Pretreatment liquid, printing method, and printer

Abstract

To provide a pretreatment liquid with which it is possible to obtain a printed matter excellent in ink bleeding prevention and color development even by wet-on-wet system.SOLUTION: A pretreatment liquid includes: a high-boiling point solvent whose boiling point is 101°C or above; a low-boiling point solvent whose boiling point is 50-95°C; a coagulant, and water. A content of the low-boiling point solvent whose boiling point is 50-95°C is 10-20 mass% with respect to a total amount of the pretreatment liquid.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a pretreatment liquid, a printing method, and a printing apparatus. [Background technology]

[0002] In recent years, it has been known that in inkjet printing using textile inks, the color development and texture of the resulting printed image can be improved by applying a pretreatment liquid to the fabric, which is the medium to be printed on. The application of the pretreatment liquid can broaden the range of types of fabric, which is the medium to be printed on, and is expected to improve media compatibility. Various methods are used to apply the pretreatment liquid to the medium to be printed, such as a wet-on-dry method that includes a drying process using a heat source after application of the pretreatment liquid, and a wet-on-wet method that does not include a drying process using a heat source after application of the pretreatment liquid and includes a drying process at room temperature.

[0003] For example, in order to suppress the occurrence of image defects such as bleeding and color unevenness and to obtain a high-quality image with sufficient image density, a pretreatment liquid has been proposed in which the content of organic solvents having a boiling point of 180° C. or higher is 15% by weight or less (see, for example, Patent Document 1). Furthermore, in order to provide a method for manufacturing an inkjet recording sheet that can improve productivity without causing cracks in the colorant receiving layer or uneven gloss, a method for manufacturing an inkjet recording sheet that specifies the drying air temperature of the coating film in the wet-on-wet process has been proposed (see, for example, Patent Document 2). Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a pretreatment liquid that can give printed matter that is excellent in bleeding prevention properties and color development even when using a wet-on-wet method. [Means for solving the problem]

[0005] The pretreatment liquid of the present invention, as a means for solving the above-mentioned problems, is a pretreatment liquid containing a high-boiling point solvent having a boiling point of 101°C or more, a low-boiling point solvent having a boiling point of 50°C or more and 95°C or less, a coagulant, and water, and the content of the low-boiling point solvent having a boiling point of 50°C or more and 95°C or less is 10% by mass or more and 20% by mass or less with respect to the total amount of the pretreatment liquid. Effect of the Invention

[0006] According to the present invention, it is possible to provide a pretreatment liquid that can obtain printed matter that is excellent in bleeding prevention properties and color development even in a wet-on-wet system. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic diagram showing an embodiment of a printing device according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] In conventional printing methods, particularly printing methods using a wet-on-wet method, ink droplets may land on the pretreatment liquid applied to the medium before it has dried sufficiently, since the method does not involve a drying process using a heat source. This may result in bleeding or unevenness in the printed image, which may reduce image quality. In addition, when the pretreatment liquid is not sufficiently dried, the metal ion concentration in the pretreatment liquid is lower than when the pretreatment liquid is sufficiently dried, which may result in poor color development of the printed image.

[0009] In the inventions described in the above Patent Documents 1 and 2, no consideration was given to a pretreatment liquid capable of obtaining printed matter having excellent bleeding prevention properties and color development properties, and there was room for further improvement.

[0010] The pretreatment liquid of the present invention contains a high-boiling point solvent having a boiling point of 101° C. or more, a low-boiling point solvent having a boiling point of 50° C. or more and 95° C. or less, a flocculant, and water, and the content of the low-boiling point solvent having a boiling point of 50° C. or more and 95° C. or less is 10% by mass or more and 20% by mass or less with respect to the total amount of the pretreatment liquid. Such a configuration can sufficiently resolve the above-mentioned concerns in the conventional technology. More specifically, by using the pretreatment liquid, even if the printing method is a wet-on-wet method, a printed matter having excellent bleeding prevention properties and color development can be obtained. In addition, although details will be described later, by applying the pretreatment liquid to a printing device and a printing method, a printing device and a printing method having excellent ejection stability can be realized.

[0011] The present invention will now be described in detail.

[0012] (Pretreatment solution) The pretreatment liquid of the present invention contains a high-boiling point solvent having a boiling point of 101°C or higher, a low-boiling point solvent having a boiling point of 50°C or higher and 95°C or lower, a coagulant, and water, and may contain other components (A) as necessary. The pretreatment liquid may or may not contain a coloring material.

[0013] <High boiling point solvent> In this specification, a high boiling point solvent refers to a solvent having a boiling point of 101° C. or higher. When the pretreatment liquid contains the high boiling point solvent, nozzle clogging is suppressed and ejection stability is improved in the pretreatment liquid application step (means) described below, which is preferable. This is particularly preferable when the pretreatment liquid application means is an inkjet.

[0014] The high boiling point solvent is not particularly limited and may be appropriately selected depending on the purpose as long as it has a boiling point (bp) of 101° C. or more, and examples thereof include glycerin (bp; 200° C.), caprolactam (bp; 270° C.), 2-pyrrolidone (bp; 245° C.), propylene glycol (bp; 188.2° C.), etc. Among these, from the viewpoint of improving the ejection stability, a high boiling point solvent having a boiling point of 150° C. or more is preferred.

[0015] The content of the high-boiling point solvent is not particularly limited and can be appropriately set depending on the purpose, but is preferably 5% by mass or more and 25% by mass or less with respect to the total amount of the pretreatment liquid. The content of the high-boiling point solvent having a boiling point of 150° C. or higher is not particularly limited and can be appropriately set depending on the purpose. From the viewpoint of improving the ejection stability, however, it is preferably 5% by mass or more and 15% by mass or less with respect to the total amount of the pretreatment liquid.

[0016] <Low boiling point solvent> In this specification, the low boiling point solvent refers to a solvent having a boiling point of 50°C or higher and 95°C or lower. When the low-boiling point solvent is contained in the pretreatment liquid, volatility is imparted to the pretreatment liquid, and the drying property of the pretreatment liquid at room temperature is improved. Specifically, in a printing method using a wet-on-wet method, the pretreatment liquid may not dry sufficiently between the time when the pretreatment liquid is applied and the time when the ink lands, which may cause problems such as bleeding and deterioration of color development. However, when the low-boiling point solvent is contained in the pretreatment liquid, the drying property of the pretreatment liquid at room temperature is improved, which is preferable because it can eliminate such problems.

[0017] The low-boiling point solvent is not particularly limited and may be appropriately selected depending on the purpose as long as it has a boiling point of 50° C. or more and 95° C. or less, and examples thereof include 2-propanol (bp; 82.4° C.), ethanol (bp; 78.4° C.), acetone (bp; 56.0° C.), etc. Among these, from the viewpoint of improving drying properties (i.e., bleeding prevention properties and color development properties), low-boiling point solvents having a boiling point of 50° C. or more and 70° C. or less are preferred.

[0018] In the pre-treatment liquid of the present invention, the content of the low boiling point solvent is 10% by mass or more and 20% by mass or less based on the total amount of the pre-treatment liquid. From the viewpoint of improving drying properties, the content of the low boiling point solvent is preferably 15% by mass or more and 20% by mass or less based on the total amount of the pre-treatment liquid. The content of the low-boiling point solvent having a boiling point of 50° C. or more and 70° C. or less is not particularly limited and can be appropriately set depending on the purpose. From the viewpoint of improving drying properties, the content is preferably 10% by mass or more and 20% by mass or less, and more preferably 15% by mass or more and 20% by mass or less, based on the total amount of the pre-treatment liquid.

