JP7119590B2 - PRINTING METHOD, PRINTING DEVICE, CONTAINER SET, AND PRINTED MATERIAL - Google Patents

Description

The present invention relates to a printing method, a printing apparatus, a container set, and printed matter.

BACKGROUND ART In industrial printing, a method of forming an image by ejecting water-based ink onto a non-absorbent substrate such as a film by an inkjet recording method is known.

In Patent Document 1, an inkjet recording sheet having a colorant-receiving layer on a support made of a material such as plastic is immersed in an acidic solution and dried. An inkjet recording method for recording an image thereon is disclosed.

However, when printing is performed by applying a coloring material ink containing a coloring material and water to a non-absorbing recording medium such as plastic, a solvent such as water in the coloring material ink applied to the non-absorbing recording medium In order to evaporate, a step of heat drying is performed. At this time, there is a problem that the dots on the non-absorbent recording medium become uneven due to the heating and drying, and the glossiness of the image formed by the dots is lowered.

The invention according to claim 1 comprises a pretreatment liquid application step of applying a pretreatment liquid containing a water-insoluble plasticizer to a non-absorbent recording medium, and a liquid layer formed by the applied pretreatment liquid. and a coloring material ink applying step of applying a coloring material ink containing a coloring material and water to a certain pretreatment layer , wherein the water-insoluble plasticizer is diisononyl phthalate or di-2-ethylhexyl adipate. is a printing method including

The printing method of the present invention exhibits an excellent effect of suppressing a decrease in glossiness of an image.

FIG. 1 is an explanatory side view showing an example of the printing apparatus of the present invention. FIG. 2 is an explanatory plan view of a main part showing an example of the printing apparatus of the present invention. FIG. 3 is an explanatory plan view showing an example of the printing apparatus of the present invention. FIG. 4 is an explanatory side view showing an example of the printing apparatus of the present invention. FIG. 5 is an explanatory plan view of a main part showing an example of the printing apparatus of the present invention. FIG. 6 is an explanatory plan view showing an example of the printing apparatus of the present invention.

Embodiments of the present invention will be described below.

[Print method]
The printing method of this embodiment includes a pretreatment liquid application step and a coloring material ink application step. Moreover, it is preferable to include other steps such as a transparent ink applying step and a heating step as necessary.

<<Pretreatment liquid application step>>
The pretreatment liquid application step is a step of applying a pretreatment liquid containing a water-insoluble plasticizer to the non-absorbent recording medium prior to the coloring material ink application step. The pretreatment liquid applied to the non-absorbent recording medium forms a pretreatment layer. After the pretreatment liquid application step, the colorant ink applied onto the pretreatment layer, which is a liquid layer, is difficult to dissolve in the pretreatment layer, so it spreads over the pretreatment layer and forms uniform and smooth dots (colorant ink). ink layer). As a result, it is possible to prevent the dots formed by the colored ink on the non-absorbent recording medium from becoming uneven due to heat drying, and to prevent the glossiness of the image formed by the dots from being lowered.

The pretreatment liquid application step includes applying the pretreatment liquid to the entire recording surface of the non-absorbent recording medium, and selectively applying the pretreatment liquid to areas of the non-absorbent recording medium to which the colored ink is to be applied. Any step such as the step of applying may be used, but the step of selectively applying the pretreatment liquid is preferable. By using this process, the amount of pretreatment liquid used can be reduced, the amount of energy required for heating and drying the pretreatment liquid and colorant ink can be reduced, and the pretreatment liquid and color ink can be dried by a simple heating process. Allow the material ink to dry. When the pretreatment liquid is applied to the entire recording surface, it is preferable to apply the pretreatment liquid by a roller coating method. When selectively applying the pretreatment liquid, it is preferable to apply the pretreatment liquid by an inkjet method. By applying the pretreatment liquid by the inkjet method, the pretreatment liquid can be applied accurately to the locations where the coloring material ink applied after applying the pretreatment liquid is applied. In addition, by applying the pretreatment liquid by an inkjet method, the pretreatment liquid can be applied only to the portions that require it. Accordingly, it is possible to provide a printing method in which the amount of pretreatment liquid used is reduced. In addition, by using the pretreatment liquid applying method by the inkjet method, a uniform pretreatment layer can be formed as compared with the roller coating method, so that the decrease in the glossiness of the image can be further suppressed.

<Non-absorbent recording medium>
A non-absorbent recording medium is a recording medium having a surface with low water permeability and low absorbency, and includes materials that have many cavities inside but do not open to the outside. A recording medium 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. The shape of the non-absorbent recording medium is preferably, for example, film-like, sheet-like, or board-like, but is not limited to these.
Materials constituting the non-absorbent recording medium include, for example, materials selected from polyethylene terephthalate, polyvinyl chloride, polyurethane, polycarbonate, polyethylene, polypropylene, etc., and materials obtained by combining a plurality of these materials. Among these, a non-absorbent recording medium containing polyvinyl chloride in the area to which the pretreatment liquid is applied is preferable, and the printable area of the non-absorbent recording medium or the entire non-absorbent recording medium contains polyvinyl chloride. is more preferable.
The non-absorbent recording medium preferably contains a plasticizer, and more preferably contains a plasticizer when the material constituting the non-absorbent recording medium is polyvinyl chloride.

