Printing method, ink set, and method of manufacturing printed matter

Abstract

To provide a printing method that suppresses bleeding of a liquid deposited on an object to be coated.SOLUTION: A printing method comprises: a first step of depositing, on an object to be coated, a first liquid having a viscosity of 1.00×103 mPa s or more at a shear rate of 1 s-1 at 25°C and a viscosity of 3.50×102 mPa s or less at a shear rate of 5,000 s-1 at 25°C; and a second step of performing printing by discharging a second liquid from a nozzle onto the first liquid deposited on the object to be coated.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a printing method, an ink set, and a method for producing a printed matter. [Background technology]

[0002] Inkjet printing methods have been known for some time, in which different types of ink are layered to form an image on a recording medium. For example, when printing labels on bottles, if the bottle or contents are dark in color, the color of the bottle or contents is combined with a color ink to provide concealment using a white ink, preventing the color of the bottle or contents from showing through the label and spoiling the appearance of the design. When printing on fabrics, color graphics are achieved by concealing the color of the fabric with white ink before printing with color inks (see, for example, Patent Document 1).

[0003] However, when conventional inks are used to paint the exterior and interior of buildings, floors, and road surfaces, if the substrate is a dark color, an uneven substrate, or a porous substrate, and then a different ink is printed on top of the ink that conceals the substrate, the ink that conceals the substrate cannot form a thick film, and therefore cannot sufficiently conceal the color of the substrate.In addition, when a different ink is printed on top of the ink that conceals the substrate, the inks bleed. Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a printing method that can suppress bleeding of a liquid that has been applied to an object to be coated. [Means for solving the problem]

[0005] The printing method according to one embodiment of the present invention is a method of printing a coating material on a substrate at a shear rate of 1 s at 25°C. -1 Viscosity at 1.00 x 10 3mPa·s or more, and a shear rate of 5,000 s at 25°C -1 Viscosity at 3.50 x 10 2 a first step of applying a first liquid having a viscosity of 0.05 mPa·s or less; a second step of printing a second liquid by ejecting it from a nozzle onto the first liquid attached to the substrate; The present invention is characterized by having the following. [Effects of the Invention]

[0006] According to a printing method according to one embodiment of the present invention, it is possible to provide a printing method that can suppress bleeding of a liquid that has been applied to an object to be coated. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic side view showing a liquid ejection device as a printing device according to one embodiment of the present invention. [Figure 2] FIG. 2 is a schematic plan view showing a liquid ejection device as a printing device according to an embodiment of the present invention. [Figure 3] FIG. 3 is a schematic diagram showing the configuration of the inkjet nozzles in a printing device according to one embodiment of the present invention when the nozzles are closed. [Figure 4] FIG. 4 is a schematic diagram showing the inkjet nozzles in an open state in a printing device according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0008] (Printing method and printing device) A printing method according to one embodiment of the present invention has a first step and a second step, and may further have other steps as necessary. A printing device according to one embodiment of the present invention has a first means and a second means, and may further have other means as necessary. The first step can be performed by a first means, and the second step can be performed by a second means.

[0009] By using the printing method according to one embodiment of the present invention, bleeding of a liquid applied to a substrate can be suppressed. In particular, when coating the exterior and interior surfaces of buildings, floors, and road surfaces, if an ink or paint that conceals the substrate is printed or painted on a substrate that is dark in color, has irregularities, or is porous, and then a different ink is printed on top of the ink or paint that conceals the substrate, the ink or paint that conceals the substrate can be made thick enough to sufficiently conceal the color of the substrate, and when a different ink is printed on top of the ink that conceals the substrate, bleeding of the ink can be suppressed.

[0010] <First step and first means> The first step is to apply the coating solution to the object at a shear rate of 1 s at 25°C. -1 Viscosity at 1.00 x 10 3 mPa·s or more, and a shear rate of 5,000 s at 25°C -1 Viscosity at 3.50 x 10 2 This is a step of applying a first liquid having a viscosity of 0.1 mPa·s or less. The first method is to apply a shear rate of 1 s at 25°C to the substrate. -1 Viscosity at 1.00 x 10 3 mPa·s or more, and a shear rate of 5,000 s at 25°C -1 Viscosity at 3.50 x 10 2 A means for applying a first liquid having a viscosity of mPa·s or less. The first step can be carried out by a first means.

[0011] The method of application is not particularly limited and can be appropriately selected depending on the purpose. Examples include an ink-jet method, a spray method, and a brush coating method.

[0012] <<First Liquid>> The first liquid is heated at a shear rate of 1 s at 25°C. -1 Viscosity at 1.00 x 10 3 mPa·s or more, and a shear rate of 5,000 s at 25°C-1 Viscosity at 3.50 x 10 2 There are no particular limitations as long as the viscosity is not more than mPa·s, and it can be appropriately selected depending on the purpose, and examples thereof include ink, paint, and treatment liquid. The ink is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include white ink, transparent ink, color ink, etc. Among these, white ink is preferred from the viewpoint of excellent hiding power.

[0013] Shear rate of the first liquid at 25°C is 1 s -1 The viscosity at is 1.00 x 10 3 mPa·s or more, 1.00×10 3 mPa·s or more 3.00×10 4 mPa·s or less is preferable, and 3.00×10 3 mPa·s or more 2.50×10 4 mPa·s or less is more preferable, and 6.00×10 3 mPa s or more 2.00×10 4 mPa·s or less is more preferable, and 7.00×10 3 mPa s or more 2.00×10 4 The shear rate of the first liquid at 25°C is 1 s -1 The viscosity at 1.00 x 10 3 If the viscosity is higher than 1 mPa·s, after the first liquid is applied to the asphalt of the road surface, the viscosity of the ink of the first liquid becomes high, making it difficult for the ink to penetrate into the road surface, resulting in a thicker coating and improved hiding power. -1 The viscosity at 3.00 x 10 4 When the viscosity is equal to or less than mPa·s, the ejection stability when the first liquid is applied by an inkjet method is improved.

[0014] First liquid at 25°C with a shear rate of 0.1 s -1 The viscosity at is 3.00 x 10 4 mPa·s or more is preferable, 3.00×10 4 mPa s or more 1.50×10 5The shear rate of the first liquid at 25°C is preferably 0.1 s -1 The viscosity at 3.00 x 10 4 If the viscosity is more than mPa·s, after the first liquid is applied to the asphalt of the road surface, the viscosity of the ink of the first liquid becomes high, making it difficult for the ink to penetrate into the road surface, resulting in a thicker coating and improved hiding power. -1 The viscosity at 1.50 x 10 5 When the viscosity is equal to or less than mPa·s, the ejection stability when the first liquid is applied by an inkjet method is improved.

[0015] First liquid at 25°C and a shear rate of 5,000 s -1 The viscosity at is 3.50 x 10 2 mPa·s or less, 3.00×10 2 mPa·s or less is preferable, and 1.30×10 2 The shear rate of the first liquid at 25°C is 5,000 s -1 The viscosity at 3.50 x 10 2 If the viscosity is equal to or less than mPa·s, the ejection stability improves when the first liquid is applied by an ink jet method, and the first liquid can be applied evenly when it is applied by a spray method.

[0016] First liquid at 25°C, shear rate 1 s -1 Viscosity at shear rate of 0.1 s -1 Viscosity and shear rate at 5,000 s -1 The method for measuring viscosity at this stage is not particularly limited and can be selected appropriately depending on the purpose. For example, the viscosity can be measured using an MCR301 (manufactured by Anton Parr) with a cone plate (cone radius: 25 mm, cone angle: 1°).

[0017] The first liquid contains a thickener, a resin, and a solvent, and preferably contains a surfactant and a coloring material, and further contains other components as necessary.

[0018] -Thickener- The "thickening" of a thickener refers to the property of a solution such as ink that contains particles, where the viscosity increases when the shear rate is reduced and decreases when the shear rate is increased. 60 g of thickener is dispersed in 100 mL of water at 25°C, and the viscosity decreases when the shear rate is increased. -1 The viscosity is 100 mPa·s or more and 900,000 mPa·s or less at a shear rate of 5,000 S -1 This means that the viscosity at shear rate is between 1 mPa·s and 200 mPa·s, and that the viscosity increases when the shear rate is decreased and decreases when the shear rate is increased.