[0019] The low-boiling solvent is not particularly limited and may be appropriately selected depending on the purpose, but is preferably a non-polar solvent or an aprotic solvent. If the low-boiling solvent is a non-polar solvent or an aprotic solvent, the metal ions can be prevented from coagulating and precipitating when the low-boiling solvent volatilizes, which is preferable because it can prevent deterioration in the quality of the printed image and improves the ejection stability in the pretreatment liquid application step (means) described later.

[0020] The non-polar solvent is not particularly limited and can be appropriately selected depending on the purpose. Examples of the non-polar solvent include hexane, benzene, toluene, and ethyl acetate. The aprotic solvent is not particularly limited and can be appropriately selected depending on the purpose. Examples of the aprotic solvent include acetone, tetrahydrofuran, and dimethyl sulfoxide.

[0021] <Flocculant> The aggregating agent is preferably contained in the pretreatment liquid because it quickly aggregates the pigment after the ink has landed, suppresses color bleeding, and improves color development. The flocculant is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include water-soluble cationic polymers, acids, polyvalent metal compounds, etc. Among these, polyvalent metal compounds are preferred.

[0022] The polyvalent metal compound is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include titanium compounds, chromium compounds, copper compounds, cobalt compounds, strontium compounds, barium compounds, iron compounds, aluminum compounds, calcium compounds, magnesium compounds, nickel compounds, and salts thereof (polyvalent metal salts), etc. Among these, from the viewpoint of more effectively agglomerating the pigment in the ink and improving color development, those containing divalent or trivalent metal ions using the polyvalent metal compound as a metal ion source are preferred. Among the above-mentioned polyvalent metal compounds, from the viewpoint of being able to more effectively aggregate the pigment in the ink, it is preferable that the polyvalent metal compound contains one or more compounds selected from calcium compounds, magnesium compounds, and nickel compounds, and it is more preferable that the polyvalent metal compound contains one or more compounds containing an alkaline earth metal, such as a calcium compound or a magnesium compound.

[0023] Specific examples of the polyvalent metal salt include calcium carbonate, calcium nitrate, calcium chloride, calcium acetate, calcium sulfate, magnesium chloride, magnesium acetate, magnesium sulfate, barium sulfate, zinc sulfide, zinc carbonate, aluminum silicate, calcium silicate, magnesium silicate, aluminum hydroxide, potassium nitrate, etc. Among these, nitrates are preferred from the viewpoint of improving ejection stability in the pretreatment liquid application step (means) described below due to their high solubility in the solvent and their difficulty in precipitating after the solvent volatilizes. Among the above-mentioned polyvalent metal salts, it is preferable to include a calcium salt from the viewpoint of improving the stability of the reaction liquid, and it is preferable to use a calcium salt or a magnesium salt from the viewpoint of solubility in the pretreatment liquid and suppression of whitening of the pretreatment liquid film when applied to a non-permeable substrate.

[0024] The molar concentration of the aggregating agent is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of achieving good ejection stability, however, it is preferably 0.1 mol / kg or more and 1.2 mol / kg or less, and more preferably 0.1 mol / kg or more and 0.5 mol / kg or less. In this specification, the term "molar concentration" refers to the number of moles of a solute per kg of solvent (high boiling point solvent, low boiling point solvent, and water).

[0025] The flocculant may be a properly synthesized one or a commercially available product, such as calcium nitrate tetrahydrate (divalent metal salt), sodium chloride (monovalent metal salt), potassium nitrate (monovalent metal salt), calcium chloride (divalent metal salt), and aluminum chloride (trivalent metal salt) (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0026] <Water> The water is not particularly limited and can be appropriately selected depending on the purpose. The content of the water is not particularly limited and can be appropriately set depending on the content of the pretreatment liquid material described above.

[0027] <Other ingredients (A)> In addition to the components described above, the pretreatment liquid may contain other components (A) as necessary. The other components (A) are not particularly limited and may be appropriately selected depending on the purpose. Examples of the other components (A) include surfactants, antifoaming agents, pH adjusters, antiseptic and antifungal agents, and rust inhibitors.

[0028] --Surfactants-- The pretreatment liquid is not particularly limited and can be appropriately selected according to the purpose, but preferably contains an ionic surfactant. When the pretreatment liquid contains an ionic surfactant, the solubility of metal ions is improved, so that even after the low boiling point solvent is evaporated, the aggregation and precipitation of the metal ions can be suppressed, which is preferable. In addition, the ejection stability in the pretreatment liquid application step (means) described later is improved accordingly, which is preferable.

[0029] The ionic surfactant is not particularly limited and can be appropriately selected depending on the purpose. Examples of the ionic surfactant include cationic surfactants, anionic surfactants, and amphoteric surfactants. Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, and imidazolinium salts. Examples of the anionic surfactant include fatty acid soap, N-acyl-N-methylglycine salts, N-acyl-N-methyl-β-alanine salts, N-acylglutamates, alkyl ether carboxylates, acylated peptides, alkyl sulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, dialkylsulfosuccinate salts, alkylsulfoacetates, α-olefinsulfonates, N-acylmethyltaurines, sulfated oils, higher alcohol sulfate salts, secondary higher alcohol sulfate salts, alkyl ether sulfates, secondary higher alcohol ethoxy sulfates, polyoxyethylene alkylphenyl ether sulfate salts, monoglycerates, fatty acid alkylolamide sulfate salts, alkyl ether phosphate salts, and alkyl phosphate salts. Examples of the amphoteric surfactant include carboxybetaine type, sulfobetaine type, aminocarboxylate, and imidazolinium betaine. These surfactants may be used alone or in combination of two or more.

[0030] As the surfactant, in addition to those mentioned above, for example, any of silicone surfactants, fluorosurfactants, acetylene glycol surfactants, amphoteric surfactants (excluding the above), nonionic surfactants (excluding the above), and anionic surfactants (excluding the above) can be used.

[0031] The silicone surfactant is not particularly limited and can be appropriately selected according to the purpose, but it is preferable that it does not decompose even at high pH (pH 11 to 14). Examples of the silicone surfactant that does not decompose even at high pH (pH 11 to 14) include side chain modified polydimethylsiloxane, both end modified polydimethylsiloxane, one end modified polydimethylsiloxane, and both end modified polydimethylsiloxane of side chain. Among these, from the viewpoint of improving hydrophilicity and increasing solubility in water, it is preferable to use a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group.

[0032] Such surfactants may be appropriately synthesized or commercially available products, such as those available from BYK-Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Dow Corning Toray Silicone Co., Ltd., Nippon Emulsion Co., Ltd., and Kyoeisha Chemical Co., Ltd.

[0033] As the silicone surfactant, a polyether-modified silicone surfactant can also be used. 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 part side chain of dimethylpolysiloxane.

[0034] [ka] (In the general formula (S-1), m, p, a, and b each independently represent an integer, R represents an alkylene group, and R' represents an alkyl group.)

[0035] As the polyether-modified silicone surfactant, commercially available products can be used, for example, under the trade names KF-353, KF-640, KF-642, KF-643, KF-644 (all manufactured by Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5051 (manufactured by Nihon Emulsion Co., Ltd.), BYK-345, BYK-347, BYK-348, BYK-375, BYK-377 (all manufactured by BYK-Chemie Japan K.K.). ), Silface SAG002, Silface SAG003, Silface SAG005, Silface SAG503A, Silface SAG008 (all manufactured by Nissin Chemical Industry Co., Ltd.), TEGO_Wet_KL245, TEGO_Wet_250, TEGO_Wet_260, TEGO_Wet_265, TEGO_Wet_270, TEGO_Wet_280 (all manufactured by Evonik Japan Co., Ltd.).

