addition, 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 surface of the pigment (for example, carbon black) can be used.
In addition, it is possible to include a pigment in a microcapsule and to disperse the pigment in water, that is, resin fine particles containing pigment particles.
In this case, the pigment contained in the ink is not necessarily sealed or adsorbed in the resin fine particles, and the pigment may be dispersed in the ink as long as the effects of the present invention are not impaired.

The number average particle diameter of the pigment is not particularly limited, and the maximum frequency in terms of the maximum number is preferably 20 nm or more and 150 nm or less. When the number average particle diameter is 20 nm or more, the dispersion operation and classification operation are facilitated. When the number average particle diameter is 150 nm or less, not only the pigment dispersion stability as the ink composition is improved, but also the ejection stability is excellent. The image quality such as the image density is also high, which is preferable.
The number average particle diameter can be measured using, for example, a particle size analyzer (Microtrac Model UPA9340, manufactured by Nikkiso Co., Ltd.).

  In the case of dispersing a pigment using a dispersant, any conventionally known pigment can be used, and examples thereof include a polymer dispersant and a water-soluble surfactant. These may be used alone or in combination of two or more.

<< Surfactant >>
The surfactant can be contained in order to ensure wettability to the printing medium.

There is no restriction | limiting in particular as said surfactant, For example, an amphoteric surfactant, a nonionic surfactant, an anionic surfactant etc. are mentioned. These may be used alone or in combination of two or more. Among these, nonionic surfactants are preferable from the viewpoints of dispersion stability and image quality.
Depending on the composition, a fluorine-based surfactant or a silicone-based surfactant can be used in combination or singly.

  Examples of the nonionic surfactant include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene propylene block polymer, sorbitan fatty acid ester, polyoxyethylene. Examples include sorbitan fatty acid esters and ethylene oxide adducts of acetylene alcohol. These may be used alone or in combination of two or more.

  As content of the said surfactant, 0.1 to 5 mass% is preferable. When the content is 0.1% by mass or more, the wettability to the non-permeable substrate can be secured, so that the image quality can be improved, and when the content is 5% by mass or less, the ink is less likely to foam. Excellent discharge stability can be obtained.

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

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

<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.

  As the ink of the present invention, for example, it can be suitably used for inkjet.

<Ink production method>
Examples of the method for producing the ink include water, an organic solvent, a compound represented by the general formula (1) and / or a compound represented by the general formula (2), resin particles, and, if necessary, other It can be produced by dispersing or dissolving the components in an aqueous medium and stirring and mixing as appropriate. As the stirring and mixing, for example, a sand mill, a homogenizer, a ball mill, a paint shaker, an ultrasonic disperser, a stirrer using a normal stirrer blade, a magnetic stirrer, a high-speed disperser, or the like can be used.

<Viscosity>
The viscosity of the ink is preferably 2 mPa · s or more and more preferably 3 mPa · s or more and 20 mPa · s or less at 25 ° C. from the viewpoint of image quality such as character quality when recorded on a printing medium. When the viscosity is 2 mPa · s or more, ejection stability can be improved.

(ink cartridge)
The ink cartridge includes an ink cartridge that stores black ink in a container and an ink cartridge that stores color ink in the container.
The ink cartridge contains the ink in a container and further includes other members appropriately selected as necessary.

  The container is not particularly limited, and its shape, structure, size, material and the like can be appropriately selected according to the purpose. For example, an ink bag formed of an aluminum laminate film, a resin film, etc. What has at least etc. is mentioned.

(Inkjet printing method)
The inkjet printing method of the present invention preferably includes an ink ejection step of applying an stimulus and ejecting the ink to record an image on a print medium, and if necessary, a heating step. It has a process.
In addition, the inkjet printing method of the present invention may include a step of stopping the circulation of ink, a step of circulating the ink before discharging the ink, and a printing step of discharging and printing the ink. Even when printing is not performed for a long time or when the power of the printing apparatus is turned off, by using the ink of the present invention, a step of circulating the ink is provided before the ink is discharged, and then the ink is discharged and printed. By doing so, it is possible to stably discharge, and it is possible to provide a good printing method.
Further, when the ink is circulated in the step of not performing printing, the step of applying pressure to the ink with such a strength that the ink is not ejected can provide better ejection stability.

<< Ink ejection process >>
The ink ejection step is a step of recording an image by applying a stimulus to the ink and ejecting the ink.

  There is no restriction | limiting in particular as said irritation | stimulation, According to the objective, it can select suitably, For example, heat | fever (temperature), a pressure, a vibration, light, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, heat and pressure are preferable.

  As an ink discharge mode used for the ink, for example, a piezoelectric element is used as pressure generating means for pressurizing the ink in the ink flow path, and the vibration plate that forms the wall surface of the ink flow path is deformed to change the ink flow. A so-called piezo method (for example, see Japanese Patent Publication No. 2-51734) in which ink drops are ejected by changing the volume in the path; bubbles are generated by heating ink in the ink flow path using a heating resistor; A so-called thermal system (for example, see Japanese Patent Publication No. 61-59911); a diaphragm and an electrode that form a wall surface of an ink flow path are arranged to face each other, and the electrostatic force generated between the diaphragm and the electrode An electrostatic system (for example, refer to Japanese Patent Laid-Open No. 6-71882) that discharges ink droplets by changing the volume of the ink flow path by deforming the diaphragm can be used.

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

<< Heating process >>
The heating step is a step of heating the print medium on which an image is recorded.
As the ink jet printing method, high image quality recording can be performed on the non-permeable substrate, but it is possible to cope with the formation of images with higher image quality, abrasion resistance, and higher adhesion, and high-speed recording conditions. For this purpose, it is preferable to heat the non-permeable substrate after recording. When a heating step is performed after recording, the film formation of the resin contained in the ink is promoted, so that the image hardness of the recorded matter can be improved.

As the apparatus used for the heating step, many known apparatuses can be used, and examples thereof include forced air heating, radiation heating, conduction heating, high frequency drying, microwave drying, and the like. These may be used alone or in combination of two or more.
The heating temperature can be changed according to the type and amount of the water-soluble organic solvent contained in the ink, and the minimum film-forming temperature of the resin emulsion to be added, and depending on the type of the substrate to be printed. Can be changed.
The heating temperature is preferably high in terms of drying property and film forming temperature, more preferably 40 ° C. or more and 120 ° C. or less, and particularly preferably 50 ° C. or more and 90 ° C. or less. When the heating temperature is 40 ° C. or higher and 120 ° C. or lower, damage to the non-permeable substrate to be printed due to heat can be prevented, and occurrence of non-ejection due to warming of the ink head can be suppressed.

  Further, as an example of the printing method in the present invention, a step of applying a clear ink containing no pigment or an ink containing a white pigment as a colorant (white ink) to a printing medium, and an ink having a pigment And a recording method of recording using the recording method. At this time, the clear ink or the white ink can be applied to the entire surface of the print medium, or may be applied to a part of the print medium. In the case of applying to a part of the print medium, for example, it may be applied to the same part as the part where recording is performed, or may be applied to a part which is partly common with the part where printing is performed.

  When the white ink is used, it is also effective to use the following recording method. White ink is applied to the print medium, and recording is performed thereon with ink of a color other than white. According to this method, for example, even when a transparent film is used, the white ink of the present invention is attached to the surface of the print medium, so that the visibility of the recording can be ensured. Since the ink of the present invention has good drying properties, high gloss, scratch resistance, etc. even for non-permeable substrates, white ink is applied to non-porous substrates such as transparent films in order to improve visibility. It is possible to apply.

  Also, it is possible to obtain a similar image with excellent visibility by applying white ink after recording on a transparent film. If clear ink is used instead of white ink, it can also function as a protective layer.

  The method of using the ink is not limited to the ink jet recording method, and can be widely used. Besides the ink jet recording method, for example, 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, a spray coating method and the like can be mentioned.