<Pretreatment liquid>
The pretreatment liquid contains a water-insoluble plasticizer. Further, for example, for the purpose of adjusting the concentration and viscosity of the pretreatment liquid, it may contain other additives such as organic solvents, oils, resins, stabilizers, and surfactants.
Moreover, it is preferable that the pretreatment liquid does not substantially contain water. “Substantially free of water” means that the water content in the pretreatment liquid is 1.0% by mass or less, preferably 0.5% by mass or less, and 0.1% by mass. % or less, and more preferably not contained. Since the pretreatment liquid does not substantially contain water, when the colorant ink containing water is applied onto the pretreatment layer, the colorant ink is prevented from mixing and permeating into the pretreatment layer. As a result, the colorant ink spreads over the pretreatment layer to form uniform and smooth dots (colorant ink layer), thereby further suppressing a decrease in the glossiness of the image.

(Water-insoluble plasticizer)
A water-insoluble plasticizer is an additive that is added to a thermoplastic resin or the like that constitutes a non-absorbent recording medium to improve flexibility, weather resistance, and the like of the non-absorbent recording medium. Further, in the present embodiment, "water-insoluble" indicates a plasticizer having a solubility in water at 25°C of less than 0.01 mg/L. In this embodiment, a water-insoluble plasticizer is contained in a pretreatment liquid and applied to a non-absorbent recording medium, and a coloring material ink is applied onto the pretreatment layer, which is a liquid layer. As a result, compared to the case where a non-absorbent recording medium coated with a water-insoluble plasticizer and dried is prepared in advance and the coloring material ink is applied, the effect of being able to suppress the decrease in the glossiness of the image can be obtained. can get.

Water-insoluble plasticizers include, for example, di-2-ethylhexyl adipate (DOA), adipates such as diisononyl adipate (DINA), di-2-ethylhexyl phthalate (DOP), and diisononyl phthalate (DINP). phthalates such as di-2-ethylhexyl fumarate (DOF), fumarate esters such as tri-2-ethylhexyl trimellitate (TOTM) and the like. , di-2-ethylhexyl adipate (DOA) and diisononyl phthalate (DINP) are preferred. When a pretreatment liquid containing these water-insoluble plasticizers is applied to a non-absorbent recording medium containing a plasticizer, the compatibility between the pretreatment liquid and the non-absorbent recording medium is improved, resulting in a uniform pretreatment layer. can be provided, which is preferable. As a result, it is possible to further suppress the decrease in the glossiness of the image. Further, when the non-absorbent recording medium is polyvinyl chloride and contains a plasticizer, compatibility is improved, which is preferable.

In addition, the content of the water-insoluble plasticizer is preferably 20% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, and 60% by mass or more of the pretreatment liquid. It is more preferably 100% by mass or less, and particularly preferably 70% by mass or more and 100% by mass or less. When the content of the water-insoluble plasticizer is 20% by mass or more and 100% by mass or less, the dots formed by the colored ink on the non-absorbent recording medium are suppressed from becoming uneven due to heat drying, A decrease in the glossiness of the image formed by the dots is suppressed.

(Organic solvent)
Examples of organic solvents include monohydric or dihydric alcohols having 4 or more carbon atoms such as 2-methyl-1-propanol, 1,5-pentanediol and 2-ethylhexanol, ethyl n-octoate, higher fatty acid esters having 8 or more carbon atoms such as ethyl laurate;

(Oils)
Examples of oils include dimethylsilicone oil and methylphenylsilicone oil. When the pretreatment liquid is ejected by an inkjet method, it is preferable to use a silicone oil having a viscosity of 50 mPa·s or less at 25°C.

(resin)
The type of resin contained in the pretreatment liquid is not particularly limited and can be appropriately selected according to the purpose. Examples include urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, Butadiene-based resins, styrene-butadiene-based resins, vinyl chloride-based resins, acrylstyrene-based resins, acrylsilicone-based resins, and the like can be mentioned.
Resin particles made of these resins may also be used. As the resin particles, appropriately synthesized ones may be used, or commercially available products may be used. Moreover, these may be used individually by 1 type, or may be used in combination of 2 or more types of resin particles.

(stabilizer)
Stabilizers are added for the purpose of suppressing decomposition of non-absorbent recording media such as polyvinyl chloride at high temperatures and for the purpose of suppressing hue change due to double bonds. Examples of stabilizers include, but are not limited to, calcium stearate and zinc stearate. The content of the stabilizer is preferably 0.05% by mass or more and 2.00% by mass or less with respect to the content of the water-insoluble plasticizer.

(Additive)
Surfactants, antifoaming agents, antiseptic and antifungal agents, antirust agents, pH adjusters and the like may be added to the pretreatment liquid, if necessary.

<<Color material ink application process>>
The coloring ink applying step is a step of applying coloring ink containing coloring material and water to the pretreatment layer, which is a liquid phase formed by the applied pretreatment liquid, after the pretreatment liquid applying step. is. By applying the color ink to a pretreatment layer formed on the non-absorbent recording medium instead of directly applying the color ink to the non-absorbent recording medium, the color ink on the non-absorbent recording medium It is possible to prevent unevenness of the dots formed by heating and drying, thereby suppressing a decrease in the glossiness of the image formed by the dots.

Further, since it is preferable that the coloring material ink application step is applied to the pretreatment layer in a uniform liquid phase state, it is preferable that the coloring material ink application step is performed without leaving an interval after the pretreatment liquid application step. Specifically, it is preferable that the coloring material ink application step is performed within 60 seconds after the pretreatment liquid application step is performed. By executing the colorant ink applying process while the pretreatment layer is in a state of a uniform liquid layer, it is possible to form uniform and smooth dots (colorant ink layer) and reduce the glossiness of the image. more restrained.

Further, in the present embodiment, since it is preferable that the colorant ink is applied to the pretreatment layer, which is in the state of a liquid layer, the colorant ink is applied by an inkjet method that can apply the colorant ink in a non-contact manner. is preferred.

