JP2017019972A - Ink, inkjet recording method, inkjet recording device and recorded matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink for inkjet recording good in dryness of images even when recorded on a non-permeable substrate and capable of providing high glossiness images.SOLUTION: There is provided an ink containing water, an organic solvent, a polycarbonate urethane resin particle and a coloring material, where the organic solvent contains an amide compound represented by the following formula, the content of the amide compound is 80 mass% or more based on the total content of the organic solvent and a mass ratio between the content of water and the content of the organic solvent (water/organic solvent) is 1/3 to 3/1. Ris a C1 to 6 linear or branched alkyl group, Rand Rare each independently H or a C1 to 4 linear or branched alkyl group.SELECTED DRAWING: None

Description

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

  In recent years, in order to improve durability such as light resistance, water resistance, and abrasion resistance in industrial applications such as displays, posters, and bulletin boards, for example, non-porous permeable substrates such as plastic films have been used. Inks have been developed for recording on the impermeable substrate.

  As the ink, a solvent-based ink containing a resin dissolved in an organic solvent and an ultraviolet curable ink containing a polymerizable monomer as a main component have been widely used. The evaporation of the organic solvent and the polymerizable monomer has been widely used. The environmental load due to was large. Accordingly, water-based inks that can be recorded on the non-permeable substrate and contain water and resin particles have been proposed (see, for example, Patent Documents 1 and 2).

However, when the proposed water-based ink is recorded on a non-permeable substrate, the drying property of the image is poor and it is difficult to obtain high gloss.
An object of the present invention is to provide an ink that has a good image drying property even when recorded on a non-permeable substrate and that can provide a highly glossy image.

The ink of the present invention as a means for solving the problems comprises water, an organic solvent, polycarbonate urethane resin particles, and a coloring material, and the organic solvent is represented by the following general formula (1). An amide compound is contained, the content of the amide compound is 80% by mass or more based on the total content of the organic solvent, and the mass ratio of the water content to the organic solvent content (water / organic Solvent) is 1/3 or more and 3/1 or less.
[General formula (1)]
In the general formula (1), R ₁ represents a linear or branched alkyl group having 1 to 6 carbon atoms. R ₂ and R ₃ may be the same or different and each represents a hydrogen atom and a linear or branched alkyl group having 1 to 4 carbon atoms.

  According to the present invention, it is possible to provide an ink that has a good image drying property even when recorded on a non-permeable substrate and can provide a highly glossy image.

FIG. 1 is a schematic view showing an example of a serial type ink jet recording apparatus. FIG. 2 is a schematic view showing a configuration in the main body of the ink jet recording apparatus of FIG. FIG. 3 is a schematic diagram illustrating an example of heating means of the ink jet recording apparatus.

(ink)
The ink of the present invention contains water, an organic solvent, polycarbonate urethane resin particles, and a coloring material, and further contains other components as necessary.

<Organic solvent>
The said organic solvent contains the amide compound represented by following General formula (1), and also contains another organic solvent as needed.
[General formula (1)]
In the general formula (1), R ₁ represents a linear or branched alkyl group having 1 to 6 carbon atoms. R ₂ and R ₃ may be the same or different and each represents a hydrogen atom and a linear or branched alkyl group having 1 to 4 carbon atoms.

  By containing the amide compound represented by the general formula (1), it can penetrate into a non-permeable substrate such as polyvinyl chloride.

In the general formula (1), R ₁ represents a linear or branched alkyl group having 1 to 6 carbon atoms. Examples of the linear or branched alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a pentyl group. Among these, a methyl group is preferable.
In the general formula (1), R ₂ and R ₃ may be the same or different, and R ₂ and R ₃ are any of a hydrogen atom and a linear or branched alkyl group having 1 to 4 carbon atoms. Represents Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Among these, a methyl group is preferable.

Examples of the compound represented by the general formula (1) include 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide represented by the following structural formula (1), Examples include 3-methoxy-N, N-diethylpropionamide. 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) is preferable in that a high gloss image can be obtained.
[Structural formula (1)]

As a commercial item of the compound represented by the general formula (1), for example, trade name “Ecamide M-100” (3-methoxy-N, N-dimethylpropionamide, manufactured by Idemitsu Kosan Co., Ltd., , R ¹ : methyl group, R ² : methyl group, R ³ : methyl group), trade name “Ecamide B-100” (3-butoxy-N, N-dimethylpropionamide, manufactured by Idemitsu Kosan Co., Ltd., the above general formula And 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.

As content of the amide compound represented by the said General formula (1), it is 80 mass% or more with respect to the total content of the said organic solvent, and 85 mass% or more is preferable. When the content is 80% by mass or more, excellent permeability is exhibited even for a non-permeable substrate such as polyvinyl chloride.
The content of the amide compound represented by the general formula (1) is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and more preferably 30% by mass with respect to the total amount of the ink. The content is particularly preferably 50% by mass or less.