As an example of the embodiment, when the white ink is applied to the entire surface of the printing medium, the coating is performed by a coating method other than the inkjet printing method, and when recording with ink of a color other than white, the recording is performed by the inkjet printing method. Embodiments are possible.
As another embodiment, recording using white ink and recording using ink of a color other than white can be performed by an inkjet printing method.
The same applies when clear ink is used instead of white ink.

  Here, an ink jet printing apparatus capable of recording using the ink will be described with reference to the drawings. In addition, although the case where a non-permeable base material is used is demonstrated, it can record similarly to permeable base materials, such as paper. The ink jet printing apparatus includes a serial type (shuttle type) scanned by a carriage, a line type equipped with a line type head, and the like. FIG. 1 is a schematic diagram illustrating an example of a serial type ink jet printing apparatus. . FIG. 2 is a schematic diagram showing a configuration in the main body of the apparatus of FIG.

  As shown in FIG. 1, the inkjet printing apparatus includes an apparatus main body 101, a paper feed tray 102 attached to the apparatus main body 101, a paper discharge tray 103, and an ink cartridge loading unit 104. On the upper surface of the ink cartridge loading unit 104, an operation unit 105 such as operation keys and a display is arranged. The ink cartridge loading unit 104 has a front cover 115 that can be opened and closed for attaching and detaching the ink cartridge 201. Reference numeral 111 denotes an upper cover, and reference numeral 112 denotes a front surface of the front cover.

In the apparatus main body 101, as shown in FIG. 2, a carriage 133 is slidably held in the main scanning direction by a guide rod 131 and a stay 132, which are guide members horizontally mounted on the left and right side plates. It is moved and scanned by a motor.
The carriage 133 has a plurality of ink ejection openings of a recording head 134 including four inkjet recording heads that eject ink droplets of each color of yellow (Y), cyan (C), magenta (M), and black (Bk). Are arranged in a direction crossing the main scanning direction, and the ink droplet ejection direction is directed downward.

As the ink jet recording head constituting the recording head 134, a piezoelectric actuator such as a piezoelectric element, a thermal actuator using phase change due to liquid film boiling using an electrothermal transducer such as a heating resistor, a metal phase due to temperature change, etc. A shape memory alloy actuator using a change, an electrostatic actuator using an electrostatic force, or the like provided as energy generating means for discharging ink can be used.
Further, the carriage 133 is equipped with sub tanks 135 for each color for supplying each color ink to the recording head 134. The sub tank 135 is supplied with the ink from the ink cartridge 201 of the present invention loaded in the ink cartridge loading unit 104 via the ink supply tube and is replenished.

  The recording head 134 in the ink ejection apparatus of the present invention may include the inflow channel for allowing ink to flow into the individual liquid chamber, and the outflow channel for allowing ink to flow out of the individual liquid chamber. Details will be described later.

On the other hand, as a sheet feeding unit for feeding the substrate 142 loaded on the substrate loading unit (pressure plate) 141 of the sheet feeding tray 102, the substrate 142 is separated and fed one by one from the substrate loading unit 141. A half paddle (sheet feeding roller 143) and a sheet feeding roller 143 are opposed to each other, and a separation pad 144 made of a material having a large friction coefficient is provided. The separation pad 144 is urged toward the sheet feeding roller 143 side.
As a transport unit for transporting the base material 142 fed from the paper feed unit on the lower side of the recording head 134, a transport belt 151 for electrostatically attracting and transporting the base material 142, and a paper feed unit On the conveyor belt 151, the counter roller 152 for transporting the base material 142 fed through the guide 145 with the transport belt 151 being sandwiched between the counter roller 152 and the base material 142 fed substantially vertically upward is changed by about 90 °. And a leading end pressure roller 155 urged toward the conveyor belt 151 by a pressing member 154, and charging as charging means for charging the surface of the conveyor belt 151. A roller 156 is provided.

  The conveyor belt 151 is an endless belt, is stretched between a heater-type conveyor roller 157 and a tension roller 158, and can circulate in the belt conveyance direction. The transport belt 151 includes, for example, a surface layer serving as a substrate adsorption surface formed of a resin material having a thickness of about 40 μm that is not subjected to resistance control, for example, a copolymer of tetrafluoroethylene and ethylene (ETFE), and the surface layer. And a back layer (medium resistance layer, grounding layer) that is controlled by carbon with the same material. A heater-type guide member 161 is disposed on the back side of the conveyance belt 151 so as to correspond to a printing area by the recording head 134. Note that, as a paper discharge unit for discharging the base material 142 recorded by the recording head 134, a separation claw 171 for separating the base material 142 from the transport belt 151, a paper discharge roller 172, and a paper discharge roller 173, The base material 142 is dried with hot air by a fan heater, and then output to the paper discharge tray 103 below the paper discharge roller 172.

A double-sided paper feeding unit 181 is detachably mounted on the back surface of the apparatus main body 101. The double-sided paper feeding unit 181 takes in the base material 142 returned by the reverse rotation of the transport belt 151, reverses it, and feeds it again between the counter roller 152 and the transport belt 151. A manual paper feed unit 182 is provided on the upper surface of the duplex paper feed unit 181.
In the inkjet printing apparatus, the base material 142 is separated and fed one by one from the paper feeding unit, and the base material 142 fed substantially vertically upward is guided by the guide 145, and the conveyance belt 151, the counter roller 152, It is sandwiched between and conveyed. Further, the leading end is guided by the conveying guide 153 and pressed against the conveying belt 151 by the leading end pressure roller 155, and the conveying direction is changed by approximately 90 °. At this time, the conveyance belt 151 is charged by the charging roller 156, and the base material 142 is electrostatically attracted to the conveyance belt 151 and conveyed.
Therefore, by driving the recording head 134 according to the image signal while moving the carriage 133, ink droplets are ejected onto the stopped base material 142 to record one line, and the base material 142 is conveyed by a predetermined amount. After that, the next line is recorded. Upon receiving a recording end signal or a signal that the rear end of the base material 142 reaches the recording area, the recording operation is finished, and the base material 142 is discharged onto the paper discharge tray 103.

  The ink discharge head in the ink discharge apparatus of the present invention may be one having the following characteristics. An example will be described with reference to FIGS. 3, 4, 5, 6, 7A to 7F, 8A, and 8B. FIG. 3 is an external perspective view showing an example of an ink discharge head in the ink discharge apparatus of the present invention. FIG. 4 is a cross-sectional explanatory diagram in a direction orthogonal to the nozzle arrangement direction of the ink discharge head of FIG. FIG. 5 is a partial cross-sectional explanatory diagram in a direction parallel to the nozzle arrangement direction of the ink discharge head of FIG. FIG. 6 is an explanatory plan view of the nozzle plate of the ink discharge head of FIG. 7A to 7F are explanatory plan views of members constituting the flow path member of the ink discharge head of FIG. 8A and 8B are plan explanatory views of each member constituting the common liquid chamber member of the ink discharge head of FIG.

  In the ink discharge head, a nozzle plate 1, a flow path plate 2, and a vibration plate member 3 as a wall surface member are laminated and joined, and a piezoelectric actuator 11 that displaces the vibration plate member 3 and a common liquid chamber member 20. And a cover 29.

The nozzle plate 1 has a plurality of nozzles 4 that eject the ink.
The flow path plate 2 is formed with an individual liquid chamber 6 that communicates with the nozzle 4, a fluid resistance portion 7 that communicates with the individual liquid chamber 6 as the inflow channel, and a liquid introduction portion 8 that communicates with the fluid resistance portion 7. The flow path plate 2 is formed by laminating and joining a plurality of plate-like members 41 to 45 from the nozzle plate 1 side, and laminating and joining these plate-like members 41 to 45 and the vibration plate member 3. A member 40 is configured.
The diaphragm member 3 has a filter part 9 as an opening through the liquid introduction part 8 and the common liquid chamber 10 formed by the common liquid chamber member 20.
The diaphragm member 3 is a wall surface member that forms the wall surface of the individual liquid chamber 6 of the flow path plate 2. The diaphragm member 3 has a two-layer structure (not limited), and is formed of a first layer that forms a thin portion and a second layer that forms a thick portion from the flow path plate 2 side. A deformable vibration region 30 is formed in a portion corresponding to the chamber 6.