<Color material ink>
Colorant ink includes a colorant and water. In addition, if necessary, other additives such as organic solvents, pigments, resin particles, and surfactants may be included.

(Organic solvent)
The organic solvent used in this embodiment is not particularly limited, and a water-soluble organic solvent can be used. Examples thereof include polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds.
Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol , 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl- 1,3-pentanediol, petriol and the like.
Examples of polyhydric alcohol alkyl ethers include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether and the like.
Examples of polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.
Nitrogen-containing heterocyclic compounds include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, γ-butyrolactone and the like. mentioned.
Amides include formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide and the like.
Amines include monoethanolamine, diethanolamine, triethylamine, and the like.
Examples of sulfur-containing compounds include dimethylsulfoxide, sulfolane, thiodiethanol and the like.
Other organic solvents include propylene carbonate and ethylene carbonate.
It is preferable to use an organic solvent having a boiling point of 250° C. or less because it not only functions as a wetting agent but also provides good drying properties.

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

The content of the organic solvent in the coloring ink is not particularly limited, and can be appropriately selected according to the purpose. The following is preferable, and 20% by mass or more and 60% by mass or less is more preferable.

(water)
The coloring material ink is preferably water-based ink containing water. The content of water in the colorant ink is not particularly limited and can be appropriately selected according to the purpose. It is preferably 20% by mass or more and 60% by mass or less.

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

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

As a method of dispersing a pigment to obtain a coloring ink, a method of introducing a hydrophilic functional group into the pigment to make it a self-dispersing pigment, a method of coating the surface of the pigment with a resin to disperse it, and a method of using a dispersant to disperse the pigment. method of dispersing, and the like.
As a method of making a self-dispersing pigment by introducing a hydrophilic functional group into a pigment, for example, a method of adding a functional group such as a sulfone group or a carboxyl group to a pigment (for example, carbon) to make it dispersible in water. is mentioned.
As a method of coating the surface of a pigment with a resin and dispersing it, there is a method of encapsulating the pigment in microcapsules to make it dispersible in water. This can be rephrased as a resin-coated pigment. In this case, it is not necessary for all of the pigments contained in the colorant ink to be coated with a resin. It may be dispersed in the ink.
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low-molecular-weight dispersant and high-molecular-weight dispersant typified by surfactants.
As the dispersant, it is possible to use, for example, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc. depending on the pigment.
As a dispersant, RT-100 (nonionic surfactant) manufactured by Takemoto Yushi Co., Ltd. and sodium naphthalenesulfonate formalin condensate can also be suitably used as a dispersant.
A dispersing agent may be used individually by 1 type, or may use 2 or more types together.

(Pigment dispersion)
Color inks can be obtained by mixing materials such as water and organic solvents with pigments. Further, it is also possible to produce a color ink by mixing a pigment, water, a dispersant, and the like to form a pigment dispersion, and then mixing materials such as water and an organic solvent.
The pigment dispersion is obtained by mixing and dispersing water, a pigment, a pigment dispersant, and optionally other components, and adjusting the particle size. Dispersion should be carried out using a disperser.
The particle diameter of the pigment in the pigment dispersion is not particularly limited, but the dispersion stability of the pigment is improved, and the image quality such as ejection stability and image density is improved. 500 nm or less is preferable, and 20 nm or more and 150 nm or less is more preferable. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).
The content of the pigment in the pigment dispersion is not particularly limited and can be appropriately selected according to the purpose. 50% by mass or less is preferable, and 0.1% by mass or more and 30% by mass or less is more preferable.
It is preferable to filter coarse particles with a filter, a centrifugal separator, or the like, and deaerate the pigment dispersion, if necessary.

(resin)
The type of resin contained in the colorant ink is not particularly limited and can be appropriately selected depending on the purpose. Examples include polyurethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, Butadiene-based resins, styrene-butadiene-based resins, vinyl chloride-based resins, acrylstyrene-based resins, acrylsilicone-based resins, and the like can be mentioned.
Resin particles made of these resins may also be used. It is possible to obtain a colored ink by mixing resin particles in a resin emulsion state in which water is dispersed as a dispersion medium with materials such as a coloring material and an organic solvent. As the resin particles, appropriately synthesized ones may be used, or commercially available products may be used. Moreover, these may be used individually by 1 type, or may be used in combination of 2 or more types of resin particles. In the present embodiment, among these, it is preferable to use polyurethane-based resin particles.

The volume average particle diameter of the resin particles is not particularly limited and can be appropriately selected according to the intended purpose. 200 nm or less is more preferable, and 10 nm or more and 100 nm or less is particularly preferable.
The volume average particle diameter can be measured, for example, using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

The content of the resin is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of fixability and storage stability of the colorant ink, the content is 1% by mass or more with respect to the total amount of the colorant ink. 30 mass % or less is preferable, and 5 mass % or more and 20 mass % or less is more preferable. When polyurethane-based resin particles are used as the resin, it is preferably contained in an amount of 1.0% by mass or more and 15.0% by mass or less based on the total amount of the colorant ink. Within this range, the fixability of the colorant image formed by applying and drying the colorant ink to the non-absorbent recording medium is improved.

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

(Additive)
Surfactants, antifoaming agents, antiseptic and antifungal agents, anticorrosive agents, pH adjusters, etc. may be added to the colored inks, if necessary.