[0019] By including a thickener in the first liquid, the viscosity of the ink can be controlled according to the shear rate. Specifically, at a shear rate of 1 s at 25°C, -1 The viscosity at 1.00 x 10 3 By controlling the viscosity to more than mPa·s, a thick coating film can be formed, providing excellent hiding power to the coated object. -1 The viscosity at 3.50 x 10 2 By controlling the viscosity to mPa·s or less, the ejection stability when applying the first liquid by inkjet printing is improved.

[0020] For road surfaces, exterior and interior wall surfaces of buildings, and wall surfaces of civil engineering structures such as bridges and tunnels, coating films that are resistant to impact and abrasion are required, so it is preferable to include a thickener to form a coating film that is highly robust and resistant to impact and abrasion.

[0021] The thickener is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include inorganic thickeners and organic thickeners. Examples of inorganic thickeners include fumed silica, precipitated silica, clay minerals, talc, calcium carbonate, barium sulfate, and polyethylene oxide. Examples of organic thickeners include wax-based, cellulose-based, polyurethane-based, and polyacrylic-based thickeners. Wax-based thickeners include hydrogenated castor oil-based, polyethylene oxide-based, amide-based, and polyether-based thickeners. Cellulose-based thickeners include carboxymethyl cellulose, hydroxyethyl cellulose, and ethyl cellulose. Polyurethane-based thickeners include polyether-transition urethane compounds, hydrophobically modified polyoxyethylene, and polyurethane copolymers. Polyacrylic acid-based thickeners include polyacrylates and acrylic acid-methacrylic acid copolymers. These may be used alone or in combination of two or more. Among these, calcium carbonate and talc are preferred from the viewpoint of fastness of the ink coating film.

[0022] The clay mineral is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include diatomaceous earth, bentonite, sepiolite, kaolinite, montmorillonite, sericite (sericite), illite, etc. Among these, diatomaceous earth, bentonite, and sepiolite are preferred.

[0023] The calcium carbonate is not particularly limited and can be selected appropriately depending on the purpose, for example, commercially available products can be used. Examples of commercially available products include UP-G (manufactured by Imerys Specialties Japan Co., Ltd., 100% solids), Luminous (manufactured by Maruo Calcium Co., Ltd., 100% solids), Caltex 5 (manufactured by Maruo Calcium Co., Ltd., 100% solids), Super #2000 (manufactured by Maruo Calcium Co., Ltd., 100% solids), Super SSS (manufactured by Maruo Calcium Co., Ltd., 100% solids), Softon 1500 (manufactured by Bihoku Powder Industry Co., Ltd., 100% solids), Softon 3200 (manufactured by Bihoku Powder Industry Co., Ltd., 100% solids), BF100 (manufactured by Bihoku Powder Industry Co., Ltd., 10% solids), and Lighton A-5 (manufactured by Bihoku Powder Industry Co., Ltd., 100% solids).

[0024] The talc is not particularly limited and can be appropriately selected depending on the purpose, and for example, commercially available products can be used. The commercially available products are not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include Nano Ace D-600 (Nippon Talc Co., Ltd., solid content 100%).

[0025] The form of the thickener is not particularly limited and can be appropriately selected depending on the purpose, but it is preferably particulate in view of good storage stability when made into a liquid such as ink or paint. The thickener may also be a mixed crystal. The thickener may also be used in combination with a non-particulate thickener. Examples of non-particulate thickeners include resins that dissolve in the paint to provide a "thickening" effect.

[0026] The content of the particulate thickener is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 20.0% by mass or more and 55.0% by mass or less relative to the total amount of the first liquid, and more preferably 30.0% by mass or more and 40.0% by mass or less in terms of being able to impart excellent abrasion resistance and mechanical strength, further suppress bleeding, and provide excellent ejection stability when the first liquid is applied by an inkjet method. When the content is 20.0% by mass or more and 55.0% by mass or less, it becomes easier to control the viscosity of the first liquid.

[0027] The content of the non-particulate thickener is not particularly limited and can be selected appropriately depending on the purpose, but from the viewpoint of solubility in ink or paint, it is preferably 0.1% by mass or more and 20.0% by mass or less, and more preferably 0.1% by mass or more and 5.0% by mass or less, relative to the total amount of the first liquid.

[0028] -resin- The resin contained in the first liquid is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, styrene-butadiene resin, vinyl chloride resin, acrylic-styrene resin, acrylic-silicone resin, etc. These may be used alone or in combination of two or more. The resin may be resin particles made of these resins, and by dispersing the resin particles in a solvent as a dispersion medium to form a resin emulsion, it is possible to obtain ink by mixing it with materials such as colorants and organic solvents. The resin particles may be appropriately synthesized or commercially available. These may be used alone or in combination of two or more types of resin particles.

[0029] The glass transition temperature of the resin is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 15°C or lower, more preferably 0°C or lower, in order to prevent cracking of the coating film when the coating film is made thick.

[0030] The method for measuring the glass transition temperature is not particularly limited and can be appropriately selected depending on the purpose. For example, in the case of a resin emulsion, the glass transition temperature can be determined as follows. Specifically, 4 g of resin emulsion was evenly spread in a 50 mm diameter petri dish made of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and dried at 50°C for one week to obtain a resin film. 5.0 mg of the obtained resin film was placed in an aluminum sample container, which was then placed on a holder unit and set in an electric furnace. Next, in a nitrogen atmosphere, the temperature is increased from 0°C to 150°C at a rate of 10°C / min, then decreased from 150°C to -80°C at a rate of 5°C / min, and then increased again to 150°C at a rate of 10°C / min to measure the DSC curve. From the obtained DSC curve, the inflection point during the second temperature rise is analyzed by the midpoint method using the analysis program in the DSC-60 system to determine the glass transition point (Tg).

[0031] The content of the resin is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of excellent fastness of the coating film, it is preferably 5% by mass or more and 30% by mass or less based on the total amount of the first liquid. Note that the content indicates the content of the solid content of the resin.

[0032] The ratio (A / B) of the particulate thickener content (A) to the resin content (B) is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.8 or more, more preferably 1.0 or more, even more preferably 1.5 or more, and is particularly preferably 2.3 to 3.0 in terms of further suppressing bleeding. When the ratio (A / B) is 0.8 or more, excellent discharge stability is achieved and a thick coating film is formed, resulting in excellent hiding power for the substrate.

[0033] -solvent- The solvent contained in the first liquid is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include organic solvents and water.

[0034] The organic solvent is not particularly limited and can be appropriately selected depending on the purpose. Examples of the organic solvent include ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, polyhydric alcohols, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene carbonate, and ethylene carbonate.

[0035] The polyhydric alcohols are not particularly limited and can be appropriately selected depending on the purpose, but examples include dihydric alcohols and trihydric alcohols, which function as wetting agents and provide excellent ejection stability.

[0036] Examples of dihydric alcohols include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 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, and 1,5-hexanediol. Examples of trihydric alcohols include 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, and petriol.

[0037] The polyhydric alcohol alkyl ethers are not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether. The polyhydric alcohol aryl ethers are not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.

[0038] The nitrogen-containing heterocyclic compound is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include nitrogen-containing heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, and γ-butyrolactone.

[0039] The amides are not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropionamide, and 3-butoxy-N,N-dimethylpropionamide.

[0040] The amines are not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include monoethanolamine, diethanolamine, and triethylamine.

[0041] The sulfur-containing compound is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include dimethyl sulfoxide, sulfolane, and thiodiethanol.

[0042] The content of the organic solvent is not particularly limited and can be selected appropriately depending on the purpose, but in terms of excellent drying properties, it is preferably 7.0 mass % or less, and more preferably 5.0 mass % or less, of the total amount of the first liquid.

[0043] The water content is not particularly limited and can be selected appropriately depending on the purpose. However, from the viewpoint of the drying property and ejection reliability of the ink, the water content is preferably 10% by mass or more and 90% by mass or less, and more preferably 20% by mass or more and 60% by mass or less, of the total amount of the first liquid.

[0044] -Surfactants- The surfactant contained in the first liquid is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include silicone surfactants, fluorine surfactants, amphoteric surfactants, nonionic surfactants, anionic surfactants, etc. These may be used alone or in combination of two or more.