Here, as shown in FIG. 6, a plurality of nozzles 4 are arranged in a staggered pattern on the nozzle plate 1.
As shown in FIG. 7A, the plate-like member 41 constituting the flow path plate 2 includes a through groove portion (meaning a groove-like through hole) 6a constituting the individual liquid chamber 6, a fluid resistance portion 51, and the outflow flow. Through-groove portions 51a and 52a constituting a circulation flow path 52 as a path are formed.
Similarly, as shown in FIG. 7B, the plate-like member 42 is formed with a through groove portion 6 b that constitutes the individual liquid chamber 6 and a through groove portion 52 b that constitutes the circulation channel 52.
Similarly, as shown in FIG. 7C, the plate-like member 43 is formed with a through groove portion 6 c constituting the individual liquid chamber 6 and a through groove portion 53 a having the nozzle arrangement direction constituting the circulation channel 53 as a longitudinal direction. .
Similarly, as shown in FIG. 7D, the plate-like member 44 includes a through groove portion 6 d constituting the individual liquid chamber 6, a through groove portion 7 a constituting the fluid resistance portion 7, a through groove portion 8 a constituting the liquid introduction portion 8, A through groove portion 53 b is formed with the nozzle arrangement direction constituting the flow channel 53 as a longitudinal direction.
Similarly, as shown in FIG. 7E, the plate-like member 45 includes a through groove portion 6e constituting the individual liquid chamber 6, and a through groove portion 8b having a nozzle arrangement direction constituting the liquid introduction portion 8 as a longitudinal direction (filter downstream side liquid And a through-groove portion 53c having a nozzle arrangement direction constituting the circulation flow path 53 as a longitudinal direction is formed.
As shown in FIG. 7F, the diaphragm member 3 is formed with a vibration region 30, a filter portion 9, and a through groove portion 53 d whose longitudinal direction is the nozzle arrangement direction constituting the circulation channel 53.
Thus, a complicated flow path can be formed with a simple configuration by configuring the flow path member by laminating and joining a plurality of plate-like members.

  With the above configuration, the flow path member 40 including the flow path plate 2 and the vibration plate member 3 includes the fluid resistance portion 51, the circulation flow path 52, and the circulation along the surface direction of the flow path plate 2 leading to each individual liquid chamber 6. A circulation channel 53 in the thickness direction of the channel member 40 that communicates with the channel 52 is formed. The circulation channel 53 communicates with a circulation common liquid chamber 50 described later.

On the other hand, the common liquid chamber member 20 is formed with a common liquid chamber 10 and a circulating common liquid chamber 50 to which the ink is supplied from the main tank and the ink cartridge.
As shown in FIG. 8A, the first common liquid chamber member 21 has a piezoelectric actuator through hole 25 a, a through groove portion 10 a serving as the downstream common liquid chamber 10 A, and a groove portion 50 a having a bottom serving as the circulating common liquid chamber 50. Is formed.
As shown in FIG. 8B, the second common liquid chamber member 22 is formed with a piezoelectric actuator through hole 25b and a groove portion 10b that becomes the upstream common liquid chamber 10B. Further, as shown in FIG. 3, the second common liquid chamber member 22 is formed with a through hole 71 a serving as a supply port portion through one end portion of the common liquid chamber 10 in the nozzle arrangement direction and the supply port 71.
The first common liquid chamber member 21 and the second common liquid chamber member 22 have a through hole through the other end of the circulating common liquid chamber 50 in the nozzle arrangement direction (the end opposite to the through hole 71a) and the circulation port 81. 81a and 81b are formed.
In FIG. 8A and FIG. 8B, the groove portion having the bottom is shown with surface coating (the same applies to the following drawings).
As described above, the common liquid chamber member 20 is constituted by the first common liquid chamber member 21 and the second common liquid chamber member 22, and the first common liquid chamber member 21 is joined to the diaphragm member 3 side of the flow path member 40. Then, the second common liquid chamber member 22 is laminated and joined to the first common liquid chamber member 21.

Here, the first common liquid chamber member 21 forms a downstream common liquid chamber 10 </ b> A that is a part of the common liquid chamber 10 that communicates with the liquid introduction unit 8, and a circulation common liquid chamber 50 that communicates with the circulation channel 53. ing. The second common liquid chamber member 22 forms an upstream common liquid chamber 10 </ b> B that is the remaining part of the common liquid chamber 10.
At this time, the downstream common liquid chamber 10A, which is a part of the common liquid chamber 10, and the circulating common liquid chamber 50 are arranged side by side in a direction orthogonal to the nozzle arrangement direction, and the circulating common liquid chamber 50 is arranged in the common liquid chamber 10. It is arranged at the position projected inside.
Thereby, the dimension (size) of the circulation common liquid chamber 50 is restricted by the dimensions required for the flow path including the individual liquid chamber 6, the fluid resistance section 7, and the liquid introduction section 8 formed by the flow path member 40. Disappears.
The circulation common liquid chamber 50 and a part of the common liquid chamber 10 are arranged side by side, and the circulation common liquid chamber 50 is arranged at a position projected into the common liquid chamber 10, thereby orthogonal to the nozzle arrangement direction. The width of the head in the direction can be suppressed, and the enlargement of the head can be suppressed. The common liquid chamber member 20 forms a circulation common liquid chamber 50 and a common liquid chamber 10 to which the ink is supplied from a head tank or the ink cartridge.

On the other hand, on the opposite side of the diaphragm member 3 from the individual liquid chamber 6, a piezoelectric actuator 11 including an electromechanical conversion element as a driving means (actuator means, pressure generating means) for deforming the vibration region 30 of the diaphragm member 3 is provided. It is arranged.
As shown in FIG. 5, the piezoelectric actuator 11 has a piezoelectric member 12 bonded on a base member 13, and the piezoelectric member 12 is grooved by half-cut dicing so that a required number of piezoelectric members 12 is provided. The columnar piezoelectric elements 12A and 12B are formed in a comb shape at a predetermined interval.
Here, the piezoelectric element 12A of the piezoelectric member 12 is a piezoelectric element that is driven by giving a drive waveform, and the piezoelectric element 12B is used as a mere support without giving a drive waveform. However, all the piezoelectric elements 12A and 12B are driven. It can also be used as a piezoelectric element.
The piezoelectric element 12 </ b> A is joined to a convex portion 30 a that is an island-shaped thick portion formed in the vibration region 30 of the diaphragm member 3. Further, the piezoelectric element 12 </ b> B is joined to the convex portion 30 b which is a thick portion of the diaphragm member 3.