<<Transparent ink application process>>
The transparent ink application step is a step of applying a transparent ink containing water but no coloring material to the non-absorbent recording medium. When the transparent ink is applied "to the non-absorbent recording medium", for example, when the transparent ink is applied directly to the non-absorbent recording medium, the transparent ink is pretreated on the non-absorbent recording medium. A case of giving to a layer is included. The timing of performing the transparent ink application step is not particularly limited, but is preferably simultaneous with or after the color ink application step, and more preferably at the same time. Note that the case where the transparent ink application process and the color material ink application process are performed simultaneously includes, for example, the case where the transparent ink application and the color material ink application are performed alternately.

Further, the transparent image area formed by applying the transparent ink is preferably adjacent to the color material image area formed by applying the color material ink. Since the colorant ink applied on the pretreatment layer is difficult to mix with the pretreatment liquid layer, the colorant ink applied on the pretreatment layer tends to wet and spread until the dots come into contact with each other, depending on the amount of the colorant ink applied. Therefore, by suppressing the wetting and spreading of the colorant ink forming the boundary portion of the colorant image area with the transparent ink, the bleeding at the boundary portion is suppressed.

<Transparent ink>
A transparent ink contains water and does not contain a coloring material. In addition, if necessary, other additives such as organic solvents, pigments, resin particles, and surfactants may be included. The various components that can be used for the transparent ink are the same as the various components that are used for the colored ink, so the description thereof will be omitted. Further, physical properties such as viscosity and surface tension of the transparent ink are preferably similar to those of the colored ink.

<<Heating process>>
The heating step is performed on the non-absorbent recording medium at at least one timing selected from after the pretreatment liquid application step and before the color ink application step, during the color ink application step, and after the color ink application step. It is a step of heating the pretreatment liquid, color ink, transparent ink, or non-absorbent recording medium applied to the recording medium. Further, the heating process is preferably performed at all timings after the pretreatment liquid applying process and before the coloring material ink applying process, during the coloring material ink applying process, and after the coloring material ink applying process. The heating step is preferably a step of drying by heating the pretreatment liquid, color ink, or transparent ink applied to the non-absorbent recording medium. It may be a heating step for the purpose of heating (preheating) the non-absorbent recording medium itself instead of the step of completely drying the non-absorbent recording medium. For example, the heating step that is performed after the pretreatment liquid application step and before the coloring material ink application step does not completely dry the pretreatment liquid applied to the non-absorbent recording medium. This step is intended to heat the medium itself. As a result, the colorant ink applied onto the pretreatment layer, which is a liquid layer, spreads over the pretreatment layer to form uniform and smooth dots (colorant ink layer). decrease in

The heating process includes, for example, a process of blowing hot air toward the non-absorbent recording medium, and a heating roller or flat heater from the surface of the non-absorbent recording medium to which the pretreatment liquid and coloring ink are not applied. A heating step and the like can be mentioned.

[Container set]
The storage container set of this embodiment is a set having a pretreatment liquid storage container that stores the pretreatment liquid and a colored ink storage container that stores the colored ink. The pretreatment liquid storage container and the coloring material ink storage container included in the storage container set may be of one kind or plural kinds. Further, the container set may be a set including a transparent ink container for containing the transparent ink, if necessary.
The shape, structure, size, material, etc. of the pretreatment liquid storage container and the colorant ink storage container can be appropriately selected according to the purpose. and a large-capacity tank are suitable.

[Printing device]
The printing apparatus includes pretreatment liquid applying means and colored ink applying means. Moreover, it is preferable to include other means such as transparent ink applying means and heating means as necessary.

<<First Embodiment of Printing Apparatus>>
A printing apparatus according to a first embodiment will be described with reference to FIGS. FIG. 1 is an explanatory side view of the printing apparatus, FIG. 2 is an explanatory plan view of the main part of the printing apparatus, and FIG. 3 is an explanatory plan view of the head.

This printing apparatus is a serial type inkjet recording apparatus, and includes a printing unit (image forming unit) 101 for printing on a printing medium (hereinafter referred to as "medium") 2 as a material to be printed, and a conveying unit 102 for conveying the medium 2. , a roll storage unit 103 for storing the medium 2, a roll winding unit 104 for winding the medium 2, and the like.

This apparatus uses a roll body 1 obtained by winding a medium 2, which is an example of a non-absorbent recording medium, into a roll. The roll body 1 is stored in the roll storage part 103, and the medium 2 is pulled out from the roll body 1 by the conveying roller pair 31 and sent out.

As shown in FIG. 2, the printing unit 101 serving as an example of pretreatment liquid application means, an example of coloring material ink application means, and an example of transparent ink application means includes a plurality of nozzle rows for ejecting liquid as liquid ejection means. A liquid ejection head (hereinafter also referred to as “head”) 11 is mounted on a carriage 12 . The carriage 12 is held by a guide member 13 so as to be reciprocatable in the main scanning direction (the direction perpendicular to the paper surface in FIG. 1).

Here, as shown in FIG. 3, the head 11 has a plurality of nozzle rows Na to Ne in which a plurality (m) of nozzles n1 to nm for ejecting liquid are arranged, and the nozzle arrangement direction is the medium transport direction ( sub-scanning direction) and mounted on the carriage 12 .

The nozzle rows Na to Nc of the head 11 include colored ink nozzle rows used for ejecting colored inks such as black (K), yellow (Y), magenta (M) and cyan (C). The nozzle row Nd of the head 11 includes, for example, a transparent ink nozzle row used for ejecting transparent ink. The nozzle array Ne of the head 11 includes, for example, a pretreatment liquid nozzle array used for ejecting the pretreatment liquid. In this example, one head has five nozzle rows Na to Ne, but a plurality of heads may have a plurality of nozzle rows.