-Other organic solvents-
There is no restriction | limiting in particular as said other 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, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl- Polyhydric alcohols such as 1,3-hexanediol, ethyl 1,2,4-butanetriol, 1,2,3-butanetriol, petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, Jie Polyethylene alcohol alkyl ethers such as lenglycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol-n-hexyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, etc. Nitrogen-containing heterocycles such as polyhydric alcohol aryl ethers, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, γ-butyrolactone Compounds, amides such as formamide, N-methylformamide, N, N-dimethylformamide, monoethanolamine, diethanolamine, triethylamine Amines such as emissions, dimethyl sulfoxide, sulfolane, sulfur-containing compounds such as thiodiethanol, propylene carbonate, and the like ethylene carbonate. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as content of the said organic solvent, Although it can select suitably according to the objective, 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% are preferable. The following is more preferable. It is preferable that the content is 20% by mass or more and 70% by mass or less from the viewpoint of showing excellent image drying properties.

<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 alone or in combination of two or more.

  The water content is preferably 15% by mass or more and 60% by mass or less, more preferably 20% by mass or more and 40% by mass or less, based on the total amount of the ink. When the content is 15% by mass or more, high viscosity can be prevented, and when the ink jet recording apparatus described later is provided, the ink ejection stability can be improved. It is preferable at the point from which the glossiness of becomes favorable.

  The mass ratio (water / organic solvent) between the water content and the organic solvent content is 1/3 or more and 3/1 or less, and preferably 1/2 or more and 2/1. When the mass ratio is 1/3 or more and 3/1 or less, the permeability of the ink to the base material is good, the film-forming property of the polycarbonate urethane resin particles contained in the ink is improved, and the drying property of the image is dramatically improved. This is preferable in terms of improvement.

<Polycarbonate urethane resin particles>
The polycarbonate urethane resin particles have the property of hardly swelling with respect to the solvent. Therefore, even in the ink containing the amide compound represented by the general formula (1), which is a solvent having high solubility in the polycarbonate urethane resin particles, the organic solvent is not included too much at the time of film formation, so that the drying property is good and smooth. An ink coating film can be formed, and the glossiness of the image can be improved.
The polycarbonate urethane resin particles are obtained by reacting polycarbonate polyol and polyisocyanate.

The polycarbonate polyol can be appropriately selected according to the purpose. For example, the polycarbonate polyol can be obtained by a transesterification reaction between a carbonate ester and a polyol in the presence of a catalyst, or a reaction between phosgene and bisphenol A. Can be obtained. 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, 1,2-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and neopentyl. Examples thereof include low molecular diol compounds such as glycol and 1,4-cyclohexanediol, polyethylene glycol, and polypropylene glycol. These may be used alone or in combination of two or more.

  There is no restriction | limiting as said polyisocyanate, According to the objective, it can select suitably, For example, 1, 3- phenylene diisocyanate, 1, 4- phenylene diisocyanate, 2, 4- tolylene diisocyanate (TDI), 2, 6-tolylene diisocyanate, 4,4′-diphenylenemethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanate Aromatic polyisocyanate compounds such as natobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate ; Echile Diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcapro Aliphatic polyisocyanate compounds such as acrylate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate; isophorone diisocyanate (IPDI) ), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TD) ), Alicyclic diisocyanate compounds such as bis (2-isocyanatoethyl) -4-dichlorohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, and the like. . 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 industrial 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, Cyclic diisocyanates are preferred.

Furthermore, the use of at least one alicyclic diisocyanate makes it easy to obtain the desired coating strength and scratch resistance.
As content of the said alicyclic diisocyanate, 60 mass% or more is preferable with respect to the said polyisocyanate whole quantity.

-Method for producing polyurethane polycarbonate urethane resin particles-
The said polycarbonate urethane resin particle can be obtained with the manufacturing method generally used conventionally, for example, the following method etc. are mentioned.
First, in the absence of a solvent or in the presence of an organic solvent, the polycarbonate polyol and the polyisocyanate are reacted at an equivalent ratio in which an isocyanate group becomes excessive to produce an isocyanate-terminated urethane prepolymer.
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 the organic solvent that can be used for the production of the polycarbonate urethane 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; Examples include amides such as dimethylformamide, N-methylpyrrolidone, N-ethylpyrrolidone, and the like. 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.

  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 alone or in combination of two or more.

  Commercially available products may be used as the polycarbonate urethane resin particles. Examples of the commercially available products include U-coat UX-485 and Permarin UA-368T (manufactured by Sanyo Chemical Industries, Ltd.). These may be used alone or in combination of two or more.

  The polycarbonate urethane resin particles are not particularly limited, and those supplied in the form of an aqueous resin 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 ability to disperse the ink in the ink as uniformly as possible, the polycarbonate urethane resin particles are stable using water as a dispersion medium. It is preferable to add to the ink in the state of a resin emulsion in a dispersed state.

  As the polycarbonate urethane 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 polycarbonate urethane resin particles is promoted with evaporation of the solvent and water. Therefore, the heating step is not necessarily required in the image recording method using the ink of the present invention.

In dispersing the polycarbonate urethane resin particles in an aqueous medium, a forced emulsification type using a dispersing agent can be used, but the molecular structure from the point of preventing the dispersant remaining in the coating film and lowering the strength. So-called self-emulsifying type polycarbonate urethane resin particles having an anionic group therein are suitable.
The acid value of the anionic group of the self-emulsifying polycarbonate urethane resin particles is preferably 5 mgKOH / g or more and 100 mgKOH / g or less, preferably 5 mgKOH / mg or more from the viewpoint of water dispersibility, abrasion resistance, and chemical resistance. 50 mgKOH / mg or less is more preferable.