[0036] The fluorosurfactant is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of low foaming, however, perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having a perfluoroalkyl ether group on the side chain are preferred. Examples of the perfluoroalkylsulfonic acid compound include perfluoroalkylsulfonic acid and perfluoroalkylsulfonate salts. Examples of the perfluoroalkyl carboxylic acid compound include perfluoroalkyl carboxylic acids and perfluoroalkyl carboxylates. Examples of the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group on the side chain 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.

[0037] Counter ions of the salts in these fluorosurfactants include, for example, Li, Na, K, NH4, NH3CH2CH2OH, NH2(CH2CH2OH)2, NH(CH2CH2OH)3, and the like.

[0038] Among these, fluorosurfactants represented by the following general formulas (F-1) and (F-2) are preferred.

[0039] [ka] In the compound represented by the above general formula (F-1), m is preferably an integer of 0 to 10, and n is preferably an integer of 0 to 40 in order to impart water solubility.

[0040] [ka] In the compound represented by the above general formula (F-2), Y is H, C m F 2m+1 (m is an integer from 1 to 6), CH2CH(OH)CH2-C m F 2m+1 (m is an integer from 4 to 6), or C p H 2p+1 (p is an integer from 1 to 19). n is an integer from 1 to 6. a is an integer from 4 to 14.

[0041] The fluorosurfactant is preferably a compound having 2 to 16 fluorine-substituted carbon atoms, and more preferably a compound having 4 to 16 fluorine-substituted carbon atoms.

[0042] The fluorosurfactant may be a commercially available product. Examples of the commercially available fluorosurfactant include Surflon S-242, Surflon S-243, Surflon S-420, and Surflon S-431 (all manufactured by AGC Seimi Chemical Co., Ltd.); Megafac F-251, Megafac F-430, Megafac F-444, Megafac F-477, Megafac F-552, Megafac F-553, and Megafac F-554 (all manufactured by DIC Corporation); CAPSTONE FS-10, CAPSTONE FS-30, CAPSTONE FS-31, CAPSTONE FS-34, CAPSTONE FS-35, CAPSTONE FS-51, CAPSTONE FS-60, CAPSTONE FS-61, CAPSTONE FS-63, CAPSTONE FS-64, CAPSTONE FS-65, and CAPSTONE FS-10. FS-3100 (all manufactured by DuPont); Ftergent 212M, Ftergent 215M, Ftergent 250, Ftergent 251, Ftergent 222F, Ftergent 245F (all manufactured by Neos Co., Ltd.), Polyfox PF-136A, Polyfox PF-156A, Polyfox PF-151N (all manufactured by Kitamura Chemical Industries Co., Ltd.), etc. Among these, CAPSTONE FS-3100 and CAPSTON FS-34 manufactured by Chemours Co., Ltd., Ftergent 250 and Ftergent 251 manufactured by Neos Co., Ltd., and Polyfox PF-151N manufactured by Kitamura Chemical Industries Co., Ltd. are preferred from the viewpoint of excellent print quality, particularly color development, penetration into paper, wettability, and uniform dyeing.

[0043] The acetylene glycol surfactant is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include nonionic surfactants having an acetylene group at the center and a symmetrical structure. These surfactants are suitable for environmental issues as "wetting agents that do not easily foam."

[0044] The acetylene glycol surfactant may be a commercially available product. Examples of the commercially available acetylene glycol surfactant include, by trade name, Surfynol 104E, Surfynol 420, Surfynol 440, Surfynol 465, Surfynol SE, Surfynol SE-F, Surfynol PSA-336, Surfynol DF110D, Surfynol DF58, Olfin E1004, Olfin E1010, Olfin E1020, Olfin PD-001, Olfin PD-002W, Olfin PD-004, Olfin PD-005, Olfin EXP.4001, Olfin EXP.4200, Olfin EXP.4123, Olfin EXP.4300 (all manufactured by Nissin Chemical Industry Co., Ltd.).

[0045] The amphoteric surfactant is not particularly limited and can be appropriately selected depending on the purpose. Examples of the amphoteric surfactant include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.

[0046] The nonionic surfactant is not particularly limited and can be appropriately selected depending on the purpose. Examples of the nonionic surfactant include polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene propylene block polymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and ethylene oxide adducts of acetylene alcohol.

[0047] The anionic surfactant is not particularly limited and can be appropriately selected depending on the purpose. Examples of the anionic surfactant include polyoxyethylene alkyl ether acetates, dodecylbenzene sulfonates, laurates, and polyoxyethylene alkyl ether sulfates.

[0048] The content of the surfactant is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of excellent wettability and ejection stability and improved image quality, the content of the surfactant is preferably from 0.001% by mass to 5% by mass, and more preferably from 0.05% by mass to 5% by mass, based on the total amount of the pretreatment liquid.

[0049] - Defoaming agent - The surfactant used as the other component (A) can be used as a defoaming agent. The defoaming agent is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include silicone-based defoaming agents, polyether-based defoaming agents, fatty acid ester-based defoaming agents, etc. Among these, silicone-based defoaming agents are preferred because of their excellent foam breaking effect. These may be used alone or in combination of two or more.

[0050] -pH adjuster- The pH adjuster is not particularly limited and may be appropriately selected depending on the purpose as long as it is capable of adjusting the pH to 7 or more. Examples of the pH adjuster include amines such as diethanolamine and triethanolamine.

[0051] -Preservative and fungicidal agent- The antiseptic and antifungal agent is not particularly limited and can be appropriately selected depending on the purpose. For example, 1,2-benzisothiazolin-3-one and the like can be mentioned.

[0052] --Rust inhibitor-- The rust inhibitor is not particularly limited and may be appropriately selected depending on the purpose. Examples of the rust inhibitor include acid sulfite and sodium thiosulfate.

[0053] The solvent and other components (A) contained in the pretreatment liquid can be qualitatively and quantitatively analyzed, for example, by gas chromatography mass spectrometry (GC-MS).Measurement equipment using gas chromatography mass spectrometry (GC-MS) can be, for example, GCMS-QP2020NX (manufactured by Shimadzu Corporation). The water contained in the pretreatment liquid can be measured by general methods such as quantifying the volatile components by gas chromatography-mass spectrometry (GC-MS) or measuring mass fluctuations by simultaneous thermogravimetry-differential thermal analysis (TG-DTA).

[0054] The physical properties of the pretreatment liquid are not particularly limited and can be appropriately selected depending on the purpose. For example, it is preferable that the viscosity, surface tension, pH, etc. are within the following ranges. The viscosity of the pretreatment liquid at 25°C is preferably from 5 mPa·s to 30 mPa·s, more preferably from 5 mPa·s to 25 mPa·s, in order to improve print density and character quality and to obtain good dischargeability. Here, the viscosity can be measured using, for example, a rotational viscometer (RE85L manufactured by Toki Sangyo Co., Ltd.). The measurement conditions are 25°C, a standard cone rotor (1°34' x R24), a sample liquid volume of 1.2 mL, a rotation speed of 50 rpm, and 3 minutes. The surface tension of the pretreatment liquid is preferably 35 mN / m or less, and more preferably 32 mN / m or less at 25° C., in order to ensure that the pretreatment liquid is appropriately leveled on the recording medium and the drying time of the pretreatment liquid is shortened. The pH of the pretreatment liquid is preferably from 7 to 12, and more preferably from 8 to 11, from the viewpoint of preventing corrosion of metal members that come into contact with the liquid.

[0055] The application of the pretreatment liquid of the present invention is not particularly limited and can be appropriately selected depending on the purpose, but it is preferably for the wet-on-wet method. Since the pretreatment liquid of the present invention has excellent drying properties at room temperature, applying the pretreatment liquid to the wet-on-wet method is preferable because it can provide a printed matter with excellent bleeding prevention properties and color development.