[0045] Silicone surfactant is not particularly limited, and can be appropriately selected according to purpose.Among these, silicone surfactant is preferably one that does not decompose even at high pH, ​​for example, side chain modified polydimethylsiloxane, both end modified polydimethylsiloxane, one end modified polydimethylsiloxane, side chain both end modified polydimethylsiloxane, etc., and those having polyoxyethylene group or polyoxyethylene polyoxypropylene group as modified group are preferred because they show good properties as aqueous surfactant.In addition, polyether modified silicone surfactant can also be used as silicone surfactant, for example, compound that polyalkylene oxide structure is introduced into Si part side chain of dimethylsiloxane, etc.

[0046] The silicone surfactant may be a synthetic product or a commercially available product. There are no particular restrictions on the commercially available products, and they can be selected appropriately depending on the purpose. Examples include those available from BYK Co., Ltd., Shin-Etsu Chemical Co., Ltd., Dow Corning Toray Silicone Co., Ltd., Nippon Emulsion Co., Ltd., Kyoeisha Chemical Co., Ltd., etc.

[0047] The polyether-modified silicone surfactant is not particularly limited and can be appropriately selected depending on the purpose. For example, it may be a surfactant in which a polyalkylene oxide structure represented by the following general formula (S-1) is introduced into the Si moiety side chain of dimethylpolysiloxane. [ka] (In the general formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R' represents an alkyl group.)

[0048] As the polyether-modified silicone surfactant, commercially available products can be used. The commercially available product is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include KF-618, KF-642, KF-643 (manufactured by Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5602, SS-1906EX (manufactured by Nippon Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (manufactured by Dow Corning Toray Silicone Co., Ltd.), BYK-33, BYK-387 (manufactured by BYK-Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (manufactured by Toshiba Silicon Co., Ltd.), and the like.

[0049] The fluorine-based surfactant is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of low foaming, perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in the side chains, etc. are preferred. These may be used alone or in combination of two or more.

[0050] The perfluoroalkylsulfonic acid compound is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include perfluoroalkylsulfonic acid and perfluoroalkylsulfonic acid salts.

[0051] The perfluoroalkyl carboxylic acid compound is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include perfluoroalkyl carboxylic acids and perfluoroalkyl carboxylates.

[0052] The polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group on the side chain is not particularly limited and can be appropriately selected depending on the purpose. Examples include sulfate ester salts of polyoxyalkylene ether polymers having a perfluoroalkyl ether group on the side chain, and salts of polyoxyalkylene ether polymers having a perfluoroalkyl ether group on the side chain.

[0053] The counter ion of the salt in the fluorosurfactant is not particularly limited and can be selected appropriately depending on the purpose, and examples include Li, Na, K, NH4, NH3CH2CH2OH, NH2(CH2CH2OH)2, NH(CH2CH2OH)3, etc.

[0054] The fluorine-based surfactant is not particularly limited and can be appropriately selected depending on the purpose, but a compound having 2 to 16 fluorine-substituted carbon atoms is preferred, and a compound having 4 to 16 fluorine-substituted carbon atoms is more preferred. Examples of fluorine-based surfactants include perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in the side chains. Among these, polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in the side chains are preferred because of their low foaming properties, and fluorine-based surfactants represented by general formula (F-1) and general formula (F-2) are more preferred. [ka] (In the general formula (F-1), m and n each independently represent an integer.) In the compound represented by formula (F-1), m is preferably an integer of 0 to 10, and n is preferably an integer of 0 to 40, in order to impart water solubility. [ka] (However, in the general formula (F-2), Y is H, C m F 2m+1 (where m is an integer from 1 to 6), CH2CH(OH)CH2-C m F 2m+1 (where m is an integer between 4 and 6), or C p H 2p+1 (wherein p represents an integer of 1 to 19, n represents an integer of 1 to 6, and a represents an integer of 4 to 14.)

[0055] The fluorine-based surfactant may be appropriately synthesized or may be a commercially available product. Commercially available products are not particularly limited and can be appropriately selected depending on the purpose. Examples include Surflon (registered trademark) S-111, S-112, S-113, S-121, S-131, S-132, S-141, and S-145 (all manufactured by AGC Seimi Chemical Co., Ltd.); Fullard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, and FC-431 (all manufactured by Sumitomo 3M Limited); Megafac F-470, F-1405, and F-474 (all manufactured by DIC Corporation); and Zonyl (registered trademark) TBS and FSP. , FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR, Capstone FS-30, FS-31, FS-3100, FS-34, FS-35 (all manufactured by Chemours); Ftergent (FT)-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW (all manufactured by Neos Co., Ltd.), Polyfox (PF)-136A, PF-156A, PF-151N, PF-154, PF-159 (all manufactured by Omnova), Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.), and the like. Among these, FS-3100, FS-34, and FS-300 manufactured by Chemours Corporation, FT-110, FT-250, FT-251, FT-400S, FT-150, and FT-400SW manufactured by Neos Corporation, PF-151N manufactured by Omnova, and Unidyne DSN-403N manufactured by Daikin Industries, Ltd. are particularly preferred, as they provide good print quality, particularly significant improvements in color development, paper penetration, wettability, and dye uniformity.

[0056] The amphoteric surfactant is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, lauryl dihydroxyethyl betaine, etc. These may be used alone or in combination of two or more.

[0057] The nonionic surfactant is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene propylene block polymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, ethylene oxide adducts of acetylene alcohol, etc. These may be used alone or in combination of two or more.

[0058] The anionic surfactant is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include polyoxyethylene alkyl ether acetates, dodecylbenzenesulfonates, laurates, polyoxyethylene alkyl ether sulfates, etc. These may be used alone or in combination of two or more.

[0059] The content of the surfactant is not particularly limited and can be selected appropriately depending on the purpose. However, in order to obtain excellent wettability and ejection stability and improve image quality, the content is preferably 0.001% by mass or more and 5% by mass or less, and more preferably 0.05% by mass or more and 5% by mass or less, relative to the total amount of the first liquid.

[0060] -Coloring materials- The coloring material contained in the first liquid is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include pigments and dyes. The first liquid may contain a coloring material to conceal the color of the object to be coated, but it may also be transparent without containing a coloring material, thereby leaving the color of the object to be coated unchanged.

[0061] The pigment is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include black pigments, yellow pigments, magenta pigments, cyan pigments, white pigments, green pigments, orange pigments, glossy color pigments such as gold and silver, metallic pigments, etc. Among these, white pigments are preferred because they can conceal the color of the coated object.

[0062] Examples of pigments include inorganic pigments and organic pigments. These may be used alone or in combination of two or more. Mixed crystals may also be used.

[0063] The inorganic pigment is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include titanium oxide, iron oxide, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black produced by known methods such as a contact method, a furnace method, or a thermal method.

[0064] The organic pigment is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include polycyclic pigments such as azo pigments, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments, dye chelates such as basic dye chelates and acid dye chelates, nitro pigments, nitroso pigments, aniline black, hollow resin particles, and hollow inorganic particles. Among these, those having good affinity with the solvent are preferred.

[0065] The pigment is not particularly limited and can be appropriately selected depending on the purpose. Examples of the pigment include carbon blacks (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black for black colors, metals such as copper, iron (CI Pigment Black 11), and titanium oxide, and organic pigments such as aniline black (CI Pigment Black 1). Also, examples of the pigments for color include CI 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, and CI Pigment Yellow 214. Range 5, 13, 16, 17, 36, 43, 51, CI Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48:2 (Permanent Red 2B (Ca)), 48:3, 48:4, 49:1, 52:2, 53:1, 57:1 (Brilliant Carmine 6B), 60:1, 63:1, 63:2, 64:1, 81, 83, 88, 101 ( Bengara), 104, 105, 106, 108 (Cadmium Red), 112, 114, 122 (Quinacridone Magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 184, 185, 190, 193, 202, 207, 208, 209, 213, 219, 224, 254, 264, CI Pigment Examples include Rhodamine Lake 1 (Rhodamine Lake), 3, 5:1, 16, 19, 23, 38, CI Pigment Blue 1, 2, 15 (Phthalocyanine Blue), 15:1, 15:2, 15:3, 15:4 (Phthalocyanine Blue), 16, 17:1, 56, 60, 63, and CI Pigment Green 1, 4, 7, 8, 10, 17, 18, 36.