  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 polycarbonate urethane resin particles, a monomer having the anionic group may be used.

Examples of the method for producing an aqueous dispersion of polycarbonate urethane 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 containing 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 polycarbonate urethane 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. These may be used alone or in combination of two or more. Among these, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene alkylamine are preferable.

  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. These may be used alone or in combination of two or more. Among these, polyoxyethylene alkyl ether sulfate and sulfosuccinate are preferable.

  There is no restriction | limiting in particular as content of the said surfactant, Although it can select suitably according to the objective, 0.1 to 30 mass% is preferable with respect to polycarbonate urethane resin particle whole quantity, and 5 More preferably, it is at least 20% by mass. When the content is in the range of 0.1% by mass or more and 30% by mass or less, the polycarbonate urethane resin particles are suitably formed into a film, and an ink having excellent adhesion and water resistance is obtained, and the recorded matter is blocked. It is preferable at the point used without doing.

The volume average particle diameter of the polycarbonate urethane resin particles is not particularly limited and may be appropriately selected depending on the intended purpose. However, considering use in an inkjet recording apparatus, it is preferably 10 nm or more and 1,000 nm or less, preferably 10 nm. It is more preferably 200 nm or less and particularly preferably 10 nm or more and 100 nm or less.
By using polycarbonate urethane resin particles having a volume average particle size of 10 nm or more and 1,000 nm or less, the contact portion between the water-soluble organic solvent and the polycarbonate urethane resin particle surface is increased, and the film forming property of the polycarbonate urethane resin particles is enhanced. Since a continuous film of tough polycarbonate urethane resin particles is formed, high image hardness can be obtained.
The volume average particle diameter can be measured using, for example, a particle size analyzer (Microtrac Model UPA9340, manufactured by Nikkiso Co., Ltd.).

  There is no restriction | limiting in particular as content of the said polycarbonate urethane resin particle, According to the objective, it can select suitably, From the point of fixability and the storage stability of an ink, 1 mass% or more 5% or more with respect to the total amount of ink. The mass% or less is preferable. When the content of the polycarbonate urethane resin particles satisfies the above range, the smoothness of the ink coating film is further improved, high gloss can be obtained, and the fixability to a non-permeable substrate is improved. Is preferable.

  Examples of the qualitative and quantitative determination of the polycarbonate urethane resin particles include, for example, “Testing method and evaluation result of each dynamic characteristic of plastic material (22); Takeo Yasuda, Plastics: Japan Plastic Industry Federation /“ Plastics ”Editorial Committee It can be confirmed according to the procedure detailed in “Division”. Specifically, it can be confirmed by analyzing by infrared spectroscopic analysis (IR), thermal analysis (DSC, TG / DTA), pyrolysis gas chromatography (PyGC), nuclear magnetic resonance method (NMR) or the like.

  When the ink of the present invention is heated after recording, the residual solvent can be reduced and the adhesiveness can be improved. In particular, when the minimum film-forming temperature of the polycarbonate urethane resin particles (hereinafter also referred to as “MFT”) exceeds 80 ° C., there is no film-forming defect of the polycarbonate urethane resin particles, and the image fastness is improved. It is preferable to heat.

When adjusting the minimum film-forming temperature of the resin emulsion containing the polycarbonate urethane resin particles in order to obtain the ink of the present invention, for example, the glass transition point of the polycarbonate urethane resin particles (hereinafter also referred to as “Tg”) may be used. ) Can be controlled, and when the polycarbonate urethane resin particles are a copolymer, it can be prepared by changing the ratio of the monomers forming the copolymer. The minimum film-forming temperature refers to the minimum temperature at which a transparent continuous film is formed when the resin emulsion is cast thinly on a metal plate such as aluminum and the temperature is raised. In the temperature range below the film-forming temperature, the resin emulsion is in the form of a white powder. Specifically, “film-forming temperature test apparatus” (manufactured by Imoto Seisakusho Co., Ltd.), “TP-801 MFT tester” ( It can be measured with a commercially available minimum film-forming temperature measuring apparatus such as Tester Sangyo Co., Ltd.
Moreover, since it changes also by control of the particle diameter of the said polycarbonate urethane resin particle, it is possible to make the minimum film forming temperature of a polycarbonate urethane resin particle into the target value by these control factors.
In addition, you may add another urethane resin particle as needed.

<Color material>
There is no restriction | limiting in particular as said coloring material, According to the objective, it can select suitably, A pigment, dye, etc. are mentioned. Among these, a pigment is preferable.
Examples of the pigment include inorganic pigments and organic pigments.

  Examples of the inorganic pigment include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, 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, use of polycarbonate urethane resin particle hollow particles and inorganic hollow particles is also possible.
Among these pigments, those having good affinity with organic solvents are preferably used.

Specific examples of the pigment include black for 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.

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.
Further, it may be a polycarbonate urethane resin particle containing the pigment in microcapsules and capable of dispersing the pigment in water, that is, pigment particles.
In this case, the pigment contained in the ink is not necessarily enclosed or adsorbed in the polycarbonate urethane resin particles, and the pigment may be dispersed in the ink as long as the effects of the present invention are not impaired. Good.