The conveying unit 102 has a conveying roller 21 and a counter roller 22 that are arranged upstream of the printing unit 101 in the medium conveying direction (direction of arrow A: sub-scanning direction), and conveys the medium 2 while sandwiching it. A platen member 25 that guides the medium 2 is arranged facing the printing unit 101 .

The roll winding unit 104 includes a winding roll 41 on which the medium 2 is wound.

A preheater 51 , a print heater 52 , and a postheater 53 , which are examples of heating means, are arranged along the transport direction of the medium 2 .

The preheater 51 is a heater that heats the medium 2 in front of the printing area by the printing unit 101 . The print heater 52 is a heater that heats the medium 2 in the printing area of the printing unit 101 . The post-heater 53 is a heater that heats the medium 2 after printing by the printing unit 101 . For the pre-heater 51, the print heater 52, and the post-heater 53, electric heaters using ceramic or nichrome wire can be used.

A hot air fan 54 for blowing hot air to the medium 2 is provided downstream of the post heater 53 . A hot air fan 54 blows hot air directly onto the liquid on the printing surface to lower the humidity of the atmosphere and dry it completely.

By installing these heaters 51 to 53 and hot air fan 54, it is possible to print on non-permeable media such as vinyl chloride, polyethylene terephthalate (PET), acrylic, etc., into which liquid does not permeate.

<<Second Embodiment of Printing Apparatus>>
A printing apparatus according to a second embodiment will be described with reference to FIGS. 4 is an explanatory side view of the printing apparatus, FIG. 5 is an explanatory plan view of the main part of the printing apparatus, and FIG. 6 is an explanatory plan view of the head.

This printing apparatus is a serial type inkjet recording apparatus, and includes a printing unit (image forming unit) 1101 that prints on a medium 2 as a printing material, a transport unit 102 that transports the medium 2, and a roll storage unit 103 that stores the medium 2. , a roll winding unit 104 for winding the medium 2, a pretreatment liquid application unit 80 for applying the pretreatment liquid to the medium 2, and the like. Among these configurations, the description of the configurations common to the printing apparatus according to the first embodiment will be omitted.

This apparatus has a pretreatment liquid application unit 80, which is an example of pretreatment liquid application means, and employs a roller application mechanism. The pretreatment liquid is stored in the pretreatment liquid storage tank 81 , is drawn up on the surface of the roller by the drawing roller 83 , and is transferred to the film pressure control roller 82 . Subsequently, the pretreatment liquid transferred to the application roller 84 is transferred and applied to the medium 2 passing between it and the application counter roller 85 .

As shown in FIG. 5, a printing unit 1101 serving as an example of color ink application means and an example of transparent ink application means is a liquid ejection head (hereinafter referred to as a liquid ejection head) having a plurality of nozzle rows for ejecting liquid as liquid ejection means. (also called a “head”) 111 is mounted on a carriage 112 . A carriage 112 is held by a guide member 113 so as to be reciprocally movable in the main scanning direction (the direction perpendicular to the paper surface in FIG. 4).

Here, as shown in FIG. 6, the head 111 has a plurality of nozzle rows Ra to Re in which a plurality (m) of nozzles r1 to rm for ejecting liquid are arranged, and the nozzle arrangement direction is the medium transport direction ( sub-scanning direction) and mounted on the carriage 112 .

The nozzle rows Na to Nd of the head 111 include colored ink nozzle rows used for ejecting colored inks such as black (K), yellow (Y), magenta (M) and cyan (C). The nozzle array Ne of the head 11 includes, for example, a transparent ink nozzle array used for ejecting transparent ink. In this example, one head has five nozzle rows Na to Ne, but a plurality of heads may have a plurality of nozzle rows.

[Print]
The printed material of the present embodiment includes a non-absorbent recording medium, a water-insoluble plasticizer-containing layer formed on the non-absorbent recording medium and containing a water-insoluble plasticizer, and a colorant formed on the water-insoluble plasticizer-containing layer. and a colorant-containing layer containing The printed material is formed by drying the non-absorbent recording medium after the pretreatment liquid application step and the color ink application step. By carrying out the pretreatment liquid application step and the coloring ink application step, it is possible to obtain a printed matter in which a decrease in the glossiness of the image is suppressed. Specifically, the printed matter has a 20-degree glossiness of 30 or more, preferably 40 or more, on the surface of the colorant-containing layer. In addition, the colorant-containing layer is formed by a printing method including the colorant ink application step, and the colorant ink application conditions are such that the ejection amount per droplet of the colorant ink is 22 pl, and the resolution is 600×. Preferably, it is 600 dpi and the amount of wet colorant ink on the non-absorbent recording medium is 12.0 g/m ² .

Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Adjustment of pretreatment liquid>
(Adjustment of pretreatment liquid 1)
After the following materials were mixed and stirred, the mixture was filtered through a 0.2 μm polypropylene filter to obtain a pretreatment liquid 1.
・ Diisononyl phthalate (DINP) 99.7% by mass
・Calcium stearate 0.2% by mass
・ Zinc stearate 0.1% by mass

(Adjustment of pretreatment liquid 2)
Pretreatment liquid 2 was prepared by changing the combination and addition amount of each material used in the preparation of pretreatment liquid 1 to the combination and addition amount shown in Table 1 below. The unit of each number in Table 1 is "% by mass".

In addition, in Table 1 above, the product names of materials and the names of manufacturers are as follows.
・Methylphenyl silicone oil (trade name: KF-56A, manufactured by Shin-Etsu Silicone Co., Ltd.)