[0066] The pigment is preferably used in a state dispersed in the ink. Methods for dispersing a pigment to obtain an ink include a method of introducing a hydrophilic functional group into the pigment to make it a self-dispersing pigment, a method of dispersing the pigment by coating the surface of the pigment with a resin, and a method of dispersing the pigment using a dispersant. An example of a method for introducing a hydrophilic functional group into a pigment to make it self-dispersible is a method in which a functional group such as a sulfonic group or a carboxyl group is added to a pigment (e.g., carbon) to make it dispersible in water. A method for dispersing a pigment by coating its surface with a resin includes a method in which the pigment is encapsulated 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 used to be coated with resin; uncoated or partially coated pigments may be included. Examples of the method of dispersing using a dispersant include a method of dispersing using a known low-molecular-weight dispersant or a polymeric dispersant, such as a surfactant. Depending on the pigment, the dispersant may be, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, or a nonionic surfactant. RT-100 (nonionic surfactant) manufactured by Takemoto Yushi Co., Ltd., or a sodium naphthalenesulfonate formalin condensate can also be suitably used as a dispersant. One type of dispersant may be used alone, or two or more types may be used in combination.

[0067] The dye is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include acid dyes, direct dyes, reactive dyes, basic dyes, etc. These may be used alone or in combination of two or more. Dyes include, for example, CI Acid Yellow 17, 23, 42, 44, 79, 142, CI Acid Red 52, 80, 82, 249, 254, 289, CI Acid Blue 9, 45, 249, CI Acid Black 1, 2, 24, 94, CI Food Black 1, 2, CI Direct Yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 142, 144, 17 3, CI Direct Red 1, 4, 9, 80, 81, 225, 227, CI Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202, CI Directed Black 19, 38, 51, 71, 154, 168, 171, 195, CI Reactive Red 14, 32, 55, 79, 249, CI Reactive Black 3, 4, 35, etc.

[0068] The content of the coloring material is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 1.0% by mass to 15.0% by mass, more preferably 1.0% by mass to 10.0% by mass, based on the total amount of the first liquid.

[0069] -Other ingredients- The other components are not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include antifoaming agents, antiseptic and antifungal agents, rust inhibitors, pH adjusters, and film-forming aids.

[0070] There are no particular limitations on the method for measuring P99 in the particle size distribution of ISO Max Distance, and it can be selected appropriately depending on the purpose. For example, it can be measured using an injection-type image analysis particle size distribution analyzer IF-3200. Specifically, the ink is diluted with water so that the particles in the ink can be observed, and the ISO Max Distance particle size distribution (P99) based on the number of particles in the ink can be measured in the range of 0.1 μm to 100 μm using an injection-type image analysis particle size distribution analyzer IF-3200. Because the amount of dilution varies depending on the amount and size of the particle components in the ink, it is necessary to adjust the dilution ratio so that the size of each particle in the ink can be observed. If the ink aggregates in water, it can be diluted with a solvent that does not aggregate the ink (such as cyclohexane).

[0071] The glass transition temperature of the dried film of the first liquid (hereinafter sometimes referred to as the "first layer") is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 15°C or lower. The method for measuring the glass transition temperature is not particularly limited and can be appropriately selected depending on the purpose, but it can be measured using a differential scanning calorimeter (TA-60WS and DSC-60, manufactured by Shimadzu Corporation). Specifically, 4 g of the first liquid was spread evenly in a 50 mm diameter petri dish made of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and dried at 50°C for one week to obtain a dried film of the first liquid. 5.0 mg of the obtained dried film of the first liquid was placed in an aluminum sample container, and the sample container was placed on a holder unit and set in an electric furnace. Next, in a nitrogen atmosphere, the temperature is increased from 0°C to 150°C at a rate of 10°C / min, then decreased from 150°C to -80°C at a rate of 5°C / min, and then increased again to 150°C at a rate of 10°C / min to measure the DSC curve. From the obtained DSC curve, the inflection point during the second temperature rise is analyzed by the midpoint method using the analysis program in the DSC-60 system to determine the glass transition point (Tg).

[0072] The resin content in the dried film of the first liquid is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10% by mass or more and 60% by mass or less. The content indicates the content of the solid content of the resin.

[0073] The solid content of the first liquid is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 45% by mass or more, and more preferably 55% by mass or more, in terms of good drying properties and excellent hiding power. The solid content refers to solid components contained in the first liquid, and examples thereof include thickeners, resins, pigments, etc. The method for measuring the solid content is not particularly limited and can be appropriately selected depending on the purpose. For example, the solid content can be measured in accordance with JIS K5601-1-2 after drying at 150°C for 30 minutes.

[0074] The static surface tension of the first liquid is not particularly limited and can be selected appropriately depending on the purpose. However, from the viewpoints of suitably leveling the first liquid on the substrate and shortening the drying time of the first liquid, the static surface tension is preferably 35 m / Nm or less at 25°C, and more preferably 30 m / Nm or less. There are no particular limitations on the method for measuring static surface tension, and it can be selected appropriately depending on the purpose. For example, it can be measured by the Wilhelmy method (plate method) using a platinum plate using an automatic surface tensiometer (DY-300, manufactured by Kyowa Interface Science Co., Ltd.).

[0075] The pH of the first liquid is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 7 or more and 12 or less, more preferably 8 or more and 11 or less, from the viewpoint of preventing corrosion of metal members that come into contact with the liquid.

[0076] The method for producing the first liquid is not particularly limited and can be selected appropriately depending on the purpose. For example, the first liquid can be obtained by dispersing or dissolving the constituent components in an aqueous medium, and further stirring and mixing as necessary. The stirring and mixing can be carried out using, for example, a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser, or the like.

[0077] <Second step and second means> The second step is a step of printing by ejecting a second liquid from a nozzle onto the first liquid attached to the substrate. The second method is a method for printing by ejecting a second liquid from a nozzle onto a first liquid that has adhered to an object to be coated. The second step can be carried out by a second means.

[0078] The method of application is not particularly limited and can be appropriately selected depending on the purpose, but ink-jet method is preferred.

[0079] <<Second Liquid>> The second liquid is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include ink, paint, and treatment liquid. The ink is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include white ink, transparent ink, color ink, etc. Among these, color ink is preferred because it can color the substrate.

[0080] Shear rate of the second liquid at 25°C is 1 s -1 The viscosity of the second liquid at a shear rate of 1 s is preferably 1.5 mPa·s or more and 3.0×10 mPa·s or less, and more preferably 3.0 mPa·s or more and 3.0×10 mPa·s or less. -1 If the viscosity of the second liquid is 1.5 mPa·s or more at a shear rate of 1 s at 25°C, the second liquid will be less likely to bleed when the second liquid is ejected from a nozzle onto the first liquid adhered to the substrate for printing after the first liquid has been adhered to the substrate. -1 If the viscosity at 1000 kJ / s is 3.0 × 10 mPa s or less, the thickness of the second liquid can be thinly spread, and colors such as red, green, and blue can be produced by mixing liquids such as cyan, yellow, and magenta.

[0081] Shear rate of the second liquid at 25°C is 1 s -1 The method for measuring the viscosity in the above step is not particularly limited and can be appropriately selected depending on the purpose. For example, the viscosity can be measured using the same method as for the first liquid.

[0082] The second liquid contains a resin and a solvent, and preferably contains a coloring material and a surfactant, and may further contain other components as necessary.

[0083] -resin- The resin contained in the second liquid is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include, as with the first liquid, urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, styrene-butadiene resin, vinyl chloride resin, acrylic-styrene resin, acrylic-silicone resin, etc. These may be used alone or in combination of two or more. The resin may be resin particles made of these resins, and by dispersing the resin particles in a solvent as a dispersion medium to form a resin emulsion, it is possible to obtain ink by mixing it with materials such as colorants and organic solvents. The resin particles may be appropriately synthesized or commercially available. These may be used alone or in combination of two or more types of resin particles.

[0084] The glass transition temperature of the resin is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 15°C or lower, more preferably 0°C or lower, in order to prevent cracking of the coating film when the coating film is made thick.

[0085] The method for measuring the glass transition temperature is not particularly limited and can be appropriately selected depending on the purpose. The glass transition temperature can be measured using the same method as that for the resin contained in the first liquid.

[0086] The content of the resin is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of excellent fastness of the coating film, it is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 1% by mass or more and 5% by mass or less, relative to the total amount of the second liquid. Note that the content indicates the content of the solid content of the resin.

[0087] -solvent- The solvent contained in the second liquid is not particularly limited and can be appropriately selected depending on the purpose. As with the first liquid, examples thereof include organic solvents and water.