The number average particle diameter of the pigment is not particularly limited and may be appropriately selected depending on the intended purpose, but the maximum frequency is preferably 20 nm or more and 150 nm or less in terms of the maximum number. When the number average particle diameter is 20 nm or more, 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 ink is improved, but also the ejection stability is excellent, and the image Image quality such as 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.).

  When the pigment is dispersed using a dispersant, there is no particular limitation, and any conventionally known one 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.

  The content of the coloring material is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 1% by mass or more and 10% by mass or less with respect to the total amount of the ink. When the content is 0.1% by mass or more and 10% by mass or less, the drying property of the image and the glossiness of the image can be improved.

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, surfactants, antiseptic / antifungal agents, rust preventives, pH adjusters, hindered phenols and hindered phenol amines. And colorless anti-aging agents for rubbers and plastics.

-Surfactant-
The surfactant can be contained in order to ensure wettability to the substrate.
There is no restriction | limiting in particular as said surfactant, According to the objective, it can select suitably, For example, an amphoteric surfactant, nonionic surfactant, 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 fungicide-
Examples of the antiseptic / antifungal agent include 1,2-benzisothiazolin-3-one, sodium benzoate, sodium dehydroacetate, sodium sorbate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, and the like. Can be mentioned. These may be used alone or in combination of two or more.

-Antirust agent-
Examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite. These may be used alone or in combination of two or more.

-PH adjuster-
The pH adjusting agent is not particularly limited, and any substance can be used as long as it can adjust the pH to a desired value without adversely affecting the ink. For example, lithium hydroxide, sodium hydroxide Alkali metal hydroxides such as potassium hydroxide; Alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate; Quaternary ammonium hydroxides and amines such as diethanolamine and triethanolamine; Ammonium hydroxide Quaternary phosphonium hydroxide and the like. These may be used alone or in combination of two or more.

<Ink production method>
The ink can be produced, for example, by stirring and mixing the water, the organic solvent, the polycarbonate urethane resin particles, the color material, and, if necessary, the other components. 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.

  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 substrate. When the viscosity is 2 mPa · s or more, the ink ejection stability can be improved when the ink jet recording apparatus described later is provided.

(Inkjet recording apparatus and inkjet recording method)
The ink jet recording apparatus of the present invention has at least ink flying means, and further has other means appropriately selected as necessary.
The ink jet recording method of the present invention includes at least an ink flying step and further includes other steps appropriately selected as necessary.
The ink jet recording method of the present invention can be preferably carried out by the ink jet recording apparatus of the present invention, and the ink flying step can be suitably carried out by the ink flying means. Moreover, the said other process can be suitably performed by the said other means.

<Ink flying process and ink flying means>
The ink flying step is a step of forming an image on a substrate by applying a stimulus to the ink of the present invention and causing the ink to fly, and can be performed by an ink flying means.
The ink flying means is means for applying a stimulus to the ink of the present invention and causing the ink to fly to form an image on a substrate. There is no restriction | limiting in particular as said ink flying means, According to the objective, it can select suitably, For example, an inkjet head etc. are mentioned.

  As the ink jet head, a piezoelectric element is used as a pressure generating means for pressurizing ink in the ink flow path, and a diaphragm that forms the wall surface of the ink flow path is deformed to change the volume in the ink flow path to eject ink droplets. A so-called piezo type (see Japanese Patent Laid-Open No. 2-51734), or a so-called thermal type that generates bubbles by heating ink in an ink flow path using a heating resistor (Japanese Patent Laid-Open No. 61-59911). The volume of the ink flow path is changed by disposing the diaphragm and the electrode that form the wall surface of the ink flow path to face each other and deforming the vibration plate by an electrostatic force generated between the vibration plate and the electrode. And an electrostatic type that discharges ink droplets (see JP-A-6-71882).

  The stimulus can be generated by, for example, the stimulus generating means, and the stimulus is not particularly limited and can be appropriately selected according to the purpose. For example, heat (temperature), pressure, vibration, light Etc. These may be used individually by 1 type and may use 2 or more types together. Among these, heat and pressure are preferable.

  There is no particular limitation on the mode of the ink flying, and it varies depending on the type of the stimulus. For example, when the stimulus is “heat”, the heat corresponding to the recording signal is applied to the ink in the recording head. A method of applying energy using, for example, a thermal head, generating bubbles in the ink by the thermal energy, and ejecting and ejecting the ink as droplets from the nozzle holes of the recording head by the pressure of the bubbles, etc. Can be mentioned. When the stimulus is “pressure”, for example, by applying a voltage to a piezoelectric element bonded to a position called a pressure chamber in an ink flow path in the recording head, the piezoelectric element is bent, and the pressure chamber For example, a method in which the volume is reduced and the ink is ejected and ejected as droplets from the nozzle holes of the recording head.

  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. The drive frequency is preferably 1 kHz or higher, and the resolution is preferably 300 dpi or higher.

-Base material-
Examples of the substrate include a permeable substrate and a non-permeable substrate. Among these, the said non-permeable base material is preferable and a vinyl chloride base material is more preferable.