[0056] (Printing method and printing device) The printing method of the present invention includes a pretreatment liquid applying step and an ink applying step, and may include other steps as necessary. The printing apparatus of the present invention has a pretreatment liquid applying unit and an ink applying unit, and may also have other units as necessary. The pretreatment liquid application step can be suitably carried out by the pretreatment liquid application means, the ink application step can be suitably carried out by the ink application means, and the other steps can be suitably carried out by the other means.

[0057] <Pretreatment Liquid Application Step and Pretreatment Liquid Application Means> The pretreatment liquid application step is a step of applying a pretreatment liquid to a fabric medium. The pretreatment liquid applying means is a means for applying a pretreatment liquid to a fabric medium. The pretreatment liquid is the same as that described in the above (Pretreatment liquid) section, and therefore a duplicate description will be omitted.

[0058] The pretreatment liquid application step (means) is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include an inkjet method, a blade coating method, a gravure coating method, a bar coating method, a roll coating method, a dip coating method, a curtain coating method, a slide coating method, a die coating method, a spray coating method, etc. Among these, the inkjet method is preferred.

[0059] <<Fabric Media>> The medium (recording medium) to be subjected to the pretreatment liquid applying means (step) and the ink applying means (step) described below is not particularly limited as long as it is a woven medium, and can be appropriately selected depending on the purpose. In this specification, the terms recording medium, media, and printed matter are all synonymous.

[0060] Examples of the woven media include cotton-based media, polyester media, cotton-polyester blend media, wool-based media, and other blend media.

[0061] <Ink application means and ink application process> The ink application step is a step of applying a water-based pigment ink by a wet-on-wet method to the fabric medium to which the pretreatment liquid has been applied. The ink applying unit is a unit that applies a water-based pigment ink to the fabric medium to which the pretreatment liquid has been applied. The ink applying step and the ink applying unit can be the same as those in the pretreatment liquid applying step and the pretreatment liquid applying unit, and therefore a duplicated description will be omitted.

[0062] As described above, in conventional printing methods, particularly printing methods using a wet-on-wet system, a drying step using a heat source is not performed, and therefore problems arise because the pretreatment liquid applied in advance to the media does not dry sufficiently. However, since the pretreatment liquid of the present invention has excellent drying properties at room temperature, this problem can be eliminated even in the case of a wet-on-wet system, and the time from when the pretreatment liquid is applied to the fabric media to when the aqueous pigment ink is applied can be set to be short, which is preferable.

[0063] <<Water-based pigment ink>> The water-based pigment ink is not particularly limited and can be appropriately selected depending on the purpose, but it is preferable that the water-based pigment ink contains an organic solvent, water, a pigment, a resin, and an additive, and may contain other components (B) as necessary. In this specification, the "water-based pigment ink" may be simply referred to as "ink".

[0064] <<<Organic solvents>>> The organic solvent is not particularly limited and can be appropriately selected depending on the purpose, and for example, a water-soluble organic solvent can be used. Examples of the water-soluble organic solvent include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohols, ethers such as aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds.

[0065] Specific examples of the water-soluble organic solvent 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, polyhydric alcohols such as hexanediol, 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, and petriol; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethyl ether, and ethyl ether; Examples of the alkyl ether include polyhydric alcohol alkyl ethers such as ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether; 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; amides such as formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropionamide, and 3-butoxy-N,N-dimethylpropionamide; amines such as monoethanolamine, diethanolamine, and triethylamine; sulfur-containing compounds such as dimethyl sulfoxide, sulfolane, and thiodiethanol; propylene carbonate; and ethylene carbonate. Among these, it is preferable to use an organic solvent having a boiling point of 250° C. or less, since it not only functions as a wetting agent but also provides good drying properties.

[0066] In addition to the above-mentioned compounds, polyol compounds having 8 or more carbon atoms and glycol ether compounds are also preferably used as the water-soluble organic solvent. Specific examples of the polyol compound having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol. Specific examples of the glycol ether compound include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, triethylene glycol monobutyl ether, 1-methyl-1 polyhydric alcohol alkyl ethers such as glycol ethers such as 2-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, and dipropylene glycol mono-iso-propyl ether; and polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether.

[0067] The content of the organic solvent is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoints of the drying property and ejection reliability of the ink, the content of the organic solvent is preferably from 10% by mass to 60% by mass, and more preferably from 20% by mass to 60% by mass, based on the total amount of the ink.

[0068] <<<Wed>>> The water is not particularly limited and can be appropriately selected depending on the purpose. The content of the water is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of the drying property and ejection reliability of the ink, the content of the water is preferably from 10% by mass to 90% by mass, and more preferably from 20% by mass to 60% by mass, based on the total amount of the ink.

[0069] <<<Pigments>>> The pigment is not particularly limited and can be appropriately selected depending on the purpose. For example, inorganic pigments or organic pigments can be used. These can be used alone or in combination of two or more. Mixed crystals can also be used.

[0070] Examples of the pigment that can be used include black pigments, yellow pigments, magenta pigments, cyan pigments, white pigments, green pigments, orange pigments, glossy pigments such as gold and silver pigments, and metallic pigments.

[0071] Examples of the inorganic pigment that can be used include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow, as well as carbon black produced by a known method such as a contact method, a furnace method, or a thermal method. Examples of the organic pigment that can be used 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 (e.g., basic dye-type chelates, acid dye-type chelate sugars), nitro pigments, nitroso pigments, aniline black, etc. 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.

[0072] Specific examples of the pigment include the following. Examples of black pigments include carbon blacks (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black; metals such as copper, iron (CI Pigment Black 11), and titanium oxide; and organic pigments such as aniline black (CI Pigment Black 1). Examples of color pigments include CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 24, CI Pigment Yellow 34, CI Pigment Yellow 35, CI Pigment Yellow 37, CI Pigment Yellow 42 (yellow iron oxide), CI Pigment Yellow 53, CI Pigment Yellow 55, CI Pigment Yellow 74, C I Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 117, CI Pigment Yellow 120, CI Pigment Yellow 138, CI Pigment Yellow 15 0, CI Pigment Yellow 153, CI Pigment Yellow 155, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 213, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 36, CI Pigment Orange 43, CI Pigment Orange 51, CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 17, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 31, CI Pigment Red 38, CI Pigment Red 48:2, CI Pigment Red 48:3, CI Pigment Red 48:4, CI Pigment Red 49:1, CI Pigment Red 52:2, CI Pigment Red 53:1, CI Pigment Red 57:1 (Brilliant Carmine 6B), CI Pigment Red 60:1, CIPigment Red 63:1, CI Pigment Red 63:2, CI Pigment Red 64:1, CI Pigment Red 81, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 101 (Red Ash), CI Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108 (Cadmium Red), CI Pigment Red 112, CI Pigment Red 114, CI Pigment Red 122 (Quinacridone Magenta) ), CI Pigment Red 123, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 172, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 184, CI Pigment Red 185, CI Pigment Red 190, CI Pigment Red 193, CI Pigment Red 202, CI Pigment Red Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 213, CI Pigment Red 219, CI Pigment Red 224, CI Pigment Red 254, CI Pigment Red 264, CI Pigment Violet 1 (Rhodamine Lake), CI Pigment Violet 3, CI Pigment Violet 5:1, CI Pigment Violet 16, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 38, CI Pigment Blue 1, CI Pigment Blue 2, CI Pigment Blue 15 (Phthalocyanine Blue), CI Pigment Blue 15:1, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 15:4 (Phthalocyanine Blue), CI Pigment Blue 16, CI Pigment Blue 17:1, CI Pigment Blue 56, CI Pigment Blue 60, CI Pigment Blue 63, CI Pigment Green 1, CI Pigment Green 4, CIPigment Green 7, CI Pigment Green 8, CI Pigment Green 10, CI Pigment Green 17, CI Pigment Green 18, CI Pigment Green 36, etc.