The piezoelectric member 12 is formed by alternately laminating piezoelectric layers and internal electrodes. The internal electrodes are drawn out to end faces, external electrodes are provided, and the flexible wiring member 15 is connected to the external electrodes.
In the ink discharge head configured as described above, for example, the voltage applied to the piezoelectric element 12A is lowered from the reference potential, the piezoelectric element 12A contracts, the vibration region 30 of the diaphragm member 3 descends, and the individual liquid chamber 6 As the volume expands, the ink flows into the individual liquid chamber 6.
Thereafter, the voltage applied to the piezoelectric element 12A is increased to extend the piezoelectric element 12A in the stacking direction, and the vibration region 30 of the diaphragm member 3 is deformed in the direction toward the nozzle 4 to contract the volume of the individual liquid chamber 6. As a result, the ink in the individual liquid chamber 6 is pressurized, and the ink is ejected from the nozzle 4.
Then, by returning the voltage applied to the piezoelectric element 12A to the reference potential, the vibration region 30 of the diaphragm member 3 is restored to the initial position, and the individual liquid chamber 6 expands to generate a negative pressure. The ink is filled into the individual liquid chamber 6 from the chamber 10. Therefore, after the vibration of the meniscus surface of the nozzle 4 is attenuated and stabilized, the operation for the next discharge is started.
Note that the driving method of the head is not limited to the above example (drawing-pushing), and striking or pushing can be performed depending on the direction of the drive waveform. In the above-described embodiment, the multilayer piezoelectric element has been described as means for applying pressure fluctuation to the individual liquid chamber 6, but the present invention is not limited to this, and a thin film piezoelectric element can also be used. Furthermore, a heating resistor can be provided in the individual liquid chamber 6 to generate a bubble by generating heat by generating heat from the heating resistor, or to generate a pressure variation using electrostatic force. .

  Next, an example of the ink circulation system using the ink discharge head according to the present embodiment will be described with reference to FIG.

FIG. 9 is a block diagram showing an example of an ink circulation system according to the present invention.
As shown in FIG. 9, the ink circulation system includes a main tank, an ink discharge head, a supply tank, a circulation tank, a compressor, a vacuum pump, a liquid feed pump, a regulator (R), a supply side pressure sensor, a circulation side pressure sensor, and the like. It consists of The supply side pressure sensor is connected between the supply tank and the ink discharge head and on the supply flow path side connected to the supply port 71 (see FIG. 3) of the ink discharge head. The circulation-side pressure sensor is connected between the ink discharge head and the circulation tank and on the circulation flow path side connected to the circulation port 81 (see FIG. 3) of the ink discharge head.
One of the circulation tanks is connected to the supply tank via the first liquid feed pump, and the other of the circulation tanks is connected to the main tank via the second liquid feed pump. As a result, the ink flows from the supply tank into the ink discharge head through the supply port 71, is discharged from the circulation port, is discharged to the circulation tank, and is further discharged from the circulation tank to the supply tank by the first liquid feed pump. Is sent, the ink circulates.
Further, a compressor (not shown) is connected to the supply tank, and the supply side pressure sensor is controlled to detect a predetermined positive pressure. On the other hand, a vacuum pump (not shown) is connected to the circulation tank, and is controlled so that a predetermined negative pressure is detected by the circulation side pressure sensor. Thereby, the negative pressure of the meniscus can be kept constant while circulating the ink through the ink discharge head.
In addition, when ink droplets are ejected from the nozzles of the ink ejection head, the amount of ink in the supply tank and the circulation tank decreases, so the second tank is appropriately used from the main tank to the circulation tank. It is desirable to replenish the ink. The timing of ink replenishment from the main tank to the circulation tank is detected by a liquid level sensor provided in the circulation tank, such as when the ink level in the circulation tank drops below a predetermined level. It can be controlled by the result.

Next, the circulation of the ink in the ink discharge head will be described. As shown in FIG. 3, a supply port 71 that communicates with the common liquid chamber and a circulation port 81 that communicates with the circulation common liquid chamber 50 are formed at the end of the common liquid chamber member 20. The supply port 71 and the circulation port 81 are connected to a supply tank and a circulation tank (see FIGS. 10 and 11) for storing the ink via tubes, respectively. Then, the ink stored in the supply tank is supplied to the individual liquid chamber 6 through the supply port 71, the common liquid chamber 10, the liquid introduction portion 8, and the fluid resistance portion 7.
Further, while the ink in the individual liquid chamber 6 is ejected from the nozzle 4 by driving the piezoelectric element 12, a part or all of the ink remaining in the individual liquid chamber 6 without being ejected is a fluid resistance portion 51. The liquid is circulated to the circulation tank through the circulation channels 52 and 53, the circulation common liquid chamber 50, and the circulation port 81.
The ink circulation can be performed not only when the ink discharge head is operating, but also when the operation is stopped. Circulation during operation stop is preferable because the ink in the individual liquid chamber is always refreshed and aggregation and sedimentation of components contained in the ink can be suppressed.

<Discharge control>
In such an ink ejection head, for example, as shown in FIG. 12, the piezoelectric member 112 is contracted by lowering the voltage applied to the piezoelectric member 112 from the reference potential Ve, and the diaphragm member 102 is deformed to deform the individual liquid. The volume of the chamber 105 expands. As a result, ink flows into the individual liquid chamber 105.

  Thereafter, as shown in FIG. 13, the voltage applied to the piezoelectric member 112 is increased to extend the piezoelectric member 112 in the stacking direction, and the diaphragm member 102 is deformed in the nozzle 104 direction to contract the volume of the individual liquid chamber 105. . As a result, the ink in the individual liquid chamber 105 is pressurized, and the droplet 301 is ejected from the nozzle 104.

  Then, by returning the voltage applied to the piezoelectric member 112 to the reference potential Ve, the diaphragm member 102 is restored to the initial position, and the individual liquid chamber 105 expands to generate a negative pressure. Ink is then filled into the individual liquid chamber 105. Therefore, after the vibration of the meniscus surface of the nozzle 104 is attenuated and stabilized, the operation proceeds to the next droplet discharge.

<Ink supply operation>
Next, an outline of the ink supply unit in the ink ejection apparatus of the present invention will be described with reference to FIGS. 14A and 14B. 14A is an explanatory diagram illustrating an example of an ink ejection head and an ink supply unit in the ink ejection apparatus of the present invention, and FIG. 14B is an enlarged explanatory diagram of the ink ejection head illustrated in FIG. 14A.

The ink discharge device supplies ink to the ink discharge device through an ink cartridge 901 containing ink 902. The ink 902 of the ink cartridge 901 is supplied by operating the liquid feed pump 906 to the ink tank 910 via the ink supply tube 905. The ink tank 910 is provided with an air release valve 912 for removing air from the ink tank above the liquid level.
In this configuration, the ink 911 can be sent from the ink tank 910 to the filter unit 914 via the head supply tube 913. The filter unit 914 is provided with a filter 919 that traps coarse components in the ink so as not to flow into the head 915. The supplied ink is supplied from the filter unit 914 to the head 915, and the ink that has not been used for printing is discharged to the head circulation tube 916 through the filter-free path of the filter unit 914. The head circulation tube 916 is provided with a circulation valve 918 and a head circulation pump 917, and the ink in the head 915 can be circulated to the ink tank 911 by driving the head circulation pump 917.

The ink supply operation is performed as follows as the initial filling operation.
First, the liquid supply pump 906 is operated with the air release valve 912 opened to supply the ink 902 from the ink cartridge 901 to the ink tank 910, and the supply operation is continued until it is detected by the full tank detection sensor 920. When the full tank detection sensor 920 detects that the tank is full, the liquid feed pump 906 stops and the atmosphere release valve 912 is closed.
Thereafter, the circulation valve 918 is opened and the head circulation pump 917 is driven, so that the head 915 is filled with ink from the filter unit 914 and the head circulation tube 916 is filled with ink.
Further, by performing the fine driving operation when the head circulation pump 917 is driven, wetting of the ink flowing into the individual liquid chamber is promoted, and bubbles adhering to the wall surface of the individual liquid chamber can be moved. it can. For this reason, wetting and bubble discharge can be promoted by the movement of the circulating ink, and the ink filling properties of the ink discharge head can be improved.
Thereafter, the amount of ink necessary for generating negative pressure is sucked from the nozzle surface of the head 915, and the printing environment can be adjusted by wiping the nozzle surface.
When the apparatus is activated, the circulation valve 918 is opened and the head circulation pump 917 is driven to circulate ink. By circulating the ink in the head even when ink is ejected,
A separation state such as aggregation or sedimentation of components contained in the ink in the head or the filter unit can be suppressed. Further, when the ink in the individual liquid chambers in the head flows against the drying from the nozzle, local drying can be suppressed and nozzle omission can be suppressed.
In addition, a step of circulating the ink may be provided before the ink is ejected after the apparatus is in a resting state.
When the ink is circulated, a step of stimulating the ink with a strength that does not cause the ink to be ejected may be provided.