<Other processes and other means>
Examples of the other steps include a stimulus generation step, a control step, and a heating step.
Examples of the other means include a stimulus generation means, a control means, and a heating process.
Examples of the stimulus generating means include a heating device, a pressurizing device, a piezoelectric element, a vibration generating device, an ultrasonic oscillator, a light, and the like. Specifically, for example, a piezoelectric actuator such as a piezoelectric element, a heating resistor, etc. Examples include a thermal actuator that uses a phase change caused by film boiling of a liquid using an electrothermal transducer such as a body, a shape memory alloy actuator that uses a metal phase change caused by a temperature change, and an electrostatic actuator that uses an electrostatic force.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

-Heating step and heating means-
The heating step is a step of heating the base material on which the image is recorded, and can be performed by a heating means.
As the ink jet recording method, high image quality recording can be performed on the non-permeable base material as the base material, but still higher image quality, abrasion resistance, and high adhesion image formation, and high speed recording conditions. It is preferable to heat the non-permeable substrate after recording. When a heating step is performed after recording, the film formation of the polycarbonate urethane resin particles contained in the ink is promoted, so that the image hardness of the recorded matter can be improved.

The heating means is means for heating the substrate on which the image is recorded.
As the heating means, many known apparatuses can be used, and examples thereof include forced air heating, radiant 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 further depending on the type of the substrate to be printed. Can be changed.
The heating temperature is more preferably 40 ° C. or more and 120 ° C. or less, and particularly preferably 50 ° C. or more and 90 ° C. or less from the viewpoints of drying properties and film forming temperature. When the heating temperature is 40 ° C. or higher and 120 ° C. or lower, damage to the non-permeable substrate due to heat can be prevented, and occurrence of non-ejection due to warming of the ink head can be suppressed.

  As an example of the ink jet recording method of 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 substrate, and an ink containing the pigment It is also possible to use a recording method having a recording step of recording by using. At this time, the clear ink or the white ink can be applied to the entire surface of the substrate, or may be applied to a part of the substrate. In the case of applying to a part of the substrate, 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 recording is performed.

  When the white ink is used, it is also effective to use the following recording method. White ink is applied to the substrate, 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 adhered to the surface of the substrate, so that the recording visibility 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 used for non-permeable 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 ink of the present invention is not limited to the ink jet recording method and can be widely used. As a recording method other than the ink jet recording method, for example, blade coating method, gravure coating method, gravure offset coating method, bar coating method, roll coating method, knife coating method, air knife coating method, comma coating method, U comma coating method, Examples thereof include an AKKU coating method, a smoothing coating method, a micro gravure coating method, a reverse roll coating method, a 4 to 5 roll coating method, a dip coating method, a curtain coating method, a slide coating method, a die coating method, and a spray coating method.
As an example of the embodiment, when the white ink is applied to the entire surface of the base material, the coating is performed by a coating method other than the ink jet recording method, and when recording with ink of a color other than white, recording is performed by the ink jet recording method. Embodiments are possible.
As another embodiment, it is possible to use an ink jet recording method for recording using white ink and recording using ink of a color other than white.
The same applies when clear ink is used instead of white ink.

  Here, an ink jet recording 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 recording apparatus includes a serial type (shuttle type) scanned by a carriage and a line type equipped with a line type head. FIG. 1 is a schematic diagram illustrating an example of a serial type ink jet recording 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 ink jet recording apparatus includes an apparatus main body 101, a paper feed tray 102 mounted on 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 left and right side plates (not shown). Then, the scanning is moved by a main scanning motor (not shown).
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.

The inkjet recording head constituting the recording head 134 includes a piezoelectric actuator such as a piezoelectric element, a thermal actuator that uses a phase change due to film boiling of a liquid using an electrothermal transducer such as a heating resistor, and a metal phase due to a temperature change. A shape memory alloy actuator using a change, an electrostatic actuator using an electrostatic force, or the like as an energy generating means for discharging ink can be used.
Further, the carriage 133 is equipped with sub tanks 135 for each color for supplying each color ink to the recording head 134. The ink is supplied to the sub tank 135 from the ink cartridge 201 of the present invention loaded in the ink cartridge loading unit 104 via an ink supply tube (not shown) and replenished.

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 is, for example, a surface layer serving as a substrate adsorption surface formed of a polycarbonate urethane resin particle material having a thickness of about 40 μm that is not subjected to resistance control, for example, a copolymer of tetrafluoroethylene and ethylene (ETFE), This surface layer has a back layer (medium resistance layer, ground layer) which is made of the same material and subjected to resistance control by carbon. 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, After the substrate 142 is dried with hot air by a fan heater (not shown), it is 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 ink jet recording apparatus, the base material 142 is separated and fed one by one from the paper feed 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.

FIG. 3 is a schematic diagram illustrating an example of a heating unit of the ink jet recording apparatus illustrated in FIGS. 1 and 2. 3 can be dried by blowing warm air 202 onto an image formed on the substrate 142 conveyed on the conveyor belt 151 by a heating fan 201 as a warm air generator. .
A heater group 203 is provided on the opposite side of the conveying belt 151 from the base material 142, and the base material 142 on which an image is formed can be heated. In FIG. 3, reference numerals 157 and 158 denote conveying rollers as conveying means.