[0088] The organic solvent is not particularly limited and can be appropriately selected depending on the purpose. Examples of the organic solvent include ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, polyhydric alcohols, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene carbonate, and ethylene carbonate.

[0089] The content of the organic solvent is not particularly limited and can be selected appropriately depending on the purpose, but from the viewpoint of excellent drying properties, it is preferably 1.0 mass % or more and 50 mass % or less, and more preferably 3.0 mass % or more and 35.0 mass % or less, relative to the total amount of the second liquid.

[0090] The water content is not particularly limited and can be selected appropriately depending on the purpose. However, from the viewpoint of the drying property and ejection reliability of the ink, the water content is preferably 10% by mass or more and 90% by mass or less, and more preferably 20% by mass or more and 60% by mass or less, of the total amount of the second liquid.

[0091] -Surfactants- The surfactant contained in the second liquid is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include, as in the first liquid, silicone surfactants, fluorine surfactants, amphoteric surfactants, nonionic surfactants, anionic surfactants, etc. These may be used alone or in combination of two or more.

[0092] The content of the surfactant is not particularly limited and can be selected appropriately depending on the purpose. However, in order to obtain excellent wettability and ejection stability and improve image quality, the content is preferably 0.001% by mass or more and 5% by mass or less, and more preferably 0.05% by mass or more and 5% by mass or less, relative to the total amount of the first liquid.

[0093] -Coloring materials- The coloring material is not particularly limited and can be appropriately selected depending on the purpose. As with the first liquid, examples of the coloring material include pigments and dyes.

[0094] The content of the coloring material is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 1.0% by mass to 15.0% by mass, more preferably 1.0% by mass to 10.0% by mass, based on the total amount of the first liquid.

[0095] -Other ingredients- The other components contained in the second liquid are not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include the same components as those in the first liquid.

[0096] The solid content of the second liquid is not particularly limited and can be selected appropriately depending on the purpose, but from the viewpoint of good drying properties, it is preferably 0.1% by mass to 80% by mass, and more preferably 1% by mass to 25% by mass. The solid content refers to solid components contained in the second liquid, and examples thereof include resins and pigments.

[0097] The static surface tension of the second liquid is not particularly limited and can be selected appropriately depending on the purpose, but from the viewpoint of suppressing bleeding in printed matter formed from the first liquid and the second liquid, it is preferably 35 m / Nm or less at 25°C, and more preferably 30 m / Nm or less. The method for measuring the static surface tension is not particularly limited and can be appropriately selected depending on the purpose, but it can be measured by the same method as for the first liquid.

[0098] The difference (CD) between the static surface tension (C) of the first liquid and the static surface tension (D) of the second liquid is not particularly limited and can be selected appropriately depending on the purpose, but from the viewpoint of suppressing bleeding in printed matter formed from the first liquid and the second liquid, it is preferable that the difference (CD) satisfies the following formula (1), and it is more preferable that the difference (CD) satisfies the following formula (2): (Number 1) C(m / Nm)-D(m / Nm)≦10(m / Nm)...Equation (1) (Number 2) C(m / Nm)-D(m / Nm)≦1(m / Nm)...Equation (2)

[0099] The method for producing the second liquid is not particularly limited and can be selected appropriately depending on the purpose. For example, the second liquid can be obtained by dispersing or dissolving the constituent components in an aqueous medium, and further stirring and mixing as necessary. The stirring and mixing can be carried out using, for example, a stirrer using a normal stirring blade, a magnetic stirrer, a high-speed disperser, or the like.

[0100] <Third step and third means> The printing method according to one embodiment of the present invention may include a third step as needed. The third step is a step of printing by ejecting a third liquid from a nozzle onto the second liquid attached to the substrate. The printing device according to one embodiment of the present invention may include a third means, if necessary. The third means is a means for printing by ejecting the third liquid from a nozzle onto the second liquid attached to the substrate. The third step can be carried out by a third means.

[0101] The method of application is not particularly limited and can be appropriately selected depending on the purpose, but ink-jet method is preferred.

[0102] <<The Third Liquid>> The third liquid is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include ink, paint, and treatment liquid. The ink is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include white ink, transparent ink, color ink, etc. Among these, transparent ink is preferred because it can protect the second liquid after drying and improve fastness, and can impart high gloss or matte properties to the surface of the printed matter after drying.

[0103] The viscosity of the third liquid is not particularly limited and can be selected appropriately depending on the purpose, but it is preferable that the viscosity is equivalent to the viscosity of the first liquid and the viscosity of the second liquid described above, since the third liquid can be applied by an inkjet method or a spray method.

[0104] The method for measuring the viscosity of the third liquid is not particularly limited and can be appropriately selected depending on the purpose. For example, the viscosity can be measured using the same method as for the first liquid and the second liquid.

[0105] The third liquid contains a resin and a solvent, and preferably contains a coloring material and a surfactant, and may further contain other components as necessary.

[0106] The resin contained in the third liquid is not particularly limited and can be appropriately selected depending on the purpose. For example, the resin of the first liquid or the resin of the second liquid described above may be used.

[0107] The content of resin contained in the third liquid is not particularly limited and can be selected appropriately depending on the purpose, but may be the content of resin in the first liquid or the content of resin in the second liquid described above.

[0108] The solvent contained in the third liquid is not particularly limited and can be appropriately selected depending on the purpose. For example, the solvent of the first liquid or the solvent of the second liquid described above may be used.

[0109] The content of the solvent is not particularly limited and can be appropriately selected depending on the purpose, but may be the content of the solvent in the first liquid or the content of the solvent in the second liquid described above.

[0110] The surfactant contained in the third liquid is not particularly limited and can be selected appropriately depending on the purpose, and the surfactant in the first liquid or the surfactant in the second liquid described above may be used.

[0111] The content of the surfactant is not particularly limited and can be selected appropriately depending on the purpose, but may be the content of the surfactant in the first liquid or the content of the surfactant in the second liquid described above.

[0112] The coloring material contained in the third liquid is not particularly limited and can be appropriately selected depending on the purpose, and the coloring material of the first liquid or the second liquid described above may be used.

[0113] The content of the coloring material contained in the third liquid is not particularly limited and can be selected appropriately depending on the purpose, but may be the content of the coloring material in the first liquid or the content of the coloring material in the second liquid described above.

[0114] The other components contained in the third liquid are not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include the same components as those in the first liquid.

[0115] The solid content of the third liquid is not particularly limited and can be selected appropriately depending on the purpose, but may be the solid content of the first liquid or the solid content of the second liquid described above.

[0116] (ink set) The ink set according to one embodiment of the present invention has a shear rate of 1 s at 25°C. -1 Viscosity at 1.00 x 10 3 mPa·s or more, and a shear rate of 5,000 s at 25°C -1 Viscosity at 3.50 x 10 2 mPa·s or less and a first liquid at a shear rate of 1 s at 25°C. -1 and a second liquid having a viscosity at 0°C of 3 mPa·s or greater and 3.0×10 mPa·s or greater.

[0117] An ink set according to one embodiment of the present invention is preferably an ink set for printing on porous substrates, which is used for printing on porous substrates.

[0118] An example of an inkjet printing apparatus as a printing apparatus according to an embodiment of the present invention will be described below with reference to the drawings. However, the present invention is not limited to the embodiment described below. FIG. 1 is a schematic side view showing a liquid ejection device as a printing device according to one embodiment of the present invention. FIG. 2 is a schematic plan view showing a liquid ejection device as a printing device according to an embodiment of the present invention. The liquid ejection device 1000 is installed so as to face the printing substrate 100. The carriage a is equipped with a head 300 for ejecting ink, which is an example of a liquid, toward the printing substrate 100. A Z-axis rail 103 holds the carriage a so that the carriage a can move in the Z-axis direction. X-axis rail 101 holds Z-axis rail 103 so that Z-axis rail 103, which holds carriage a, can move in the X-axis direction. Furthermore, Y-axis rail 102 holds X-axis rail 101 so that X-axis rail 101 can move in the Y-axis direction. Here, the X-axis is an example of a "first axis," the Y-axis is an example of a "second axis intersecting the first axis," and the Z-axis is an example of a "third axis intersecting the first and second axes." Furthermore, carriage a is an example of a "liquid ejection unit," and head 300 is an example of a "liquid ejection head."