When cleaning the ink path, the cleaning liquid is set in the ink cartridge 901 in place of the ink, and the ink path of the apparatus is easily diluted by the circulation described above, and ink replacement can be easily performed.

<Recorded material>
The recorded matter has an image recorded with the ink on a print medium.

<Recording medium>
The recording medium is not particularly limited, and plain paper, glossy paper, special paper, cloth, and the like can be used. Good image formation is possible even with a non-permeable substrate.
The non-permeable base material is a base material having a surface with low water permeability and absorbability, and includes materials that do not open to the outside even if there are many cavities inside, more quantitatively. In the Bristow method, the water absorption amount from the start of contact to 30 msec ^1/2 is 10 mL / m ² or less.
As said non-permeable base material, plastic films, such as a vinyl chloride resin film, a polyethylene terephthalate (PET) film, a polypropylene, polyethylene, a polycarbonate film, can be used conveniently, for example.
The recording medium is not limited to those used as general recording media, and wallpaper, flooring, building materials such as tiles, cloth for clothing such as T-shirts, textiles, leather, and the like can be used as appropriate. Moreover, ceramics, glass, metal, etc. can also be used by adjusting the structure of the path | route which conveys a recording medium.

   Further, the terms “image formation”, “recording”, “printing”, “printing”, etc. in the terms of the present invention are all synonymous.

In addition, even when the printing medium is colored by applying white ink before the color ink during color recording (colored printing medium), the color of the printing medium can be made white. The color development can be improved.
Representative examples of the colored printing medium include colored paper, the film, fabric, clothes, ceramics, and the like.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these Examples. In the examples, “part” is “part by mass” and “%”.
Is “% by mass” except for those in the evaluation criteria.

<Preparation of resin particles>
Preparation examples of the resin particles are described below.
The following commercially available products were used as the polyvinyl chloride resin particles and the polyester resin particles.
-Polyvinyl chloride resin emulsion (made by Wacker Chemie AG, trade name: VINNOL E15 / 48A, solid content: 50%)
-Polyvinyl chloride-ethylene copolymer (manufactured by Sumika Chemtex Co., Ltd., trade name: Sumilite 1210, solid content concentration: 50 ± 1% by mass)
-Vinyl chloride-acrylic copolymer (manufactured by Nissin Chemical Industry Co., Ltd., trade name: VINYBRAN 711, solid content concentration: 50% by mass)
Polyester emulsion (trade name: Pesresin A-124GP, solid content concentration: 30% by mass, manufactured by Takamatsu Yushi Co., Ltd.)

<< Preparation of polycarbonate urethane resin emulsion >>
Into a reaction vessel into which a stirrer, a reflux condenser and a thermometer were inserted, 1,500 g of polycarbonate diol (reaction product of 1,6-hexanediol and dimethyl carbonate (number average molecular weight (Mn): 1200)), 2,2-di Methylolpropionic acid (hereinafter sometimes referred to as “DMPA”) (220 g) and N-methylpyrrolidone (hereinafter also referred to as “NMP”) (1,347 g) were charged in a nitrogen stream and heated to 60 ° C. DMPA was dissolved.
Next, 1,445 g of 4,4′-dicyclohexylmethane diisocyanate and 2.6 g of dibutyltin dilaurate (catalyst) were added and heated to 90 ° C. to carry out a urethanization reaction for 5 hours to obtain an isocyanate-terminated urethane prepolymer. It was. The reaction mixture was cooled to 80 ° C., 4,340 g was extracted from the mixture in which 149 g of triethylamine was added and mixed, and added to a mixed solution of 5,400 g of water and 15 g of triethylamine with vigorous stirring. Next, 1,500 g of ice was added, 626 g of 35% 2-methyl-1,5-pentanediamine aqueous solution was added to carry out a chain extension reaction, and the solvent was distilled off so that the solid concentration was 30%. A polycarbonate urethane resin emulsion was obtained.
Using the polycarbonate urethane resin emulsion, the minimum film-forming temperature measured with a “film-forming temperature test apparatus” (manufactured by Imoto Seisakusho Co., Ltd.) was 55 ° C.

<< Preparation of polyether urethane resin emulsion >>
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 100.2 parts of polyether polyol ("PTMG1000" manufactured by Mitsubishi Chemical Corporation, average molecular weight: 1,000), 2,2- 15.7 parts of dimethylolpropionic acid, 48.0 parts of isophorone diisocyanate, 77.1 parts of methyl ethyl ketone as the organic solvent, and 0.06 part of dibutyltin diureate (hereinafter sometimes referred to as “DMTDL”) as the catalyst And reacted.
After the reaction was continued for 4 hours, 30.7 parts of methyl ethyl ketone was supplied as a diluent solvent, and the reaction was further continued.
When the average molecular weight of the reactant reached a range of 20,000 to 60,000, 1.4 parts of methanol was added to complete the reaction, thereby obtaining an organic solvent solution of urethane resin.
13.4 parts of 48% potassium hydroxide aqueous solution is added to the organic solvent solution of the urethane resin to neutralize the carboxyl group of the urethane resin, and then 715.3 parts of water is added and stirred sufficiently, followed by aging. By removing the solvent, a polyether urethane resin emulsion having a solid content of 30% by mass was obtained.
For the polyether-based urethane resin emulsion, the minimum film-forming temperature measured with a “film-forming temperature test apparatus” (manufactured by Imoto Seisakusho Co., Ltd.) in the same manner as in Preparation Example 1 for the polycarbonate-based urethane resin emulsion was 43 ° C. .

<< Preparation of polyester urethane resin emulsion >>
Except for changing the polyether polyol ("PTMG1000" manufactured by Mitsubishi Chemical Corporation, average molecular weight: 1,000) to a polyester polyol ("Polylite OD-X-2251" manufactured by DIC Corporation, average molecular weight: 2,000). A polyester urethane resin emulsion having a solid content of 30% by mass was obtained in the same manner as in Preparation Example 2 of the polyether urethane resin emulsion.
About the said polyester-type urethane resin emulsion, the minimum film-forming temperature measured with the "film-forming temperature test apparatus" (made by Imoto Seisakusho Co., Ltd.) similarly to preparation of the said polycarbonate-type urethane resin emulsion was 74 degreeC.

<< Preparation of acrylic resin emulsion >>
A reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer was charged with 900 g of ion-exchanged water and 1 g of sodium lauryl sulfate, and the temperature was raised to 70 ° C. while purging with nitrogen under stirring. Maintaining the internal temperature at 70 ° C., adding 4 g of potassium persulfate as a polymerization initiator, dissolving, and previously stirring 450 g of ion exchange water, 3 g of sodium lauryl sulfate, 20 g of acrylamide, 615 g of styrene, 30 g of butyl acrylate, and 350 g of methacrylic acid The emulsion prepared in addition to the chemical conversion was continuously dropped into the reaction solution over 4 hours. After completion of the dropwise addition, the mixture was reacted for 3 hours to obtain an aqueous emulsion.
The obtained aqueous emulsion was cooled to room temperature, and then ion exchange water and an aqueous sodium hydroxide solution were added to obtain an acrylic resin emulsion having a solid content of 30% by mass and a pH of 8.
About the said acrylic resin emulsion, it carried out similarly to the preparation example 1 of the said polycarbonate-type urethane resin emulsion, and the minimum film-forming temperature measured with the "film-forming temperature test apparatus" (made by Imoto Seisakusho Co., Ltd.) was 53 degreeC.