(Recorded material)
The recorded matter of the present invention has an image recorded with the ink of the present invention on a substrate.
The substrate is not particularly limited and may be appropriately selected depending on the purpose. For example, plain paper, glossy paper, special paper, cloth, and the like can be used. When applied to a transmissive substrate, an image with good color development can be provided.
The non-permeable substrate refers to a substrate having a surface with low water permeability, absorbability and / or adsorptivity, and includes a material that does not open to the outside even if there are many cavities inside, More quantitatively, it refers to a base material having a water absorption of 10 mL / m ² or less from the start of contact to 30 msec ^1/2 in the Bristow method.
As the non-permeable base material, for example, plastic films such as a vinyl chloride film, a polyethylene terephthalate (PET) film, and a polycarbonate film are suitable, but other non-permeable base materials and plain paper or inorganic coating permeable media. It shows sufficient performance even for permeable media that have been used in the past.

In addition, even when the base material is colored (colored base material) by applying white ink before the color ink at the time of color recording, the color of the base material can be aligned with white. The color development can be improved.
Examples of the colored substrate include colored paper, the film, fabric, clothing, and ceramic.

  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.

(Preparation example of polycarbonate urethane resin particles)
<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): 1,200)), 2, 2-dimethylolpropionic acid (hereinafter sometimes referred to as “DMPA”) (220 g) and N-methylpyrrolidone (hereinafter also referred to as “NMP”) (1347 g) were charged in a nitrogen stream at 60 ° C. DMPA was dissolved by heating.
Next, 1,445 g of 4,4′-dicyclohexylmethane diisocyanate and 2.6 g of dibutyltin dilaurate (catalyst) are added and heated to 90 ° C., and a urethanation reaction is performed over 5 hours to obtain an isocyanate-terminated urethane prepolymer. Obtained. The reaction mixture was cooled to 80 ° C., 149 g of triethylamine was added thereto, 4,340 g was extracted from the mixture, 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 is added, and 626 g of a 35% by mass 2-methyl-1,5-pentanediamine aqueous solution is added to carry out a chain extension reaction, and the solvent is kept so that the solid content concentration becomes 30% by mass. To obtain a polycarbonate urethane resin emulsion.
-Measurement of surface hardness-
Next, the obtained polycarbonate urethane resin emulsion was applied on a slide glass so as to have an average thickness of 10 μm, and dried at 100 ° C. for 30 minutes to prepare a polycarbonate urethane resin particle film. When the Vickers indenter was pushed into the obtained polycarbonate urethane resin film with a load of 9.8 mN using a micro surface hardness tester (FISCHERSCOPE HM2000, manufactured by Fischer), the surface hardness (Martens hardness) was 120 N / mm. ² .

(Preparation Example 1 of Pigment Dispersion)
<Preparation of black pigment dispersion>
After premixing the following prescription mixture, it was 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 (pigment solids concentration 15 Mass%).
Carbon black pigment (trade name: Monarch 800, manufactured by Cabot Corporation), 15 parts by weight Anionic surfactant (Pionin A-51-B, manufactured by Takemoto Yushi Co., Ltd.) ... 2 parts by weight Ion exchange water ... ... 83 parts by mass

(Pigment Dispersion Preparation Example 2)
<Preparation of cyan pigment dispersion>
A cyan pigment dispersion liquid was prepared in the same manner as in Preparation Example 1 of the pigment dispersion liquid except that the carbon black pigment was changed to Pigment Blue 15: 4 (manufactured by Toyo Ink Co., Ltd.). (Pigment solid content concentration of 15% by mass) was obtained.

(Pigment Dispersion Preparation Example 3)
<Preparation of magenta pigment dispersion>
Except for changing the carbon black pigment to Pigment Red 122 (trade name: Toner Magenta EO02, manufactured by Clariant Japan Co., Ltd.) A magenta pigment dispersion (pigment solid content concentration of 15% by mass) was obtained.

(Pigment Dispersion Preparation Example 4)
<Preparation of yellow pigment dispersion>
Similar to Preparation 1 of Pigment Dispersion, except that the carbon black pigment in Pigment Dispersion Preparation Example 1 was changed to Pigment Yellow 74 (trade name: First Yellow 531, manufactured by Dainichi Seika Kogyo Co., Ltd.). Thus, a yellow pigment dispersion (pigment solid content concentration of 15% by mass) was obtained.

Example 1
<Preparation of ink>
20% by mass of the black pigment dispersion (pigment solid content concentration of 15% by mass) of Preparation Example 1, 15% by mass of the polycarbonate urethane resin emulsion (solid content concentration of 30%), 3-methoxy-N, N-dimethylpropionamide ( Product name: Ecamide M-100, manufactured by Idemitsu Kosan Co., Ltd.) 30% by mass, surfactant (trade name: BYK349, manufactured by Big Chemie Japan Co., Ltd.) 2% by mass, 1,3-butanediol 5% by mass, preservative 1, 2-benzisothiazolin-3-one (trade name: Proxel LV, manufactured by Arch Chemicals Japan Co., Ltd.) 0.1 mass% and high-pure water 27.9 mass% were mixed and stirred, and the average pore size was adjusted to 0. The ink of Example 1 was produced by filtering through a 2 μm polypropylene filter.

(Examples 2 to 11 and Comparative Examples 1 to 4)
In Example 1, except having changed into the composition of Table 1-Table 3, and content (mass%), it is the same as that of Example 1, and Examples 2-11 and Comparative Examples 1-4. An ink was prepared.