<Adjustment of Magenta Pigment Dispersion>
After premixing the following formulation mixture, the mixture was circulated and dispersed for 7 hours in a disk-type bead mill (KDL type by Shinmaru Enterprises, media: using zirconia balls with a diameter of 0.3 mm) to obtain a magenta pigment dispersion.
・Pigment Red 122 (trade name: Toner Magenta EO02, manufactured by Clariant Japan Co., Ltd.) 15.0% by mass
・ Anionic surfactant (Pionin A-51-B, manufactured by Takemoto Oil Co., Ltd.) 2.0% by mass
・Ion-exchanged water 83.0% by mass

<Adjustment of colored ink>
After mixing and stirring the following materials, the mixture was filtered through a 0.2 μm polypropylene filter to obtain a coloring material ink (magenta ink). Table 2 below also shows the combination and amount of each material used in the preparation of the colorant ink. The unit of each number in Table 2 is "% by mass".
・Magenta pigment dispersion 20.0% by mass
・ Polyurethane resin particles (trade name: Superflex 150, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 8.0% by mass
・ 1,2-propanediol 10.0% by mass
・ 3-methoxy-N,N-dimethylpropionamide 10.0% by mass
・ 3-methoxy-3-methylbutanol 4.0% by mass
・ 2-ethyl-1,3-hexanediol 3.0% by mass
・ Surfactant (trade name: SAG002, manufactured by Nissin Chemical Industry Co., Ltd.) 3.0% by mass
・ Antiseptic mold agent (trade name: Proxel LV) 0.05% by mass
・ Rust inhibitor (trade name: BT-120, manufactured by Johoku Chemical Industry Co., Ltd.) 0.05% by mass
・ Antifoaming agent (trade name: AD01, manufactured by Nissin Chemical Industry Co., Ltd.) 0.1% by mass
・Highly pure water 41.8% by mass

<Adjustment of transparent ink>
After the following materials were mixed and stirred, the mixture was filtered through a 0.2 μm polypropylene filter to obtain a transparent ink. Table 2 below also shows the combination and amount of each material used in the preparation of the transparent ink. The unit of each number in Table 2 is "% by mass".
・ Polyurethane resin particles (trade name: Superflex 150, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 12.0% by mass
・ 1,2-propanediol 20.0% by mass
・ 3-methoxy-N,N-dimethylpropionamide 10.0% by mass
・ 3-Methoxy-3-methylbutanol 7.0% by mass
・ 2-ethyl-1,3-hexanediol 6.0% by mass
・ Surfactant (trade name: SAG002, manufactured by Nissin Chemical Industry Co., Ltd.) 3.0% by mass
・ Antiseptic mold agent (trade name: Proxel LV) 0.05% by mass
・ Rust inhibitor (trade name: BT-120, manufactured by Johoku Chemical Industry Co., Ltd.) 0.05% by mass
・ Antifoaming agent (trade name: AD01, manufactured by Nissin Chemical Industry Co., Ltd.) 0.1% by mass
・Highly pure water 41.8% by mass

(Example 1)
The obtained pretreatment liquid 1 is filled into the pretreatment liquid storage container, and the colorant ink storage container is filled with the colorant ink to create a storage container set, which is a set of the pretreatment liquid storage container and the colorant ink storage container. did. Next, the pretreatment liquid storage container and the colored ink storage container were mounted on the inkjet printer shown in FIG. Then, a polyethylene terephthalate film (E-5100, manufactured by Toyobo Co., Ltd., hereinafter sometimes referred to as "PET film") is subjected to the following pretreatment liquid application step, coloring material ink application step, and heating step, A 50 mm square solid image and a character image with a font size of 8 pt were obtained.

- Pretreatment liquid application step -
As shown in FIG. 4, the pretreatment liquid was applied to the entire printed surface of the film by roller coating. The amount of the pretreatment liquid applied to the film was adjusted so that the amount of the undried pretreatment liquid on the film was 1.0 g/m ² .

-Color material ink application process-
As shown in FIG. 4, the coloring material ink was applied by an inkjet method to the surface of the film to which the pretreatment liquid had been applied. The colorant ink application means was adjusted so that the ejection amount per colorant ink droplet was 22 pl and the resolution was 600×600 dpi. In addition, the amount of the coloring ink applied to the film was adjusted so that the amount of the coloring ink in the undried state on the film was 12.0 g/m ² . Also, bi-directional printing, 2 passes, and 1/4 interlaced printing were performed.

-Heating process-
The preheater and print heater shown in FIG. 4 were set at 60.degree. Also, the post heater and the hot air fan were set to 70°C.
Further, the pretreatment layer on the film in the coloring material ink application step was visually observed to be in the state of a uniform liquid layer.

(Example 2)
The obtained pretreatment liquid 2 is filled into the pretreatment liquid storage container, and the colorant ink storage container is filled with the colorant ink to create a storage container set, which is a set of the pretreatment liquid storage container and the colorant ink storage container. did. Next, the ink jet printer shown in FIG. 1 was filled with the pretreatment liquid storage container and the coloring ink storage container. Then, the following pretreatment liquid application step, coloring material ink application step, Then, through a heating process, a 50 mm square solid image and a character image with a font size of 8 pt were obtained.

- Pretreatment liquid application step -
As shown in FIG. 1, the pretreatment liquid was applied by an inkjet method to the area of the film to which the coloring material ink was to be applied. The pretreatment liquid application unit was adjusted so that the ejection amount per droplet of the pretreatment liquid was 15 pl and the resolution was 150×150 dpi. The amount of pretreatment liquid applied to the film was adjusted so that the amount of undried pretreatment liquid on the film was 0.5 g/m ² .