<Preparation of pigment dispersion>
<< Preparation of Black Pigment Dispersion >>
The following prescription mixture was premixed and then circulated and dispersed for 7 hours in a disk type bead mill (Shinmaru Enterprises KDL type, media: 0.3 mm diameter zirconia ball used) to obtain a black pigment dispersion.
Carbon black pigment (trade name: Monarch 800, manufactured by Cabot) · 15 parts Anionic surfactant (Pionin A-51-B, manufactured by Takemoto Yushi Co., Ltd.) ··· 2 parts Ion-exchanged water ···・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 83 parts

<< Preparation of Cyan Pigment Dispersion >>
Except for changing the carbon black pigment to Pigment Blue 15: 3 (trade name: LIONOL BLUE FG-7351, manufactured by Toyo Ink Co., Ltd.), a cyan pigment dispersion was prepared in the same manner as in Preparation Example 1 of the black pigment dispersion. Obtained.

<< Preparation of magenta pigment dispersion >>
A magenta pigment dispersion was obtained in the same manner as in Preparation Example 1 of a black pigment dispersion, except that the carbon black pigment was changed to Pigment Red 122 (trade name: Toner Magenta EO02, manufactured by Clariant Japan Co., Ltd.).

<< Preparation of Yellow Pigment Dispersion >>
A yellow pigment dispersion was obtained in the same manner as in Preparation Example 1 of the black pigment dispersion, except that the carbon black pigment was changed to Pigment Yellow 74 (trade name: First Yellow 531, manufactured by Dainichi Seika Kogyo Co., Ltd.). .

<< Preparation of white pigment dispersion >>
Titanium oxide (trade name: STR-100W, manufactured by Sakai Chemical Industry Co., Ltd.) 25 parts, pigment dispersant (trade name: TEGO Dispers 651, manufactured by Evonik Co., Ltd.) 5 parts, and water 70 parts are mixed, and a bead mill (trade name: Research). (Lab, manufactured by Shinmaru Enterprises Co., Ltd.) 0.3 mmφ zirconia beads were dispersed for 5 minutes at a filling rate of 60% and 8 m / s to obtain a white pigment dispersion.

Example 1
<Preparation of black ink 1>
Black pigment dispersion 20%, polycarbonate urethane resin emulsion (solid content concentration 30%) 10% in terms of resin solid content, polyether urethane resin emulsion (solid content concentration 30%) 1% in terms of solid content 1 , 2-propanediol 12%, 1,2-butanediol 5%, 3-methoxy-N, N-dimethylpropionamide (trade name: Ecamide M-100, manufactured by Idemitsu Kosan Co., Ltd.) 20%, product as a preservative Name: Proxel LV (manufactured by Avicia Co., Ltd.) 0.1%, surfactant (trade name: Softanol EP-5035, manufactured by Nippon Shokubai Co., Ltd.) 0.01%, and high purity water 6.2% are mixed and stirred. Ink 1 was prepared by filtration through a 2 μm polypropylene filter.

(Examples 2 to 15 and Comparative Examples 1 to 6)
Inks 2 to 21 were produced in the same manner as in Example 1 except that Examples 2 to 15 and Comparative Examples 1 to 6 were changed to the ink compositions and contents shown in Tables 1 to 3. Tables 1 to 3 show the compositions and contents of the inks of Examples 1 to 15 and Comparative Examples 1 to 6.

In Tables 1 to 3, the following commercially available products were used as the organic solvent.
・ 3-Butoxy-N, N-dimethylpropionamide (manufactured by Idemitsu Kosan Co., Ltd., trade name: Ecamide B-100)
・ 3-Methyl-3-oxetanemethanol (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: 3-methyl-3-oxetanemethanol)
-3-ethyl-3-oxetanemethanol (manufactured by Tokyo Chemical Industry Co., Ltd., trade name: 3-ethyl-3-oxetanemethanol)

The obtained inks 1 to 21 of Examples 1 to 15 and Comparative Examples 1 to 6 were filled in a remodeling machine of an ink jet printer (trade name: IPSiO GXe5500, manufactured by Ricoh Co., Ltd.), and a polyvinyl chloride film (hereinafter referred to as “PVC film”). The solid image was printed on the substrate and dried at 80 ° C. for 1 hour. The produced images were evaluated for “high gloss”, “ink supply stability” and “ejection reliability” as follows. The results are shown in Table 54.
The modified GXe5500 is a modified GXe5500 so that the substrate can be heated during recording.
Further, this is a modification to an ink discharge apparatus having an ink discharge head having a circulation mechanism.

(Example 16)
The obtained ink 15 of Example 15 was applied to a PET film heated to 50 ° C. on a hot plate with a bar coater (manufactured by Matsuo Sangyo Co., Ltd., No. 5), and dried as it was for 5 minutes. A magenta solid image was formed on the white solid image using an inkjet printer (IPSiO GXe5500 remodeled machine, manufactured by Ricoh Co., Ltd.) remodeled with the ink 3 described above. The recorded matter was then dried at 80 ° C. for 1 hour. The produced images were evaluated for “high gloss”, “ink supply stability” and “ejection reliability” by an evaluation method described later. The results are shown in Table 4.

(Example 17)
In Example 17, the ink 3 of Example 3 was used and dried at 25 ° C. overnight. “High glossiness” was evaluated on the produced images as follows.

<High glossiness>
The 60 ° glossiness of the solid portion of the image produced on the substrate was measured four times with a gloss meter (trade name: 4501, manufactured by BYK Gardener), the average value was obtained, and “high gloss” "Sex" was evaluated.
It is desirable in practical use that the evaluation is B or more.
-Evaluation criteria-
A: Gloss value was 100 or more A: Gloss value was 90 or more and less than 100 B: Gloss value was 80 or more and less than 90 C: Gloss value was less than 80

<Ink supply stability>
Ink jet printer (device name: IPSiO GXe5500 remodeled machine, manufactured by Ricoh Co., Ltd.) is filled with ink 1 to 15 in a printer equipped with circulation means shown in FIGS. 14A and 14B, and continuously for 24 hours while circulating the ink. After the circulation operation, the ink supply amount per unit time was measured, and it was evaluated how much the ink supply was decreasing compared with the initial flow rate. It is desirable in practical use that the evaluation is B or more. The results are shown in Table 4.
-Evaluation criteria-
A: Flow rate change is less than 1% A: Flow rate drop is 1% or more and less than 5% B: Flow rate drop is 5% or more and less than 10% C: Flow rate drop is 10% or more and less than 20% D: Flow rate drop is 20% or more

<Discharge reliability>
Ink jet printer (device name: IPSiO GXe5500 modified machine, manufactured by Ricoh Co., Ltd.) is filled with ink 1-21 in a printer equipped with circulation means shown in FIGS. 14A and 14B, and the circulation is stopped for 30 minutes. After leaving, a step of stimulating the ink with a strength that does not discharge the ink while circulating the ink is provided, and then a nozzle check pattern is printed on the PVC film while circulating the ink, so that the total number of nozzles is 384. The number of ejection nozzles from which ink was ejected was confirmed and evaluated according to the following criteria. It is desirable in practical use that the evaluation is B or more.
The evaluation results are shown in Table 4.
-Evaluation criteria-
A: The number of discharge nozzles is 384
B: The number of discharge nozzles is 368 or more and less than 384 C: The number of discharge nozzles is 192 or more and less than 368 D: The number of discharge nozzles is less than 192