In Tables 1 to 3, the amide compound and the polycarbonate urethane resin particles are as follows.
・ 3-Butoxy-N, N-dimethylpropionamide (trade name: Ecamide B-100, manufactured by Idemitsu Kosan Co., Ltd.)
・ Acrylic resin emulsion (trade name: Boncoat R-3380-E, manufactured by DIC Corporation)
・ Polyether urethane resin emulsion (trade name: ACRITT WBR-016U, manufactured by Taisei Fine Chemical Co., Ltd.)
・ Polyester urethane resin emulsion (trade name: ACRITT WBR-2000U, manufactured by Taisei Fine Chemical Co., Ltd.)

<Evaluation>
With respect to the obtained inks of Examples 1 to 11 and Comparative Examples 1 to 4, “drying” and “image gloss” were evaluated as follows, and the results are shown in Table 4.

<< Image dryness >>
The obtained inks of Examples 1 to 11 and Comparative Examples 1 to 4 were filled into an inkjet printer (IPSiO GXe5500 remodeling machine), and a polyvinyl chloride film (hereinafter referred to as “PVC film”, CPPVWP 1300, manufactured by Sakurai Co., Ltd.). ) Was recorded. After recording, the film was dried for a predetermined time (5 minutes, 8 minutes, 10 minutes, 15 minutes) on a hot plate (NINOS ND-1, manufactured by ASONE CORPORATION) set to 50 ° C.
The filter paper was pressed against the solid image after drying, and the determination was made based on the following evaluation criteria from the degree of ink transfer to the filter paper. It is practically desirable that the evaluation is B or more.
The IPSiO GXe5500 remodeling machine was remodeled from the IPSiO GXe5500 machine (manufactured by Ricoh Co., Ltd.) so that the printing corresponding to a printing speed of 30 m ² / hr with a printing width of 150 cm can be reproduced in A4 size. A plate was installed and modified so that the heating conditions (heating temperature, heating time) after recording could be changed.
[Evaluation criteria]
A: No transfer to filter paper under 50 ° C, 5 minutes drying condition B: No transfer to filter paper under 50 ° C, 8 minute drying condition C: Transfer to filter paper under 50 ° C, 10 minute drying condition D: Transfer to filter paper does not disappear even when drying at 50 ° C for 15 minutes

<< Image glossiness >>
The obtained inks of Examples 1 to 11 and Comparative Examples 1 to 4 were filled in an ink jet printer (IPSiO GXe5500, manufactured by Ricoh Co., Ltd.), a solid image was printed on the PVC film, and then set to 80 ° C. It was dried for 1 hour on a hot plate (NINOS ND-1, manufactured by ASONE Co., Ltd.).
The 60 ° glossiness of the solid image after drying was measured with a gloss meter (4501, manufactured by BYK Gardner Co., Ltd.), and judged based on the following evaluation criteria. It is practically desirable that the evaluation is B or more.
[Evaluation criteria]
A: 60 ° gloss is greater than 100% B: 60 ° gloss is 81% to 100%
C: 60 ° gloss is 60% to 80%
D: 60 ° gloss is less than 60%

Examples 1 to 4 are particularly preferred examples of the present invention, and it was found that even if the pigments are different, both high image drying properties and high image glossiness can be achieved.
In Examples 5 and 10, since R _{1 to} R ₃ of the amide compound represented by the general formula (1) in the organic solvent contain an amide compound that is not a methyl group, the images are compared with Examples 1 to 4. The result was slightly inferior in dryness.
In Example 6, since the content of the polycarbonate urethane resin particles was more than 5% by mass, the image glossiness was slightly inferior to those of Examples 1 to 4.
Examples 7 and 8 are examples in which the addition amount of the amide compound was changed. When the content of the amide compound is 80% by mass or more with respect to the total content of the organic solvent, high image drying property and high It was found that the image gloss was compatible.
In Example 9, the solvent to be added was changed. When the content of the amide compound was 80% by mass or more based on the total content of the organic solvent, high image drying was performed regardless of the type of the organic solvent. It has been found that the image quality and the high image glossiness are compatible.

Comparative Examples 1 to 4 were results that could not be used practically.
Comparative Examples 1 to 3 are comparative examples using resin particles that are not polycarbonate polyurethane particles, and the resin particles swelled and a smooth film could not be formed, resulting in poor image gloss.
In Comparative Example 4, the content of the amide compound was 67% by mass with respect to the total content of the organic solvent, the permeability to the substrate was insufficient, and the image drying property was inferior.