[0073] The content of the pigment is preferably from 0.1% by mass to 15% by mass, and more preferably from 1% by mass to 10% by mass, based on the total amount of the ink, from the viewpoints of improving image density, good fixability, and ejection stability.

[0074] Methods for dispersing pigments to obtain inks include (1) introducing hydrophilic functional groups into the pigment to make it a self-dispersing pigment, (2) coating the surface of the pigment with a resin and dispersing it, and (3) using a dispersant to disperse the pigment. As the method (1) of introducing a hydrophilic functional group into a pigment to make it a self-dispersing pigment, for example, a method of adding a functional group such as a sulfone group or a carboxyl group to a pigment (e.g., carbon) to make it dispersible in water can be mentioned. The above-mentioned (2) method of dispersing a pigment by coating its surface with a resin includes a method of encapsulating the pigment in a microcapsule to make it dispersible in water. A pigment whose surface is coated with a resin and dispersed can be called a resin-coated pigment. When a pigment whose surface is coated with a resin and dispersed is dispersed, it is not necessary for all of the pigments blended in the ink to be coated with a resin, and uncoated or partially coated pigments may be dispersed in the ink as long as the effect of the present invention is not impaired. The (3) method of dispersing using a dispersant includes a method of dispersing using a known low molecular weight dispersant or polymeric dispersant, such as a surfactant. As the dispersant, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, etc., can be used depending on the pigment. Paionin RT-100 (nonionic surfactant) manufactured by Takemoto Oil Co., Ltd. and a formalin condensate of sodium naphthalenesulfonate can also be suitably used as a dispersant. The dispersant may be used alone or in combination of two or more kinds.

[0075] --Pigment dispersion-- It is possible to obtain ink by mixing the pigment with materials such as water and organic solvents. It is also possible to manufacture ink by mixing a pigment with other materials such as water and a dispersant to prepare a pigment dispersion, and then mixing the pigment with materials such as water and organic solvents. The pigment dispersion is obtained by mixing and dispersing water, a pigment, a pigment dispersant, and other components as necessary, and adjusting the particle size. A dispersing machine is preferably used for dispersion. Furthermore, it is preferable to filter coarse particles from the pigment dispersion using a filter, a centrifugal separator, or the like, and degas the pigment dispersion as necessary.

[0076] The particle size of the pigment in the pigment dispersion is not particularly limited, but the maximum frequency in terms of maximum number is preferably 20 nm or more and 500 nm or less, and more preferably 20 nm or more and 150 nm or less, in order to improve the dispersion stability of the pigment and the image quality such as ejection stability and image density. The particle size of the pigment can be measured using a particle size analyzer (Nanotrac WaveII-UT151, manufactured by Microtrac MRB Co., Ltd.).

[0077] The content of the pigment in the pigment dispersion is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoints of obtaining good ejection stability and increasing image density, the content of the pigment in the pigment dispersion is preferably from 0.1% by mass to 50% by mass, and more preferably from 0.1% by mass to 30% by mass, based on the total amount of the pigment dispersion.

[0078] <<<Resin>>> The resin 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, and acrylic silicone resin. Resin particles made of these resins may be used. The resin particles are dispersed in water as a dispersion medium in a resin emulsion state, and the ink can be obtained by mixing the resin particles with materials such as coloring materials and organic solvents. The resin particles may be appropriately synthesized or commercially available products may be used. These resin particles may be used alone or in combination of two or more kinds of resin particles.

[0079] The volume average particle diameter of the resin particles is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of obtaining good fixing property and high image hardness, it is preferably 10 nm to 1,000 nm, more preferably 10 nm to 200 nm, and even more preferably 10 nm to 100 nm. The volume average particle diameter can be measured, for example, using a particle size analyzer (Nanotrac WaveII-UT151, manufactured by Microtrac MRB Co., Ltd.).

[0080] The content of the resin is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoints of fixation property and storage stability of the ink, the content of the resin is preferably from 1 mass % to 30 mass % and more preferably from 5 mass % to 20 mass % of the total amount of the ink.

[0081] The particle size of the solid content in the ink is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of improving the ejection stability and image quality such as image density, the maximum frequency of the particle size of the solid content in the ink is preferably 20 nm or more and 1000 nm or less, and more preferably 20 nm or more and 150 nm or less, calculated as the maximum number. The solid content includes the resin particles and the pigment particles. The particle size can be measured using a particle size analyzer (Nanotrac WaveII-UT151, manufactured by Microtrac MRB Co., Ltd.).

[0082] <<<Additives>>> If necessary, additives such as surfactants, antifoaming agents, antiseptic and antifungal agents, rust inhibitors, and pH adjusters may be added to the ink. The surfactant, the defoaming agent, the antiseptic / antifungal agent, the rust inhibitor, and the pH adjuster are not particularly limited and can be appropriately selected depending on the purpose. For example, the same agents as those described in the above section (Pretreatment liquid) can be used.

[0083] The content of the surfactant is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoints of excellent wettability and ejection stability and improved image quality, the content is preferably from 0.001% by mass to 5% by mass, and more preferably from 0.05% by mass to 5% by mass, relative to the total amount of the ink.

[0084] The contents of the antifoaming agent, the antiseptic / antifungal agent, the rust inhibitor, and the pH adjuster are not particularly limited, and can be appropriately set depending on the contents of the various materials.

[0085] The organic solvent, resin, coloring material, and other components (B) contained in the ink can be qualitatively and quantitatively analyzed, for example, by gas chromatography mass spectrometry (GC-MS).Measurement devices using gas chromatography mass spectrometry (GC-MS) include, for example, GCMS-QP2020NX (manufactured by Shimadzu Corporation). The water contained in the ink can be measured by general methods such as quantifying the volatile components by gas chromatography-mass spectrometry (GC-MS) or measuring mass changes by simultaneous thermogravimetry-differential thermal analysis (TG-DTA).

[0086] The physical properties of the ink are not particularly limited and can be appropriately selected depending on the purpose. For example, it is preferable that the viscosity, surface tension, pH, etc. are within the following ranges. The viscosity of the ink at 25°C is preferably from 5 mPa·s to 30 mPa·s, more preferably from 5 mPa·s to 25 mPa·s, in order to improve print density and character quality and to obtain good ejection properties. Here, a rotational viscometer (RE85L manufactured by Toki Sangyo Co., Ltd.) can be used, for example, to measure the viscosity. The measurement conditions are 25°C, a standard cone rotor (1°34'×R24), a sample liquid volume of 1.2 mL, a rotation speed of 50 rpm, and 3 minutes. The surface tension of the ink is preferably 35 mN / m or less, and more preferably 32 mN / m or less at 25° C., in order to ensure that the ink is appropriately leveled on the recording medium and the drying time of the ink is shortened. The pH of the ink is preferably from 7 to 12, and more preferably from 8 to 11, from the viewpoint of preventing corrosion of metal members that come into contact with the ink.

[0087] The method of using the ink is not limited to the inkjet recording method, and can be widely used. In addition to the inkjet recording method, examples of the method include blade coating, gravure coating, bar coating, roll coating, dip coating, curtain coating, slide coating, die coating, and spray coating.