-Color material ink application process-
As shown in FIG. 1, the color ink was applied by an inkjet method to the surface of the film to which the pretreatment liquid had been applied. The colorant ink application means was adjusted so that the ejection amount per colorant ink droplet was 22 pl and the resolution was 600×600 dpi. In addition, the amount of the coloring ink applied to the film was adjusted so that the amount of the coloring ink in the undried state on the film was 12.0 g/m ² . Also, bi-directional printing, 2 passes, and 1/4 interlaced printing were performed.

-Heating process-
The preheater and print heater shown in FIG. 1 were set at 60.degree. Also, the post heater and the hot air fan were set to 70°C.
Further, the pretreatment layer on the film in the coloring material ink application step was visually observed to be in the state of a uniform liquid layer.

(Example 3)
The obtained pretreatment liquid 1 is filled into the pretreatment liquid container, the colorant ink is filled into the colorant ink container, the transparent ink is filled into the transparent ink container, and the pretreatment liquid container and the colorant ink are filled. A storage container set, which is a set of a storage container and a transparent ink storage container, was created. Next, the ink jet printer shown in FIG. 4 was filled with the pretreatment liquid storage container, the colored ink storage container, and the transparent ink storage container. Then, the PVC film was subjected to the same pretreatment liquid applying process, coloring material ink applying process, and heating process as in Example 1, and the next transparent ink applying process, so that a 50 mm square solid image and font size were obtained. An 8pt character image was obtained.

-Transparent ink application process-
As shown in FIG. 4, the transparent image area formed by applying the transparent ink to the surface of the film to which the pretreatment liquid has been applied is the color material image area formed by applying the color material ink. A transparent ink was applied by an inkjet method so as to be adjacent. The transparent ink applying means was adjusted so that the ejection amount per transparent ink droplet was 22 pl and the resolution was 600×600 dpi. The amount of transparent ink applied to the film was adjusted so that the amount of undried transparent ink on the film was 12.0 g/m ² . Also, bi-directional printing, 2 passes, and 1/4 interlaced printing were performed.

(Example 4)
The obtained pretreatment liquid 2 is filled into the pretreatment liquid storage container, the colorant ink is filled into the colorant ink storage container, the transparent ink is filled into the transparent ink storage container, and the pretreatment liquid storage container and the colorant ink are filled. A storage container set, which is a set of a storage container and a transparent ink storage container, was created. Next, the ink jet printer shown in FIG. 1 was filled with the pretreatment liquid storage container, the colored ink storage container, and the transparent ink storage container. Then, the PVC film was subjected to the same pretreatment liquid application process, color ink application process, and heating process as in Example 2, and the next transparent ink application process, so that a 50 mm square solid image and font size were obtained. An 8pt character image was obtained.

-Transparent ink application process-
As shown in FIG. 1, the transparent image area formed by applying the transparent ink to the surface of the film to which the pretreatment liquid has been applied is the color material image area formed by applying the color material ink. A transparent ink was applied by an inkjet method so as to be adjacent. The transparent ink applying means was adjusted so that the ejection amount per transparent ink droplet was 22 pl and the resolution was 600×600 dpi. The amount of transparent ink applied to the film was adjusted so that the amount of undried transparent ink on the film was 12.0 g/m ² . Also, bi-directional printing, 2 passes, and 1/4 interlaced printing were performed.

(Comparative example 1)
The colored ink storage container filled with the colored ink thus obtained was mounted on the inkjet printer shown in FIG. Then, a 50 mm square solid image and a character image with a font size of 8 pt were obtained on the PET film through the following coloring material ink applying process and heating process. Note that the pretreatment liquid application step was not performed by making the pretreatment liquid application means inoperative.

-Color material ink application process-
As shown in FIG. 4, the color ink was applied to the film by an inkjet method. The colorant ink application means was adjusted so that the ejection amount per colorant ink droplet was 22 pl and the resolution was 600×600 dpi. In addition, the amount of the coloring ink applied to the film was adjusted so that the amount of the coloring ink in the undried state on the film was 12.0 g/m ² . Also, bi-directional printing, 2 passes, and 1/4 interlaced printing were performed.

-Heating process-
The preheater and print heater shown in FIG. 4 were set at 60.degree. Also, the post heater and the hot air fan were set to 70°C.

(Comparative example 2)
The colored ink storage container filled with the colored ink and the transparent ink container filled with the transparent ink thus obtained were mounted on the inkjet printer shown in FIG. Then, a 50 mm square solid image and a character image with a font size of 8 pt were obtained on the PVC film through the same coloring material ink application process and heating process as in Comparative Example 1, and the next transparent ink application process. rice field. Note that the pretreatment liquid application step was not performed by making the pretreatment liquid application means inoperative.

-Transparent ink application process-
As shown in FIG. 4, the transparent ink is applied to the film so that the transparent image area formed by applying the transparent ink is adjacent to the color material image area formed by applying the color material ink. given by the method. The transparent ink applying means was adjusted so that the ejection amount per transparent ink droplet was 22 pl and the resolution was 600×600 dpi. The amount of transparent ink applied to the film was adjusted so that the amount of undried transparent ink on the film was 12.0 g/m ² . Also, bi-directional printing, 2 passes, and 1/4 interlaced printing were performed.

Next, using the printed matter obtained in each example and each comparative example, the image glossiness of solid images and the sharpness of character images were evaluated according to the methods and evaluation criteria shown below. Table 3 shows the evaluation results.