[0119] The liquid ejection device 1000 includes a Z-direction drive unit 92 that moves the carriage a in the Z-axis direction along the Z-axis rail 103, and an X-direction drive unit 72 that moves the Z-axis rail 103 in the X-axis direction along the X-axis rail 101. The liquid ejection device 1000 also includes a Y-direction drive unit 82 that moves the X-axis rail 101 in the Y-axis direction along the Y-axis rail 102. The Z-direction drive unit 92 is an example of a "first drive means" and moves the carriage a in the Z-axis direction, which intersects with the X-axis and Y-axis. Note that the movement of the carriage a and the head 300 in the Z-axis direction does not have to be parallel to the Z-axis direction, and may be oblique movement as long as it includes at least a component in the Z-axis direction. The carriage a further includes a Z-direction drive unit 93. The Z-direction drive unit 93 is an example of a "second drive means" and moves the head 300 in the Z-axis direction relative to the carriage a. The liquid ejection device 1000 configured as described above ejects ink from the head 300 toward the drawing object 100 while moving the carriage a in the X-axis, Y-axis, and Z-axis directions, thereby drawing on the drawing object 100. Note that although the printing object 100 is shown in the form of a flat plate, it may also be a nearly vertical surface or a surface with a large radius of curvature, such as a car, truck, or airplane.

[0120] --Ink ejection means-- The ink ejection means of the present invention is not particularly limited as long as it is a means for ejecting ink from an inkjet nozzle, but for example, the ink ejection means may include a nozzle hole from which ink is ejected, an ink chamber that supplies pressurized ink to the nozzle hole, and an ejection means that is provided in the ink chamber and controls the ejection by a needle valve that opens and closes the nozzle hole. An example of an inkjet nozzle that realizes this ejection means is the inkjet nozzle described in Japanese Patent No. 4123897, and schematic configuration diagrams of the nozzle are shown in FIGS. 3 and 4.

[0121] (Printed material) The printed matter according to one embodiment of the present invention is a coated object and a coated object to which a shear rate of 1 s at 25°C is applied. -1 Viscosity at 1.00 x 10 3 mPa·s or more, and a shear rate of 5,000 s at 25°C -1 Viscosity at 3.50 x 10 2 A first layer made of a first liquid having a viscosity of less than mPa·s and a shear rate of 1 s at 25°C on the first layer. -1 and a second layer made of a second liquid having a viscosity at 0°C of 3 mPa·s or more and 3.0×10 mPa·s or less.

[0122] (Manufacturing method for printed matter) A method for producing a printed matter according to one embodiment of the present invention is to perform a printing process using a shear rate of 1 s at 25°C. -1 Viscosity at 1.00 x 10 3 mPa·s or more, and a shear rate of 5,000 s at 25°C -1 Viscosity at 3.50 x 10 2 forming a first layer made of a first liquid having a viscosity of not more than mPa·s; and applying a shear rate of 1 s at 25°C to the first layer. -1 and forming a second layer made of a second liquid having a viscosity at 0°C of 3 mPa·s or more and 3.0×10 mPa·s or less.

[0123] The step of forming the first layer can be performed in the same manner as the first step in the printing method according to one embodiment of the present invention.

[0124] The step of forming the second layer can be performed in the same manner as the second step in the printing method according to one embodiment of the present invention.

[0125] <Object to be coated> The substrate (hereinafter sometimes referred to as "substrate", "printed material", etc.) refers to an object to be printed on by a printing method and printing device according to one embodiment of the present invention, and refers to an object to which ink or treatment liquid can be attached, even temporarily. The substrate to be coated is not particularly limited and can be appropriately selected depending on the purpose. Preferred examples include road surfaces, exteriors, floors, porous substrates such as porous substrates, and building sheet materials. The shape, structure, and material of the substrate are not particularly limited and can be selected appropriately depending on the purpose. Examples include siding (ceramic, resin, wood, metal), asphalt, asphalt felt, concrete, glass, cloth, paper, plastic, wood, metal (brass, iron, aluminum, SUS (stainless steel), copper, etc.), and non-metallic substrates that have been metal coated by techniques such as vapor deposition.

[0126] Examples of porous substrates include substrates with high ink permeability, such as asphalt and sponge.

[0127] In the present invention, the terms image formation, recording, printing, printing, etc. are all synonymous. Recording medium, media, and printed material are all synonymous terms. [Example]

[0128] Examples of the present invention will be described below, but the present invention is not limited to these examples in any way.

[0129] <Pigment Dispersion Preparation Example 1> A mixture of 200 parts by mass of CI Pigment White 6 (manufactured by Teika Corporation, product name "JR-403," number average primary particle diameter 250 nm, aspect ratio 2, surface treatment: Al, Si) as a pigment, 56 parts by mass of a pigment dispersant (product name: TEGO Dispers 651, manufactured by Evonik Corporation), and 744 parts by mass of distilled water was premixed. Then, using a bead mill disperser (Kotobuki Industries Co., Ltd., UAM-015), zirconia beads with a diameter of 0.03 mm (density 6.03 × 10 -6 g / m 2 ) at a peripheral speed of 10 m / s and a liquid temperature of 30°C for 15 minutes, and then coarse particles were separated by centrifugation using a centrifuge (Model-3600, manufactured by Kubota Shoji Co., Ltd.) to obtain White Pigment Dispersion 1 (solid content 20.0% by mass) with an average particle size of 250 nm.

[0130] <Pigment Dispersion Preparation Example 2> Yellow Pigment Dispersion 1 (solid content 25.0% by mass) having an average particle size of 90 nm was obtained in the same manner as in Pigment Dispersion Preparation Example 1, except that CI Pigment White 6 in Pigment Dispersion Preparation Example 1 was changed to Pigment Yellow 110 (Corimax Yellow 3RL, manufacturer: ZEYA CHEMICALS (HAIMEN) CO., LTD.).

[0131] <Pigment Dispersion Preparation Example 3> Cyan pigment dispersion 1 (solid content 20.0% by mass) having an average particle size of 80 nm was obtained in the same manner as in pigment dispersion preparation example 1, except that CI pigment white 6 in pigment dispersion preparation example 1 was changed to pigment blue 15:3 (Cyanine blue A-385, manufactured by Dainichi Seika Chemicals Co., Ltd.).

[0132] <Pigment Dispersion Preparation Example 4> Magenta pigment dispersion 1 (solid content 20.0% by mass) having an average particle size of 120 nm was obtained in the same manner as in pigment dispersion preparation example 1, except that CI pigment white 6 in pigment dispersion preparation example 1 was changed to pigment red 122 (manufactured by Ciba Specialty Chemicals, Cromophtal JET Magenta DMQ).

[0133] <Resin emulsion preparation example 1> A mixture of 55.4 parts by mass of methyl methacrylate as a monomer, 44.6 parts by mass of 2-ethylhexyl acrylate, 1.5 parts by mass of Aqualon KH-20 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an emulsifier, and 53.1 parts by mass of ion-exchanged water was emulsified in a batch homomixer to prepare a monomer pre-emulsion. 89.4 parts by mass of ion-exchanged water was placed in a 2 L four-neck flask equipped with a stirrer, a nitrogen inlet tube, a reflux condenser, a thermometer, and a raw material inlet, and the liquid temperature was heated to 60°C while introducing nitrogen and stirring. Into a reaction vessel, 0.5 parts by mass of Aqualon KH-20 as an emulsifier and 6 parts by mass of a 5% aqueous solution of ammonium persulfate (0.3 parts by mass of ammonium persulfate) were added. Thereafter, 10 minutes after the addition of the 5% aqueous ammonium persulfate solution to the reaction vessel, the monomer pre-emulsion was continuously added dropwise from a dropping tank over a period of 5 hours, and 6 parts of a 5% aqueous ammonium persulfate solution (0.3 parts as ammonium persulfate) was intermittently added dropwise from another dropping tank over a period of 5 hours at 70°C. After the dropwise addition, the mixture was kept at 70°C for 3 hours for aging. Thereafter, the mixture was cooled to 50°C, and aqueous ammonia was added thereto. The mixture was filtered through a 180-mesh polyester filter cloth to obtain a resin emulsion A. A portion of the obtained resin emulsion A was dried at 150°C for 30 minutes, and the solid content was measured in accordance with JIS K5601-1-2 and found to be 50.0%. The glass transition temperature of resin emulsion A was measured by the following method and found to be 0°C.