[0088] The application of the ink is not particularly limited and can be appropriately selected depending on the purpose, and can be applied to, for example, printed matter, paint, coating material, undercoat, etc. Furthermore, the ink can be used not only to form two-dimensional characters and images, but also as a material for three-dimensional modeling for forming three-dimensional solid images (three-dimensional models). The three-dimensional modeling device for forming the three-dimensional object may be a known one, and is not particularly limited. For example, a device equipped with an ink storage means, supply means, discharge means, drying means, etc. may be used. The three-dimensional object includes a three-dimensional object obtained by applying ink over and over. Also included is a molded product obtained by processing a structure to which ink is applied on a substrate such as a recording medium. The molded product is, for example, a recording material or structure formed in a sheet or film form, which is molded by heat stretching, punching, etc., and is preferably used for applications in which the surface is molded after decoration, such as meters and operation panels for automobiles, office automation equipment, electric and electronic equipment, and cameras.

[0089] <Other steps and other means> The other steps are not particularly limited and may be appropriately selected depending on the purpose. Examples of the other steps include a transport step, a post-treatment liquid application step, a heating step, and a drying step. The other means are not particularly limited and may be appropriately selected depending on the purpose. Examples of the other means include a transport means, a post-treatment liquid applying means, a heating means, and a drying means.

[0090] <<Transportation process and transport means>> The transport step is a step of transporting the fabric medium to which the pretreatment liquid has been applied, specifically, a step related to feeding, transporting, and discharging the fabric medium. The transport means is a means for transporting the fabric medium to which the pretreatment liquid has been applied, specifically, a means for feeding, transporting, and discharging the fabric medium. The transport step can be suitably carried out by the transport means.

[0091] The transporting step (means) preferably includes a step (means) of transporting the fabric medium to which the pretreatment liquid has been applied by the pretreatment liquid application means to a position where the water-based pigment ink is applied.

[0092] The surface temperature of the fabric medium in the transport step is preferably room temperature. Here, the "room temperature" is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10°C or higher and 40°C or lower. Since the pretreatment liquid of the present invention has excellent drying properties at room temperature, there is no need to provide a heating step (means) and a drying step (means) to be described later for the transport step (means). This makes it possible to simplify the configuration of the printing device, and it is preferable that the time from the time when the pretreatment liquid is applied to the fabric medium to the time when the aqueous pigment ink is applied can be set to be short. In other words, in a printing method using a wet-on-wet system, it is preferable that the occurrence of problems such as reduced image quality due to bleeding or unevenness in the printed image can be suppressed, and the transport of the fabric medium can be performed quickly.

[0093] <<Post-treatment liquid application step and post-treatment liquid application means>> The pre-treatment liquid application step is a step of applying a post-treatment liquid to the fabric medium to which the water-based pigment ink has been applied. The post-treatment liquid applying unit is a unit that applies a post-treatment liquid to the fabric medium to which the water-based pigment ink has been applied. The post-treatment liquid application step can be suitably carried out by the post-treatment liquid application unit.

[0094] The post-treatment liquid is not particularly limited as long as it can form a transparent layer. The post-treatment liquid is obtained by selecting and mixing organic solvents, water, resins, surfactants, antifoaming agents, pH adjusters, antiseptic and antifungal agents, rust inhibitors, etc. as necessary. Note that, each of these components can be the same as those described in the above (pre-treatment liquid), so duplicate descriptions will be omitted. The post-treatment liquid may be applied to the entire recording area formed on the fabric medium, or may be applied only to the area on which the ink image is formed.

[0095] As one embodiment of the post-treatment liquid application means, a liquid storage section having the post-treatment liquid and a liquid ejection head are added, as in the case of water-based pigment inks such as black (K), cyan (C), magenta (M), and yellow (Y), and the like, and the post-treatment liquid is ejected by an inkjet recording method. The post-treatment liquid applying means is not particularly limited and can be appropriately selected depending on the purpose. For example, the same means as the pre-treatment liquid applying means described above can be used.

[0096] <<Heating step and heating means, and drying step and drying means>> The heating step includes, for example, a step of heating the print surface and the back surface of the fabric medium. The heating means includes, for example, a means for heating the print surface or the back surface of the fabric medium. The heating step can be suitably carried out by the heating means. The drying step includes, for example, a step of drying the printed surface and the back surface of the fabric medium. The drying means includes, for example, a means for drying the print surface and the back surface of the fabric medium. The drying step can be suitably carried out by the drying means.

[0097] The printing method and printing apparatus of the present invention may include the heating step and the heating means, and the drying step and the drying means, but it is preferable that they do not include these steps.

[0098] The heating step and the drying means are not particularly limited, but for example, a hot air heater, an infrared heater, etc. Heating and drying can be carried out before, during, or after printing.

[0099] The printing apparatus according to the present invention can be applied to various recording apparatuses using an inkjet recording method, such as printers, facsimile machines, copying machines, printer / fax / copier combination machines, and three-dimensional modeling apparatuses.

[0100] The printing method and printing device of the present invention are not limited to those that visualize meaningful images such as characters and figures with ink. For example, they also include those that form patterns such as geometric designs and those that create three-dimensional images. In addition, unless otherwise specified, the printing device includes both a serial type device in which the ejection head moves and a line type device in which the ejection head does not move. Furthermore, the printing device includes not only desktop types, but also wide recording devices that can print on A0 size recording media, and continuous feed printers that can use continuous paper wound into a roll as the recording medium.

[0101] In the present invention, the terms image formation, recording, printing, printing, etc. are all synonymous.

[0102] <Printed material> A printed matter can be produced by printing on a fabric medium using the printing method and printing apparatus of the present invention. The printed matter has an image formed on the fabric medium using the pretreatment liquid and the ink.

[0103] Here, an embodiment of a printing apparatus according to the present invention will be described with reference to the drawings, although the present invention is not limited to this embodiment. In addition, in each drawing, the same components are denoted by the same reference numerals, and duplicated explanations may be omitted. Furthermore, the number, position, shape, etc. of the following components are not limited to the present embodiment, and may be any number, position, shape, etc. that is preferable for implementing the present invention.

[0104] FIG. 1 is a schematic diagram showing an embodiment of a printing device according to the present invention. The printing apparatus 100 in FIG. 1 includes a pretreatment liquid deposition unit 110, an ink deposition unit 120, a posttreatment liquid deposition unit 130, a drying unit 140, and a transport unit 150. The pretreatment liquid deposition unit 110 deposits the pretreatment liquid onto a recording medium M. It is to be noted that the post-treatment liquid application unit 130, the drying unit 140, and the transport unit 150 may be omitted. Furthermore, in the printing apparatus of the present invention, the step of applying the ink and the step of applying the pre-treatment liquid may be performed by the same printing device, or may be performed by different printing devices.

[0105] The method for applying the pretreatment liquid is not particularly limited, but examples thereof include an inkjet method, a roller coating method, a blade coating method, a gravure coating method, a gravure offset coating method, a bar coating method, a roll coating method, a knife coating method, an air knife coating method, a comma coating method, a U comma coating method, an AKKU coating method, a smoothing coating method, a microgravure coating method, a reverse roll coating method, a four- or five-roll coating method, a dip coating method, a curtain coating method, a slide coating method, and a die coating method.

[0106] The recording medium M used for recording is not particularly limited as long as it is a woven medium.

[0107] The ink application unit 120 applies inkjet ink to the surface of the recording medium M to which the pretreatment liquid has been applied. As the ink applying section 120, for example, a known inkjet head can be used. The ink application unit 120 may be a head that ejects ink of any color, and for example, heads that eject ink of the colors Y (yellow), M (magenta), C (cyan), K (black), and W (white) may be provided as necessary.