Examples 1 and 2 are examples in which the polyurethane resin particles and the polyvinyl chloride resin are not used at the same time, and the ink supply stability is inferior to the combination of the polyurethane resin and the polyvinyl chloride resin in Example 3.
Examples 3 and 4 and Example 8 are particularly preferred examples of the present invention, and are ink ejection devices that can obtain highly glossy images and are excellent in ink supply stability and ejection reliability. I understand.
Examples 5 to 7 and Examples 12 to 14 select the most preferable 3-methoxy-N, N-dimethylpropionamide from the compounds represented by the general formula (1) or the general formula (2). In this example, the high gloss was slightly inferior to that of Example 3.
Example 9 is an example in which the amount of the compound represented by the general formula (1) is slightly less, and is slightly inferior in the miscibility of the two types of resin particles used. Was inferior.
Example 10 is an example in which the amount of the compound represented by the general formula (1) is slightly less, and is slightly inferior in the miscibility of the two types of resin particles used. Was inferior.
Example 5 is an example in which no polyurethane resin particles are used, and the high glossiness and ejection reliability are inferior to the combination of the polyurethane resin and polyvinyl chloride resin of Example 2.
Examples 9 to 11 are examples in which polyurethane resin particles are used for the resin particles having the highest content, and polyester resins are used for resin particles other than the resin particles having the highest content. One of high gloss, ink supply stability, and ejection reliability is inferior to the combination with vinyl resin.
Examples 12 to 14 are examples in which a polyurethane resin is used for the resin particles having the highest content, and an acrylic resin is used for the resin particles other than the resin particles having the highest content. The polyurethane resin and polyvinyl chloride of Example 3 are used. One of high glossiness, ink supply stability, and ejection reliability is inferior to the combination with resin.
Example 16 was an example in which an image was recorded on white ink, and was excellent in gloss as in Example 3.
Example 17 does not include a heating step after recording, but gloss equivalent to that of Example 3 is obtained.

Comparative Example 1 is an example that does not include the compound represented by the general formula (1) and the compound represented by the general formula (2). Compared to Example 3, the ink supply stability, ejection reliability, and gloss are higher. Inferior.
Comparative Examples 2 to 5 are examples in which only one kind of resin particles is used, and the ejection reliability is particularly inferior to that of Example 3.
Comparative Example 6 is an example in which an ink ejection jet having a circulation mechanism was not introduced into the ejection device, and in particular, ejection reliability was inferior to that of Example 3.

The solvent-based inkjet ink is fixed with the recording substrate being swollen by the solvent in the ink, and thus has excellent adhesion to the substrate. However, the water-based ink has a final recording material that has an ink coating on the recording substrate. Therefore, there is a problem that the substrate adhesion of the ink film is insufficient.
In addition, the non-permeable base material is often very glossy, and when recording, if the recording part is not glossy with no sense of incongruity with respect to the non-recording part, the sense of unity as a recorded matter is impaired, Ink with high glossiness is required, but solvent-based ink-jet inks have a resin that is dissolved in the system, resulting in a smooth film after drying, resulting in high glossiness. Since the ink film is formed by fusing, the glossiness tends to be lower than that of the solvent-based inkjet ink. Furthermore, since a large amount of resin is used, the resin tends to agglomerate when circulating in the discharge device or in the vicinity of the nozzle, and it is necessary to improve ink supply stability and discharge reliability.

  From the evaluation results, it can be seen that the ink of the present invention is suitable for outdoor use. In addition, the inks of Examples 1 to 15 had high glossiness that is comparable to that of the solvent-based inkjet ink. In addition, ink supply stability and ejection reliability were ensured.

（ただし、前記一般式（１）中、Ｒ^１、Ｒ^２、及びＲ^３は、それぞれ、炭素数１以上５以下のアルキル基を示し、Ｒ^１、Ｒ^２、及びＲ^３は同一であっても、異なっていてもよい）

（ただし、前記一般式（２）中、Ｒ^４は、メチル基及びエチル基のいずれかを示し、Ｒ^５は、水素原子、炭素数１以上８以下のアルキル基、シクロアルキル基、及びアリール基のいずれかを示す）
＜２＞ 一般式（１）で表される化合物及び下記一般式（２）で表される化合物のインク中の総含有量Ｓ（質量％）と、前記樹脂粒子のインク中の総固形分濃度Ａ（質量％）との質量比（Ｓ／Ａ）が、１．０以上４．０以下である上記＜１＞に記載のインク。
＜３＞ 前記一般式（１）で表される化合物が、３−メトキシ−Ｎ，Ｎ−ジメチルプロピオンアミドである上記＜１＞又は＜２＞に記載のインク。
＜４＞ 前記二種の樹脂粒子のうちの少なくとも一種が、ポリウレタン樹脂粒子である上記＜１＞〜＜３＞のいずれか１項に記載のインク。
＜５＞ 前記二種の樹脂粒子が、ポリウレタン樹脂粒子及びポリ塩化ビニル樹脂粒子である上記＜１＞〜＜４＞のいずれか１項に記載のインク。
＜６＞ 個別液室と、該個別液室にインクを流入させるための流入流路と、インクを前記個別液室から流出させるための流出流路とを有する、インクを吐出するインク吐出ヘッドと、上記＜１＞〜＜５＞のいずれか１項に記載されたインクと、を有するインクジェット印刷装置。
＜７＞ 前記インクを前記流入流路から前記流出流路に向かって循環させる循環手段を有する上記＜６＞に記載のインクジェット印刷装置。
＜８＞ インク吐出ヘッドとして、インクを個別液室に流入させるための流入流路と、インクを前記個別液室から流出させるための流出流路と、を有するインク吐出ヘッドを用い、熱エネルギー及び力学的エネルギーのいずれかをインクに作用させてインクを吐出して印刷する印刷工程を有し、インクとして、水と、下記一般式（１）で表される化合物及び／又は下記一般式（２）で表される化合物と、少なくとも二種の樹脂粒子と、を含有するインクを用いることを特徴とするインクジェット印刷方法。

（ただし、前記一般式（１）中、Ｒ^１、Ｒ^２、及びＲ^３は、それぞれ、炭素数１以上５以下のアルキル基を示し、Ｒ^１、Ｒ^２、及びＲ^３は同一であっても、異なっていてもよい）

（ただし、前記一般式（２）中、Ｒ^４は、メチル基及びエチル基のいずれかを示し、Ｒ^５は、水素原子、炭素数１以上８以下のアルキル基、シクロアルキル基、及びアリール基のいずれかを示す）
＜９＞ 印刷工程が、インクを循環させながらインクを吐出して印刷する印刷工程である上記＜８＞に記載のインクジェット印刷方法。
＜１０＞ インクの循環を休止する工程と、インクを吐出する前に、前記インクを循環させる工程とを有する上記＜９＞に記載のインクジェット印刷方法。
＜１１＞ 前記インクを循環させる際に、前記インクを吐出させない強さで前記インクに圧力を与える工程を有することを特徴とする上記＜９＞又は＜１０＞に記載のインクジェット印刷方法。
＜１２＞ 印刷後に印刷物を加熱する加熱工程を有する上記＜８＞から＜１１＞のいずれか１項に記載のインクジェット印刷方法。 As an aspect of this invention, it is as follows, for example.
<1> An ink discharge head that discharges ink having an individual liquid chamber, an inflow channel for allowing ink to flow into the individual liquid chamber, and an outflow channel for allowing ink to flow out from the individual liquid chamber. In the ink used for the ink discharge device provided,
An ink in which the ink contains water, a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2), and at least two kinds of resin particles.