[0134] <Measurement of the glass transition temperature (Tg) of resin emulsion> 4 g of the resin emulsion was evenly spread in a 50 mm diameter petri dish made of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) and dried at 50°C for one week to obtain a resin film. 5.0 mg of the obtained resin film was placed in an aluminum sample container, which was then placed on a holder unit and set in an electric furnace. Next, under a nitrogen atmosphere, the temperature was raised from 0°C to 150°C at a rate of 10°C / min, then lowered from 150°C to -80°C at a rate of 5°C / min, and then further raised to 150°C at a rate of 10°C / min, and the DSC curve was measured. From the obtained DSC curve, the inflection point during the second temperature rise was analyzed by the midpoint method using the analysis program in the DSC-60 system to determine the glass transition temperature (Tg).

[0135] (Synthesis Example 1 of First Liquid) 3.0% by mass of propylene glycol and 9.3% by mass of ion-exchanged water as a solvent, 31.0% by mass of Resin Emulsion A as a resin, 20.0% by mass of White Pigment Dispersion 1 as a colorant, and 0.7% by mass of FS-300 as a surfactant were mixed and stirred for 30 minutes to become uniform, and 36.0% by mass of calcium carbonate (UP-G, manufactured by Imerys Specialties Japan Co., Ltd., solids content: 100% by mass) as a thickener was added, and the mixture was stirred at high speed for another hour to become uniform, thereby obtaining a first liquid 1. The viscosity, solid content, and static surface tension of the obtained First Liquid 1 were measured by the following methods. The measurement results are shown in Table 1.

[0136] <Viscosity> -25℃, shear rate 1S -1 , 5,000S -1 and 0.1S -1 Viscosity at - The first liquid 1 was subjected to shear at a shear rate of 1 s using a cone plate (cone radius: 25 mm, cone angle: 1°) in an MCR301 (manufactured by Anton Parr). -1 Viscosity (mPa·s) at 25°C and shear rate of 5,000 S -1 Viscosity (mPa·s) at 25°C and shear rate of 0.1S -1 The viscosity (mPa·s) at 25°C was measured.

[0137] <Solid content> A portion of the obtained first liquid 1 was dried at 150° C. for 30 minutes, and the solid content concentration was measured in accordance with JIS K5601-1-2.

[0138] <Static surface tension> The static surface tension of the first liquid 1 was measured by the Wilhelmy method (plate method) using a platinum plate, using an automatic surface tensiometer (DY-300, manufactured by Kyowa Interface Science Co., Ltd.).

[0139] (Synthesis Examples 2 to 12 of First Liquid) First Liquids 2 to 12 were obtained in the same manner as in First Liquid Synthesis Example 1, except that the composition of the first liquid was changed to the compositions shown in Tables 1 and 2 below. Furthermore, the viscosity, solid content, and static surface tension of the obtained First Liquids 2 to 12 were measured in the same manner as in First Liquid Synthesis Example 1. The measurement results are shown in Tables 1 and 2.

[0140] [Table 1]

[0141] [Table 2]

[0142] (Synthesis Example 1 of Second Liquid) A mixture of 22.0% by weight of glycerin, 11.0% by weight of 1,3-butanediol, and 2.0% by weight of 1,3-octanediol as solvents, 1.0% by weight of Wet-270 as surfactant, and 54.0% by weight of ion-exchanged water was mixed and stirred for 30 minutes to achieve uniformity. 2.0% by weight of Hamalic R-100 (rosin-modified maleic acid resin, solids content: 100% by weight) was added and stirred for an additional hour to achieve uniform mixing. 8.0% by weight of Cyan Pigment Dispersion 1 as colorant was then added and stirred for an additional hour to achieve uniform mixing. This mixture was pressure-filtered through a polyvinylidene fluoride membrane filter with an average pore size of 0.8 μm to remove coarse particles and debris, yielding Second Liquid 1. The viscosity, solid content concentration, and static surface tension of the obtained Second Liquid 1 were measured in the same manner as in First Liquid Synthesis Example 1. In addition, the viscosity was measured using an E-type viscometer by the method shown below.

[0143] - Viscosity measured using a cone-and-plate rotational viscometer - The second liquid was measured using a cone-plate type rotational viscometer (RE-85L, manufactured by Toki Sangyo Co., Ltd.) with a cone plate (cone radius: 24 mm, cone angle: 1°34').

[0144] (Synthesis Examples 2 to 9 of Second Liquid) Second Liquids 2 to 9 were obtained in the same manner as in Second Liquid Synthesis Example 1, except that the composition of the second liquid was changed to the compositions shown in Tables 3 and 4 below. The viscosity, solids concentration, and static surface tension of the obtained second liquids 2 to 9 were measured in the same manner as in Second Liquid Synthesis Example 1. The measurement results are shown in Tables 3 and 4.

[0145] [Table 3]

[0146] [Table 4]

[0147] (Examples 1 to 18 and Comparative Examples 1 to 3) In Examples 1 to 18 and Comparative Examples 1 to 3, the first liquid and the second liquid were combined as shown in Tables 5 to 7 below to form ink sets 1 to 18.

[0148] Printed materials were produced using ink sets 1 to 21 in Examples 1 to 18 and Comparative Examples 1 to 3, respectively. Specifically, a first liquid was applied to a substrate (open-graded asphalt mixture) using either an inkjet method, a spray method, or a brush coating method to form a first layer on the substrate. Then, a second liquid was applied to the first layer using the inkjet method to form a second layer (a 3 cm x 3 cm solid image) on the first layer, thereby obtaining a printed material. When applying the first liquid to the substrate (open-graded asphalt), it was difficult to measure the thickness of the film formed by the first liquid on the substrate (open-graded asphalt) because the substrate was porous. Therefore, the second liquid was placed in a Teflon (registered trademark) dish in advance and allowed to dry. The amount of the first liquid applied per unit area that would result in a film thickness of 250 μm when dry was confirmed, and the first liquid was applied to the substrate (open-graded asphalt) in that amount. When applying the second liquid to the first layer using the inkjet method, the second liquid was first applied to a non-permeable film using the inkjet method, and the amount of the first liquid applied per unit area that would result in a film thickness of 1 μm when dried was confirmed, and the second liquid was applied to the first layer in that amount. For printing the first liquid using the inkjet method, a Leta Robo head (the head installed in Leta Robo, manufactured by Ricoh Digital Painting Co., Ltd.) was modified to have a nozzle diameter of 600 μm, and a liquid ejection device such as that shown in Figures 1 and 2 was used. For printing using the spray method, an airless spray gun with a nozzle diameter of 1.5 mm was used. In addition, for printing the second liquid using the inkjet method, a Leta Robo head (the head installed in Leta Robo, manufactured by Ricoh Digital Painting Co., Ltd.) was modified to have a nozzle diameter of 60 μm, and a liquid ejection device such as that shown in Figures 1 and 2 was used. The resulting prints were evaluated for "bleeding," "opacity," and "color unevenness." The evaluation results are shown in Tables 5 to 7. Tables 5 to 7 also show the difference (CD) between the static surface tension (C) of the first liquid and the static surface tension (D) of the second liquid for ink sets 1 to 21.

[0149] <Concealment> The resulting printed matter was evaluated for "hiding ability" based on the following evaluation criteria. A rating of "B" or higher is considered to be within the practical range. The results are shown in Tables 5 to 7. Items with a rating of "-" were not tested. In addition, for Examples 16 to 18, the first liquid could not be ejected by the inkjet method. [Evaluation criteria] A: The same color as when printed on white paper can be reproduced, and the coated object is completely hidden. B: The color changes slightly compared to when printed on white paper, but the coated object is sufficiently hidden. C: The color is significantly different from when printed on white paper, and the coated object is not concealed.

[0150] <Bleeding> The resulting printed matter was evaluated for "bleeding" based on the following evaluation criteria. A rating of "B" or higher is within the practical range. The results are shown in Tables 5 to 7. Items with a rating of "-" were not tested. In addition, for Examples 16 to 18, the first liquid could not be ejected by the inkjet method. [Evaluation criteria] A: No bleeding was observed even when observed from a distance of 30 cm from the coated object, and it was very good. B: No bleeding is visible even when observed from a distance of more than 30 cm and up to 1 m from the coated object, and the result is good. C: No bleeding is visible even when observed from a distance of more than 1m but less than 3m from the coated object. D: Bleeding is visible when observed from a distance of 3m from the coated object.