[0108] The post-treatment liquid application unit 130 may be configured to apply the post-treatment liquid to the area on the surface of the recording medium M to which the inkjet ink has been applied, and may be configured, for example, by a spray, a roller, or the like other than an inkjet head. The post-treatment liquid application unit 130 may be omitted.

[0109] The method for applying the post-treatment liquid is not particularly limited, but examples thereof include an inkjet method, a roller coating method, a blade coating method, a gravure coating method, a gravure offset coating method, a bar coating method, a roll coating method, a knife coating method, an air knife coating method, a comma coating method, a U comma coating method, an AKKU coating method, a smoothing coating method, a microgravure coating method, a reverse roll coating method, a four to five roll coating method, a dip coating method, a curtain coating method, a slide coating method, and a die coating method.

[0110] The drying section 140 uses hot air to dry the recording medium M to which the post-treatment liquid has been applied. If there is no post-treatment liquid application section, the drying section 140 may be omitted. The drying section 140 may use infrared rays, microwaves, a roll heater, or the like instead of hot air to heat and dry the recording medium M to which the post-treatment liquid has been applied, or the drying section 140 may not be operated and the recording medium M to which the post-treatment liquid has been applied may be naturally dried.

[0111] The conveying section 150 conveys the recording medium M. The conveying unit 150 is not particularly limited as long as it is capable of conveying the recording medium M, but examples of the conveying unit 150 include a conveying belt and a platen.

[0112] The printing apparatus 100 may further include a fixing unit that heats and fixes the image formed on the recording medium M. The fixing unit is not particularly limited, but may be a fixing roller or the like. EXAMPLES

[0113] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples and comparative examples, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass". Unless otherwise specified, preparation and evaluation were carried out under conditions of 25°C and humidity of 60%.

[0114] [Production Examples of Pretreatment Solutions 1 to 23 and Comparative Pretreatment Solutions 1 to 7] Each material having the composition and content shown in Tables 1 to 4 below was stirred to mix uniformly, and the resulting mixture was filtered through a filter with an average pore size of 5 μm (Minisart, manufactured by Sartorius) to produce pretreatment solutions 1 to 23 and comparative pretreatment solutions 1 to 7.

[0115] [Ink preparation example] <Preparation of pigment dispersion> The following materials were premixed and then circulated and dispersed for 7 hours in a disk-type bead mill (KDL type manufactured by Shinmaru Enterprises, media: zirconia balls with a diameter of 0.3 mm) to obtain a black pigment dispersion (pigment solids concentration 15% by mass). Carbon black pigment (product name: Monarch 800, manufactured by Cabot Corporation) 15 parts by weight Anionic surfactant (product name: Paionin A-51-B, manufactured by Takemoto Oil Co., Ltd.) 2 parts by weight Ion-exchanged water: 83 parts by weight

[0116] <Ink Preparation> The following materials were mixed uniformly for 1 hour by stirring. 1,2-propanediol (Tokyo Chemical Industry Co., Ltd.) 11.5 parts by mass 3-Methoxy-3-methylbutanol (Tokyo Chemical Industry Co., Ltd.) 1.5 parts by mass 2-Ethyl-1,3-hexanediol (Tokyo Chemical Industry Co., Ltd.) 1.3 parts by mass Urethane resin emulsion (product name: Superflex 210, 35% by weight, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 8.0 parts by weight Silicone surfactant (product name: KF-640, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.4 parts by mass pH adjuster (2-amino-2-ethyl-1,3-propanediol, manufactured by Tokyo Chemical Industry Co., Ltd.) 0.1 part by mass ·Ion-exchanged water···Remaining amount (57.2 parts by mass) The content of the resin emulsion is the amount of the entire resin emulsion. Next, 20.0% by mass of black pigment dispersion was added and further stirred for 1 hour to mix uniformly. The content of the pigment dispersion is the amount of the entire pigment dispersion. This mixture was pressure filtered through a polypropylene filter (product name: Profile Star, average pore size: 1.5 μm, manufactured by Nippon Pole Co., Ltd.) to remove coarse particles and dust, and an ink was prepared.

[0117] Example 1 Two inkjet printers (device name: Ri100, manufactured by Ricoh Co., Ltd.) were prepared, one of which was filled with pretreatment liquid 1, and the other was filled with ink. The inkjet printer filled with pretreatment liquid 1 was used to measure the deposition amount of 10 g / m 2 A solid image was printed on a polyester medium (product name: Polyester Tropical, manufactured by Shikisen Co., Ltd.) so that the image was as shown in FIG. 15 seconds after the application of the pretreatment liquid 1 was completed, an image was further printed on the polyester medium to which the pretreatment liquid 1 had been applied, using an inkjet printer filled with ink. In the inkjet printer, a heating and drying mechanism was not provided in the transport path until the image was printed, and the surface temperature was kept at room temperature (10°C to 40°C). The obtained print was then heated and dried for 5 minutes in a thermostatic chamber set at 100°C, to obtain the printed image of Example 1.

[0118] [Color development evaluation] The image density of the Bk solid image portion in the printed image of Example 1 was measured with a spectrophotometric densitometer (X-Rite938, manufactured by X-Rite Corporation) and evaluated based on the following criteria. In the following evaluation criteria, ranks S, A, and B are practically acceptable ranges. The results are shown in Tables 1 to 4. -Evaluation criteria for "color development"- Rank S: BkOD value is 1.3 or more Rank A: BkOD value is 1.1 or more and less than 1.3 Rank B: BkOD value is 1.0 or more and less than 1.1 Rank C: BkOD value is less than 1.0

[0119] [Evaluation of anti-bleeding properties] The printed image of Example 1 was visually observed and the bleeding prevention property was evaluated based on the following criteria. In the following evaluation criteria, ranks S, A, and B are in the range of practically acceptable ranges. The results are shown in Tables 1 to 4. -Evaluation criteria for "anti-bleeding"- Rank S: No bleeding is observed. Rank A: Slight smudging is observed, and slight hair-like bleeding is observed in the text and images. Rank B: Blurring is observed, and unevenness is observed on the edges of letters and images, and colors are mixed together. Rank C: Blurring is observed and the text and images are significantly distorted. Rank D: Blurring is observed and characters and images cannot be read.

[0120] [Evaluation of ejection stability] An inkjet printer (device name: Ri100, manufactured by Ricoh Co., Ltd.) was filled with the pretreatment liquid 1, and it was confirmed that there were no missing nozzles. Thereafter, the pretreatment liquid 1 was applied to a polyester medium (product name: Polyester Tropical, manufactured by Shikisen Co., Ltd.) in an amount of 10 g / m 2A solid image of the pretreatment liquid was printed on 20 sheets in succession so that the number of missing nozzles was counted. Then, a nozzle check pattern was printed to count the number of missing nozzles, and the ejection stability was evaluated based on the following criteria. In the following evaluation criteria, ranks S, A, and B are in the range where there is no problem in practical use. The results are shown in Tables 1 to 4. -Evaluation criteria for "discharge stability"- Rank S: No missing nozzles at all in the nozzle check pattern after 20 consecutive prints Rank A: The nozzle check pattern after 20 consecutive prints shows 1 to 2 missing nozzles Rank B: 3 to 4 nozzles missing in the nozzle check pattern after 20 consecutive prints Rank C: 5 to 10 nozzles missing in the nozzle check pattern after 20 consecutive prints Rank D: 11 or more nozzles missing in the nozzle check pattern after 20 consecutive prints

[0121] (Examples 2 to 23, Comparative Examples 1 to 7) Printed images were prepared and evaluated in the same manner as in Example 1, except that pretreatment liquid 1 was replaced with pretreatment liquids 2 to 23 or comparative pretreatment liquids 1 to 7. For the media in Example 18, cotton broadcloth, unmercerized (not mercerized, manufactured by Shikisen Co., Ltd.) was used. The results are shown in Tables 1 to 4.