As an aspect of this invention, it is as follows, for example.
<1> Contains water, an organic solvent, polycarbonate urethane resin particles, and a coloring material,
The organic solvent contains an amide compound represented by the following general formula (1), and the content of the amide compound is 80% by mass or more based on the total content of the organic solvent,
The ink is characterized in that a mass ratio (water / organic solvent) between the water content and the organic solvent content is 1/3 or more and 3/1 or less.
[General formula (1)]
In the general formula (1), R ₁ represents a linear or branched alkyl group having 1 to 6 carbon atoms. R ₂ and R ₃ may be the same or different and each represents a hydrogen atom and a linear or branched alkyl group having 1 to 4 carbon atoms.
<2> The ink according to <1>, wherein R ₂ and R ₃ in the general formula (1) are methyl groups.
<3> The ink according to any one of <1> and <2>, wherein R ₁ in the general formula (1) is any one of a methyl group, an ethyl group, and a butyl group.
<4> The ink according to any one of <1> to <3>, wherein the amide compound is an amide compound represented by Structural Formula (1).
[Structural formula (1)]
<5> The ink according to any one of <1> to <4>, wherein the organic solvent further contains a water-soluble organic solvent.
<6> The ink according to any one of <1> to <5>, wherein the water-soluble organic solvent is 1,3-butanediol and diethylene glycol-n-hexyl ether.
<7> The ink according to any one of <1> to <6>, wherein the total content of the organic solvent is 20% by mass or more and 70% by mass or less.
<8> The ink according to any one of <1> to <7>, wherein the content of the polycarbonate urethane resin particles is 1% by mass or more and 5% by mass or less.
<9> The ink according to any one of <1> to <8>, wherein the number average particle diameter of the polycarbonate urethane resin particles is 10 nm to 1,000 nm.
<10> The ink according to any one of <1> to <9>, wherein the color material is a pigment.
<11> The ink according to any one of <1> to <10>, wherein the pigment is an organic pigment.
<12> The ink according to any one of <1> to <11>, wherein a content of the pigment is 0.1% by mass or more and 10% by mass or less.
<13> At least an ink flying step of recording an image on a substrate by applying a stimulus to the ink according to any one of <1> to <12> and causing the ink to fly. Inkjet recording method.
<14> The inkjet recording method according to <13>, further including a heating step of heating the substrate on which the image is recorded.
<15> The inkjet recording method according to any one of <13> to <14>, wherein the base material is a vinyl chloride base material.
<16> The ink according to any one of <1> to <12>, wherein the ink includes at least an ink flying unit that applies a stimulus and causes the ink to fly to record an image on a substrate. Inkjet recording apparatus.
<17> The inkjet recording apparatus according to <16>, further including a heating unit configured to heat the base material on which an image is recorded.
<18> The inkjet recording apparatus according to <17>, wherein the heating by the heating unit is 40 ° C. or higher and 120 ° C. or lower.
<19> A recorded matter comprising an image recorded with the ink according to any one of <1> to <12> on a base material.
<20> The recorded matter according to <19>, wherein the base material is a vinyl chloride base material.

  The ink according to any one of <1> to <12>, the ink jet recording method according to any one of <13> to <15>, and the ink jet according to any one of <16> to <18>. The recording device and the recorded matter according to any one of <19> to <20> have an object to solve the conventional problems and achieve the following object. That is, the ink, the ink jet recording method, the ink jet recording apparatus, and the recorded matter have good drying properties and high gloss even when recorded on a non-permeable substrate, the ink It is an object of the present invention to provide an ink jet recording method, an ink jet recording apparatus, and a recorded matter using the above.

JP 2012-52042 A JP 2014-101517 A

DESCRIPTION OF SYMBOLS 101 Main body 102 Paper feed tray 103 Paper discharge tray 104 Ink cartridge loading part 105 Operation part 111 Upper cover 112 Front surface 115 Front cover 131 Guide rod 132 Stay 133 Carriage 134 Recording head 135 Sub tank 141 Paper placement part 142 Paper 143 Paper supply roller 144 Separator Pad 145 Guide 151 Conveyor Belt 152 Counter Roller 153 Conveyor Guide 154 Pressing Member 155 Pressing Roller 156 Charging Roller 157 Conveying Roller 158 Densation Roller 161 Guide Member 171 Separation Claw 172 Discharge Roller 173 Discharge Roller 181 Double-sided Paper Feed Unit 182 Manual paper feeder

Claims (10)

Containing water, organic solvent, polycarbonate urethane resin particles, and coloring material,
The organic solvent contains an amide compound represented by the following general formula (1), and the content of the amide compound is 80% by mass or more based on the total content of the organic solvent,
An ink having a mass ratio (water / organic solvent) of the water content to the organic solvent content of 1/3 or more and 3/1 or less.
[General formula (1)]
In the general formula (1), R ₁ represents a linear or branched alkyl group having 1 to 6 carbon atoms. R ₂ and R ₃ may be the same or different and each represents a hydrogen atom and a linear or branched alkyl group having 1 to 4 carbon atoms. The ink according to claim 1, wherein the amide compound is an amide compound represented by the following structural formula (1).
[Structural formula (1)]
  The ink according to claim 1, wherein a content of the polycarbonate urethane resin particles is 1% by mass or more and 5% by mass or less.   The ink according to claim 1, wherein the color material is a pigment.   An ink jet recording method comprising at least an ink flying step of recording an image on a substrate by applying a stimulus to the ink according to claim 1 and causing the ink to fly.   The inkjet recording method according to claim 5, further comprising a heating step of heating the substrate on which an image is recorded.   The inkjet recording method according to claim 5, wherein the substrate is a vinyl chloride substrate.   An ink jet recording apparatus comprising at least ink flying means for applying a stimulus to the ink according to claim 1 and causing the ink to fly to record an image on a substrate.   A recorded matter comprising an image recorded with the ink according to any one of claims 1 to 4 on a substrate.   The recorded matter according to claim 9, wherein the base material is a vinyl chloride base material.