[0151] <Color unevenness> The resulting printed matter was evaluated for "color unevenness" based on the following evaluation criteria. A rating of "B" or higher is within the practical range. The results are shown in Tables 5 to 7. Items with a rating of "-" were not tested. In addition, for Examples 16 to 18, the first liquid could not be ejected by the inkjet method. [Evaluation criteria] A: The color unevenness is not noticeable to the naked eye. B: The color unevenness is slightly noticeable when visually inspected. C: Color unevenness is noticeable to the naked eye.

[0152] [Table 5]

[0153] [Table 6]

[0154] [Table 7]

[0155] The embodiments of the present invention are as follows, for example. <1> On the substrate, a shear rate of 1 s at 25°C -1 Viscosity at 1.00 x 10 3 mPa·s or more, and a shear rate of 5,000 s at 25°C -1 Viscosity at 3.50 x 10 2 a first step of applying a first liquid having a viscosity of 0.05 mPa·s or less; a second step of printing a second liquid by ejecting it from a nozzle onto the first liquid attached to the substrate; The printing method is characterized by comprising: <2> The first liquid is subjected to a shear rate of 5,000 s at 25°C. -1 The viscosity at 3.00 x 10 2 mPa·s or less, <1> This is a printing method described in <3> The first liquid is subjected to a shear rate of 5,000 s at 25°C.-1 The viscosity at 1.30 x 10 2 mPa·s or less, <1> or <2> This is a printing method described in <4> The shear rate of the first liquid at 25°C is 1 s -1 The viscosity at 3.00 x 10 3 mPa·s or more, <1> from <3> 10. The printing method according to claim 9, wherein the ink is a liquid. <5> The shear rate of the first liquid at 25°C is 0.1 s -1 The viscosity at 3.00 x 10 4 mPa·s or more, <1> from <4> 10. The printing method according to claim 9, wherein the ink is a liquid. <6> The static surface tension (C)m / Nm of the first liquid and the static surface tension (D)m / Nm of the second liquid satisfy the following formula (1): <1> from <5> 10. The printing method according to claim 9, wherein the ink is a liquid. (Number 3) C(m / Nm)-D(m / Nm)≦10(m / Nm)...Equation (1) <7> The static surface tension (C)m / Nm of the first liquid and the static surface tension (D)m / Nm of the second liquid satisfy the following formula (2): <1> from <6> 10. The printing method according to claim 9, wherein the ink is a liquid. (Number 4) C(m / Nm)-D(m / Nm)≦1(m / Nm)...Equation (2) <8> The shear rate of the second liquid at 25°C is 1 s -1 The viscosity is 3 mPa s or more and 3.0 × 10 mPa s or more. <1> from <7> 10. The printing method according to claim 9, wherein the ink is a liquid. <9> the first liquid having a thickening agent; <1> from <8> 10. The printing method according to claim 9, wherein the ink is a liquid. <10> The solid content of the first liquid is 40% by mass or more. <1> from <9> 10. The printing method according to claim 9, wherein the ink is a liquid. <11> The substrate is a porous substrate. <1> from <10> 10. The printing method according to claim 9, wherein the ink is a liquid. <12> At least one of the first liquid and the second liquid is ejected onto the substrate by an inkjet method. <1> from <11> 10. The printing method according to claim 9, wherein the ink is a liquid. <13> On the substrate, a shear rate of 1 s at 25°C -1 Viscosity at 1.00 x 10 3 mPa·s or more, and a shear rate of 5,000 s at 25°C -1 Viscosity at 3.50 x 10 2 a first means for applying a first liquid having a viscosity of 0.05 mPa·s or less; a second means for printing by ejecting a second liquid from a nozzle onto the first liquid attached to the substrate; The printing device is characterized by comprising: <14> Shear rate 1 s at 25°C -1 Viscosity at 1.00 x 10 3 mPa·s or more, and a shear rate of 5,000 s at 25°C -1 Viscosity at 3.50 x 10 2 a first liquid having a viscosity of less than or equal to mPa·s; Shear rate 1 s at 25°C -1 a second liquid having a viscosity of 3 mPa s or more and 3.0 × 10 mPa s at The ink set is characterized by comprising: <15> <14> The ink set according to The ink set for printing on porous substrates is characterized by being used for printing on porous substrates. <16> Shear rate 1 s at 25°C -1 Viscosity at 1.00 x 10 3 mPa·s or more, and a shear rate of 5,000 s at 25°C -1 Viscosity at 3.50 x 10 2 forming a first layer made of a first liquid having a viscosity of 0.05 mPa·s or less; On the first layer, a shear rate of 1 s at 25°C was applied. -1 forming a second layer made of a second liquid having a viscosity at 1000 rpm of 3 mPa s to 3.0×10 mPa s; The method for producing a printed matter is characterized by comprising the steps of: [Explanation of symbols]

[0156] 1 Base 2 nozzle holes 3 ink chamber 4 needle valve 5 Ink input passage 6 Ink output passage 7 Elastic diaphragm 8 moving core 9 Drive mechanism housing space 10 Spring material 11 Fixed core 12 Solenoid 13 Pressurized passage 14 Screw rattle prevention spring 15 Gap adjustment bolt 16 Nut 17 Ink tank 18 Pump 20 Circulation path 400 Image forming device 401 Exterior of image forming device 401c Device body cover 404 Cartridge Holder 410 Main Tank 410k, 410c, 410m, 410y Main tanks for black (K), cyan (C), magenta (M), and yellow (Y) 411 Ink storage unit 413 Ink outlet 414 Storage container case 420 Mechanism Department 434 Discharge Head 436 Supply Tube [Prior art documents] [Patent documents]

[0157] [Patent Document 1] Patent No. 5337351

Claims

1. On the substrate, a shear rate of 1 s at 25°C －１ The viscosity at 1.00 x 10 ３ mPa·s or more, and a shear rate of 5,000 s at 25°C －１ The viscosity at 3.50 x 10 ２ a first step of applying a first liquid having a viscosity of 0.05 mPa·s or less; a second step of printing a second liquid by ejecting it from a nozzle onto the first liquid attached to the substrate; A printing method comprising:

2. The shear rate of the first liquid at 25°C is 5,000 s －１ The viscosity at 3.00 x 10 ２ The printing method according to claim 1 , wherein the viscosity is 0.05 mPa·s or less.

3. The shear rate of the first liquid at 25°C is 1 s －１ The viscosity at 3.00 x 10 ３ The printing method according to claim 1 or 2, wherein the viscosity is 100 mPa·s or more.

4. The shear rate of the first liquid at 25°C is 0.1 s －１ The viscosity at 3.00 x 10 ４ The printing method according to claim 1 or 2, wherein the viscosity is 100 mPa·s or more.

5. 3. The printing method according to claim 1, wherein the static surface tension (C)m / Nm of the first liquid and the static surface tension (D)m / Nm of the second liquid satisfy the following formula (1): (Equation 1) C(m / Nm)-D(m / Nm)≦10(m / Nm)...Formula (1)

6. The shear rate of the second liquid at 25°C is 1 s －１ 3. The printing method according to claim 1, wherein the viscosity at 1000 kJ / s is 3 mPa·s or more and 3.0×10 mPa·s or less.

7. The printing method according to claim 1 or 2, wherein the first liquid has a solid content of 40% by mass or more.

8. The printing method according to claim 1 or 2, wherein the substrate is a porous substrate.

9. The printing method according to claim 1 or 2, wherein at least one of the first liquid and the second liquid is ejected onto the substrate by an inkjet method.

10. Shear rate 1 s at 25 ° C －１ The viscosity at 1.00 x 10 ３ mPa·s or more, and a shear rate of 5,000 s at 25°C －１ The viscosity at 3.50 x 10 ２ a first liquid having a viscosity of 0.05 mPa·s or less; Shear rate 1 s at 25 ° C －１ a second liquid having a viscosity of 3 mPa s or more and 3.0 × 10 mPa s at An ink set comprising:

11. Shear rate 1 s at 25 ° C －１ The viscosity at 1.00 x 10 ３ mPa·s or more, and a shear rate of 5,000 s at 25°C －１ The viscosity at 3.50 x 10 ２ forming a first layer made of a first liquid having a viscosity of 0.1 mPa·s or less; On the first layer, a shear rate of 1 s at 25°C was applied. －１ forming a second layer made of a second liquid having a viscosity at 3 mPa s or more and 3.0 × 10 mPa s or less; A method for producing a printed matter, comprising:

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