[0122] [Table 1]

[0123] [Table 2]

[0124] [Table 3]

[0125] [Table 4]

[0126] The details of the materials listed in Tables 1 to 4 above are as follows. Calcium nitrate tetrahydrate (divalent metal salt): Fujifilm Wako Pure Chemical Industries, Ltd. Sodium chloride (monovalent metal salt): Fujifilm Wako Pure Chemical Industries, Ltd. Potassium nitrate (monovalent metal salt): Fujifilm Wako Pure Chemical Industries, Ltd. Calcium chloride (divalent metal salt): Fujifilm Wako Pure Chemical Industries, Ltd. Aluminum chloride (trivalent metal salt): Fujifilm Wako Pure Chemical Industries, Ltd. Ionic surfactant: Cationic surfactant benzalkonium chloride, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Non-ionic surfactant: Fluorosurfactant FS-300, manufactured by Chemours

[0127] The aspects of the present invention include, for example, the following. <1> A pretreatment liquid containing a high-boiling point solvent having a boiling point of 101° C. or more, a low-boiling point solvent having a boiling point of 50° C. or more and 95° C. or less, a flocculant, and water, The pretreatment liquid is characterized in that the content of the low-boiling point solvent having a boiling point of 50° C. or more and 95° C. or less is 10% by mass or more and 20% by mass or less with respect to the total amount of the pretreatment liquid. <2> The content of the low boiling point solvent is 15% by mass or more and 20% by mass or less with respect to the total amount of the pretreatment liquid. <1> 2. The pretreatment liquid according to claim 1, <3> Contains a low-boiling point solvent having a boiling point of 50°C or more and 70°C or less, The content of the low-boiling point solvent having a boiling point of 50° C. or more and 70° C. or less is 10% by mass or more and 20% by mass or less with respect to the total amount of the pretreatment liquid. <1> or the above <2> 2. The pretreatment liquid according to claim 1, <4> The content of the low-boiling point solvent having a boiling point of 50° C. or more and 70° C. or less is 15% by mass or more and 20% by mass or less with respect to the total amount of the pretreatment liquid. <3> 2. The pretreatment liquid according to claim 1, <5> The low boiling point solvent is a non-polar solvent or an aprotic solvent. <1> From the above <4> 1. The pretreatment liquid according to claim 1 , <6> Contains a high boiling point solvent having a boiling point of 150°C or higher, The content of the high-boiling point solvent having a boiling point of 150° C. or higher is 5% by mass or more and 15% by mass or less with respect to the total amount of the pretreatment liquid. <1> From the above <5> 1. The pretreatment liquid according to claim 1 , <7> The pretreatment liquid contains at least one kind of divalent or trivalent metal ion having the flocculant as a metal ion source. <1> From the above <6> 1. The pretreatment liquid according to claim 1 , <8> The flocculant is a nitrate. <1> From the above <7> 1. The pretreatment liquid according to claim 1 , <9> The molar concentration of the flocculant is 0.1 mol / kg or more and 1.2 mol / kg or less. <1> From the above <8> 1. The pretreatment liquid according to claim 1 , <10> The above-mentioned contains an ionic surfactant. <1> From the above <9> 1. The pretreatment liquid according to claim 1 , <11> The above <1> From the above <10> a pretreatment liquid application step of applying the pretreatment liquid according to any one of the above to a fabric medium; and applying an aqueous pigment ink by a wet-on-wet method to the fabric medium to which the pretreatment liquid has been applied. <12> a conveying step of conveying the fabric medium to which the pretreatment liquid has been applied, The surface temperature of the fabric medium during the conveying step is 10° C. or higher and 40° C. or lower. <11> 2 is a printing method according to the present invention. <13> The pretreatment liquid application step and / or the ink application step are performed by an inkjet method. <11> or the above <12> 13. The printing method according to claim 12, wherein <14> The above <1> From the above <10> a pretreatment liquid applying means for applying the pretreatment liquid according to any one of the preceding claims to a fabric medium; and an ink applying unit that applies a water-based pigment ink to the fabric medium to which the pretreatment liquid has been applied.

[0128] The above <1> from <10> The pretreatment liquid according to any one of the preceding claims. <11> From the above <13> The printing method according to any one of the preceding claims, <14> The printing apparatus described in the above is capable of solving the above-mentioned problems in the prior art and achieving the object of the present invention. [Explanation of symbols]

[0129] 100 Printing device 110 Pretreatment liquid application section 120 Ink application section 130 Post-processing liquid application section 140 Drying section 150 Conveyor M Recording medium [Prior art documents] [Patent documents]

[0130] [Patent Document 1] JP 2018-114748 A [Patent Document 2] JP 2003-103912 A

Claims

1. A pretreatment liquid containing a high-boiling point solvent having a boiling point of 101° C. or more, a low-boiling point solvent having a boiling point of 50° C. or more and 95° C. or less, a flocculant, and water, The pretreatment liquid has a content of the low-boiling point solvent having a boiling point of 50° C. or more and 95° C. or less in an amount of 10% by mass or more and 20% by mass or less based on the total amount of the pretreatment liquid.

2. The pretreatment liquid according to claim 1 , wherein the content of the low boiling point solvent is 15% by mass or more and 20% by mass or less with respect to the total amount of the pretreatment liquid.

3. Contains a low-boiling point solvent having a boiling point of 50° C. or more and 70° C. or less, 3. The pretreatment liquid according to claim 1, wherein the content of the low-boiling point solvent having a boiling point of 50° C. or more and 70° C. or less is 10% by mass or more and 20% by mass or less with respect to the total amount of the pretreatment liquid.

4. The pretreatment liquid according to claim 3 , wherein the content of the low-boiling point solvent having a boiling point of 50° C. or more and 70° C. or less is 15% by mass or more and 20% by mass or less with respect to the total amount of the pretreatment liquid.

5. The pretreatment liquid according to claim 1 , wherein the low boiling point solvent is a non-polar solvent or an aprotic solvent.

6. Contains a high boiling point solvent having a boiling point of 150° C. or higher, The pretreatment liquid according to claim 1 , wherein the content of the high-boiling point solvent having a boiling point of 150° C. or higher is 5% by mass or more and 15% by mass or less with respect to the total amount of the pretreatment liquid.

7. The pretreatment liquid according to claim 1 or 2, which contains at least one kind of divalent or trivalent metal ion having the flocculant as a metal ion source.

8. The pretreatment solution according to claim 1 or 2, wherein the flocculant is a nitrate.

9. The pretreatment liquid according to claim 1 or 2, wherein the flocculant has a molar concentration of 0.1 mol / kg or more and 1.2 mol / kg or less.

10. The pretreatment liquid according to claim 1 or 2, further comprising an ionic surfactant.

11. A pretreatment liquid application step of applying the pretreatment liquid according to claim 1 or 2 to a fabric medium; an ink applying step of applying a water-based pigment ink by a wet-on-wet method to the fabric medium to which the pretreatment liquid has been applied.

12. a conveying step of conveying the fabric medium to which the pretreatment liquid has been applied, The printing method according to claim 11 , wherein a surface temperature of the fabric medium during the transport step is 10° C. or higher and 40° C. or lower.

13. The printing method according to claim 11 , wherein the pretreatment liquid applying step and / or the ink applying step are performed by an inkjet system.

14. A pretreatment liquid applying means for applying the pretreatment liquid according to claim 1 or 2 to a fabric medium; an ink applying unit that applies a water-based pigment ink to the fabric medium to which the pretreatment liquid has been applied.

Images