[Image Glossiness]
After leaving the resulting printed matter to stand for 24 hours, the 20 degree glossiness of the solid image portion was measured using a glossmeter (Micro Trigloss, manufactured by BYK Gardener). When the evaluation was B or higher, it was judged to be practicable.
-Evaluation criteria-
A: 20° glossiness of 40 or more B: 20° glossiness of 30 or more and less than 40 C: 20° glossiness of less than 30

[Sharpness]
After leaving the resulting printed matter to stand for 24 hours, the sharpness (clearness) of the character image portion was visually evaluated according to the following evaluation criteria. A case with an evaluation of B or higher was judged to be practically preferable.
-Evaluation criteria-
A: Clear characters B: Slightly inferior in clarity, but characters can be read C: Characters are blurred and difficult to read

In Example 1, by applying the coloring material ink to the pretreatment layer of the liquid layer formed by applying the pretreatment liquid containing the water-insoluble plasticizer, even when high-temperature drying was performed, Uniform and smooth dots can be formed, thereby obtaining an image with high image gloss. In addition, since high-temperature drying can be performed without degrading image quality, printed matter can be obtained in a short time by high-temperature drying, and a highly productive printing method can be provided.
In Example 2, the pretreatment liquid is ejected by an inkjet method, so that the pretreatment liquid can be applied only to the portions that require it. Accordingly, it is possible to provide a printing method in which the amount of pretreatment liquid used is reduced.
In Example 3, a transparent image area formed by applying transparent ink is formed at a position adjacent to a color material image area formed by applying color material ink. As a result, the occurrence of bleeding is suppressed, and a printing method with high definition can be provided.
In Example 4, as in Example 2, the pretreatment liquid is ejected by an ink jet method, so that the pretreatment liquid can be applied only to the portions that require it. Accordingly, it is possible to provide a printing method in which the amount of pretreatment liquid used is reduced. Further, as in the third embodiment, a transparent image area formed by applying transparent ink is formed at a position adjacent to a color material image area formed by applying color material ink. As a result, the occurrence of bleeding is suppressed, and a printing method with high definition can be provided.

1 roll body 2 print medium (medium)
11 liquid ejection head (head)
12 Carriage 13 Guide member 21 Conveyance roller 22 Counter roller 25 Platen member 31 Conveyance roller pair 41 Winding roll 51 Preheater 52 Print heater 53 Postheater 54 Hot air fan 80 Pretreatment liquid application section 81 Pretreatment liquid storage tank 82 Film pressure control Roller 83 Draw-up roller 84 Application roller 85 Application counter roller 101 Printing unit (image forming unit)
102 Conveying Section 103 Roll Storage Section 104 Roll Winding Section 111 Liquid Ejection Head (Head)
112 Carriage 113 Guide Member 1101 Printing Unit (Image Forming Unit)
n1 to nm nozzles r1 to rm nozzles A sub-scanning direction Na to Ne nozzle rows Ra to Re nozzle rows

JP-A-2004-25723

Claims (10)

A pretreatment liquid application step of applying a pretreatment liquid containing a water-insoluble plasticizer to a non-absorbent recording medium;
a coloring material ink application step of applying coloring material ink containing coloring material and water to the pretreatment layer, which is a liquid layer formed by the applied pretreatment liquid ,
The printing method wherein the water-insoluble plasticizer comprises diisononyl phthalate or di-2-ethylhexyl adipate . 2. The printing method according to claim 1, wherein the pretreatment liquid applying step is a step of ejecting the pretreatment liquid from an inkjet head. A transparent ink application step of applying a transparent ink containing water and no coloring material to a non-absorbent recording medium;
3. The printing method according to claim 1, wherein the transparent image area formed by applying the transparent ink is adjacent to the color material image area formed by applying the color material ink. The printing method according to any one of claims 1 to 3, wherein the coloring ink application step is a step of ejecting the coloring ink from an inkjet head. 5. The printing method according to any one of claims 1 to 4, wherein the area of the non-absorbent recording medium to which the pretreatment liquid is applied contains polyvinyl chloride. The colorant ink contains polyurethane-based resin particles,
The printing method according to any one of claims 1 to 5, wherein the content of the polyurethane-based resin particles is 1.0% by mass or more and 15.0% by mass or less with respect to the colorant ink. The printing method according to any one of claims 1 to 6, wherein the pretreatment liquid does not substantially contain water. a pretreatment liquid containing a water-insoluble plasticizer;
a coloring material ink containing a coloring material and water;
pretreatment liquid application means for applying the pretreatment liquid to a non-absorbent recording medium;
coloring material ink applying means for applying the coloring material ink to the pretreatment layer , which is a liquid layer formed by the applied pretreatment liquid ,
The printing device wherein the water-insoluble plasticizer comprises diisononyl phthalate or di-2-ethylhexyl adipate . a pretreatment liquid storage container having a pretreatment liquid applied to a non-absorbent recording medium and containing a water-insoluble plasticizer;
a colorant ink storage container having a colorant ink containing a colorant and water applied to a pretreatment layer, which is a liquid layer formed by the applied pretreatment liquid ;
The container set wherein the water-insoluble plasticizer comprises diisononyl phthalate or di-2-ethylhexyl adipate . A non-absorbent recording medium, a water-insoluble plasticizer-containing layer formed on the non-absorbent recording medium and containing a water-insoluble plasticizer, and a coloring material formed on the water-insoluble plasticizer-containing layer and containing a coloring material a containing layer;
The water-insoluble plasticizer has diisononyl phthalate or di-2-ethylhexyl adipate,
A printed material having a 20-degree glossiness of 30 or more on the surface of the colorant-containing layer.

Images