(In the general formula ^(1), R 1, ^{R 2,} and ^{R 3} each represents a an alkyl group having 1 to 5 carbon ^atoms, R 1, ^{R 2,} and ^{R 3} are the same May be different)

(In the general formula (2), R ⁴ represents any of methyl and ethyl, R ⁵ is a hydrogen atom, the number 1 to 8 alkyl group carbon atoms, a cycloalkyl group and an aryl group, Indicate one of
<2> The total content S (% by mass) in the ink of the compound represented by the general formula (1) and the compound represented by the following general formula (2), and the total solid content concentration of the resin particles in the ink The ink according to <1>, wherein a mass ratio (S / A) to A (mass%) is 1.0 or more and 4.0 or less.
<3> The ink according to <1> or <2>, wherein the compound represented by the general formula (1) is 3-methoxy-N, N-dimethylpropionamide.
<4> The ink according to any one of <1> to <3>, wherein at least one of the two types of resin particles is polyurethane resin particles.
<5> The ink according to any one of <1> to <4>, wherein the two kinds of resin particles are polyurethane resin particles and polyvinyl chloride resin particles.
<6> an ink discharge head for discharging ink, having an individual liquid chamber, an inflow channel for allowing ink to flow into the individual liquid chamber, and an outflow channel for allowing ink to flow out of the individual liquid chamber; And an ink described in any one of <1> to <5> above.
<7> The inkjet printing apparatus according to <6>, further including a circulation unit that circulates the ink from the inflow channel toward the outflow channel.
<8> An ink discharge head having an inflow channel for allowing ink to flow into the individual liquid chamber and an outflow channel for allowing ink to flow out from the individual liquid chamber is used as the ink discharge head. It has a printing process in which any of the mechanical energy is applied to the ink to eject the ink for printing. As the ink, water, a compound represented by the following general formula (1) and / or the following general formula (2 And an ink containing at least two kinds of resin particles.

(In the general formula ^(1), R 1, ^{R 2,} and ^{R 3} each represents a an alkyl group having 1 to 5 carbon ^atoms, R 1, ^{R 2,} and ^{R 3} are the same May be different)

(In the general formula (2), R ⁴ represents any of methyl and ethyl, R ⁵ is a hydrogen atom, the number 1 to 8 alkyl group carbon atoms, a cycloalkyl group and an aryl group, Indicate one of
<9> The inkjet printing method according to <8>, wherein the printing process is a printing process in which ink is discharged while the ink is circulated to perform printing.
<10> The inkjet printing method according to <9>, further comprising a step of pausing ink circulation and a step of circulating the ink before discharging the ink.
<11> The inkjet printing method according to <9> or <10>, further comprising a step of applying pressure to the ink with a strength that does not cause the ink to be ejected when the ink is circulated.
<12> The inkjet printing method according to any one of <8> to <11>, further including a heating step of heating the printed matter after printing.

(About Figures 1 and 2)
101 apparatus main body 102 paper feed tray 103 paper discharge tray 104 ink cartridge loading unit 105 operation unit 111 upper cover 112 front cover front surface 115 front cover 131 guide rod 132 stay 133 carriage 134 recording head 135 sub tank 141 base material stacking part 142 base material 143 Paper feeding roller 144 Separation pad 145 Guide 151 Conveying belt 152 Counter roller 153 Conveying guide 154 Pressing member 155 Tip pressure roller 156 Charging roller 157 Heating heater type conveying roller 158 Tension roller 161 Heating heater type guide member 171 Separating claw 172 Roller 173 Paper discharge roller 181 Double-sided paper feed unit 182 Manual paper feed unit 201 Ink cartridge

(About FIGS. 3-14)
DESCRIPTION OF SYMBOLS 1 Nozzle plate 2 Flow path plate 3 Vibration plate member 4 Nozzle 6 Individual liquid chamber 6a, 6b, 6c, 6d, 6e Through-groove part 7 Fluid resistance part 7a Through-groove part 8 Liquid introduction part 8a Through-groove part 8b Through-groove part 9 Filter part 10 Common Liquid chamber 10A Downstream common liquid chamber 10a Through groove 10B Upstream common liquid chamber 10b Groove 11 Piezoelectric actuator 12 Piezoelectric members 12A, 12B Piezoelectric element 13 Base member 15 Flexible wiring member 20 Common liquid chamber member 21 First common liquid chamber member 22 Second common liquid chamber member 25a, 25b Piezoelectric actuator through hole 29 Cover 30 Vibration region 30a, 30b Protrusion 40 Channel member 41, 42, 43, 44, 45 Plate member 50 Circulating common liquid chamber 50a Groove 51 Fluid resistance Part 51a Through-groove part 52 Circulation channel 52a, 52b Through-groove part 53 Circulation channel 53a, 53b, 53c, 53d Through groove portion 71 Supply port 71a Through hole 81 Circulation port 81a, 81b Through hole 102 Moving plate member 104 Nozzle 105 Individual liquid chamber 110 Common liquid chamber 112 Piezoelectric member 301 Liquid droplet 901 Ink cartridge 902 Ink 905 Ink supply tube 906 Liquid feed pump 910 Ink tank 911 Ink 912 Atmospheric release valve 913 Head supply tube 914 Filter unit 915 Head 916 Head circulation tube 917 Head circulation pump 918 Circulation valve 919 Filter 920 Full sensor

JP 2005-220352 A JP 2011-094082 A Japanese Patent Laying-Open No. 2015-071289

Claims (12)

Ink provided with an ink discharge head for discharging ink having an individual liquid chamber, an inflow channel for allowing ink to flow into the individual liquid chamber, and an outflow channel for allowing ink to flow out from the individual liquid chamber In the ink used in the ejection device,
An ink in which the ink contains water, a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2), and at least two kinds of resin particles.

(In the general formula ^(1), R 1, ^{R 2,} and ^{R 3} each represents a an alkyl group having 1 to 5 carbon ^atoms, R 1, ^{R 2,} and ^{R 3} are the same May be different)

(In the general formula (2), R ⁴ represents any of methyl and ethyl, R ⁵ is a hydrogen atom, the number 1 to 8 alkyl group carbon atoms, a cycloalkyl group and an aryl group, Indicate one of   The total content S (mass%) in the ink of the compound represented by the general formula (1) and the compound represented by the following general formula (2), and the total solid content concentration A (mass in the ink of the resin particles) 2) The ink according to claim 1, wherein a mass ratio (S / A) to 1.0% is 4.0 or more and 4.0 or less.   The ink according to claim 1 or 2, wherein the compound represented by the general formula (1) is 3-methoxy-N, N-dimethylpropionamide.   The ink according to any one of claims 1 to 3, wherein at least one of the two types of resin particles is polyurethane resin particles.   The ink according to any one of claims 1 to 4, wherein the two kinds of resin particles are polyurethane resin particles and polyvinyl chloride resin particles.   An ink discharge head for discharging ink, comprising: an individual liquid chamber; an inflow channel for allowing ink to flow into the individual liquid chamber; and an outflow channel for allowing ink to flow out of the individual liquid chamber. An ink jet printing apparatus comprising: the ink according to any one of 1 to 5;   The inkjet printing apparatus according to claim 6, further comprising a circulation unit that circulates the ink from the inflow channel toward the outflow channel. As the ink discharge head, an ink discharge head having an inflow channel for allowing ink to flow into the individual liquid chamber and an outflow channel for allowing ink to flow out from the individual liquid chamber is used. Thermal energy and mechanical energy A printing process in which any one of the above is applied to the ink to eject the ink and printing, and the ink is represented by water, a compound represented by the following general formula (1) and / or the following general formula (2). And an ink containing at least two kinds of resin particles.

(In the general formula ^(1), R 1, ^{R 2,} and ^{R 3} each represents a an alkyl group having 1 to 5 carbon ^atoms, R 1, ^{R 2,} and ^{R 3} are the same May be different)

(In the general formula (2), R ⁴ represents any of methyl and ethyl, R ⁵ is a hydrogen atom, the number 1 to 8 alkyl group carbon atoms, a cycloalkyl group and an aryl group, Indicate one of   The inkjet printing method according to claim 8, wherein the printing process is a printing process in which ink is ejected while the ink is circulated.   The ink jet printing method according to claim 9, further comprising a step of stopping circulation of the ink and a step of circulating the ink before discharging the ink.   The inkjet printing method according to claim 9, further comprising a step of applying pressure to the ink with a strength that does not cause the ink to be ejected when the ink is circulated.   The inkjet printing method according to any one of claims 8 to 11, further comprising a heating step of heating the printed matter after printing.

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