Printing method, processing solution and ink set, and method for manufacturing printed materials

Abstract

To provide a printing method which is excellent in initial discharge stability of ink and scratch resistance of a formed image, and can suppress occurrence of bleeding and cracking of an image.SOLUTION: A printing method includes a treatment liquid applying step of applying a treatment liquid containing a polyvalent metal salt and a resin A to a base material, and an ink applying step of applying, onto the treatment liquid, ink which contains a coloring material, an organic solvent having a boiling point of 290°C or higher, a silicone-based surface active agent, and a resin B and the content of the organic solvent having a boiling point of 290°C or higher is 0.5 mass% or more, with respect to the total amount of the ink.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a printing method, a set of a treatment liquid and an ink, and a method for manufacturing a printed matter.

Background Art

[0002] In recent years, inkjet printers are used not only for home use but also for industrial use such as, for example, cloth, plastic film, wallpaper, window film, and the like.

[0003] In the inkjet method, generally, dye ink, solvent ink, or ultraviolet curable ink (UV ink) is used. In recent years, there is also a method of applying a treatment liquid to a substrate before printing such ink and then applying the ink on the applied treatment liquid. As the ink and the treatment liquid used in such a method, for example, an inkjet ink containing a pigment, a water-soluble organic solvent, a surfactant, and water, a treatment liquid containing a flocculant and a compound having three or more hydroxyl groups, and an ink set including the same have been proposed (see, for example, Patent Document 1).

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide a printing method that is excellent in the initial ejection stability of ink and the rub resistance of the formed image and can suppress the occurrence of bleeding and cracking of the image.

Means for Solving the Problems

[0005] The printing method of the present invention as means for solving the above problems includes a treatment liquid application step of applying a treatment liquid containing a polyvalent metal salt and a resin A to a substrate, a coloring material, a boiling point 360℃ or higher of an organic solvent, a silicone-based surfactant, and a resin B, and the boiling point 360℃ or higherThe printing method includes an ink application step of applying ink to the processing liquid, wherein the content of the organic solvent is 0.5% by mass or more relative to the total amount of ink. [Effects of the Invention]

[0006] According to the present invention, it is possible to provide a printing method that offers excellent initial ink ejection stability and scratch resistance of the formed image, and that can suppress the occurrence of image blurring and cracking. [Brief explanation of the drawing]

[0007] [Figure 1] Figure 1 is a perspective view illustrating an example of a printing apparatus according to the present invention. [Figure 2] Figure 2 is a perspective view illustrating an example of a main tank in the printing apparatus of the present invention. [Figure 3] Figure 3 is a schematic diagram showing an example of an image forming apparatus used in the image forming method of the present invention. [Modes for carrying out the invention]

[0008] (Printing method and printing apparatus) The printing method of the present invention includes a processing solution application step of applying a processing solution containing a polyvalent metal salt and resin A to a substrate, and an ink application step of applying an ink containing a colorant, an organic solvent having a boiling point of 290°C or higher, a silicone-based surfactant, and resin B, wherein the content of the organic solvent having a boiling point of 290°C or higher is 0.5% by mass or more of the total amount of ink, and further includes other steps as necessary. The printing apparatus according to the printing method of the present invention comprises: a processing liquid container containing a processing liquid containing a polyvalent metal salt and resin A; a processing liquid dispensing means for applying the processing liquid contained in the processing liquid container to a substrate; an ink container containing ink containing a colorant, an organic solvent having a boiling point of 290°C or higher, a silicone-based surfactant, and resin B, wherein the content of the organic solvent having a boiling point of 290°C or higher is 0.5% by mass or more of the total amount of ink; and an ink dispensing means for applying the ink contained in the ink container onto the processing liquid, and further comprising other means as necessary.

[0009] The inventors of the present invention have found that in conventional technology, when forming a coating film of aqueous inkjet ink using an inkjet recording device, initial ejection failure of ink droplets may occur depending on the amount of solvent or activator, and the abrasion resistance of the formed coating film may be reduced.

[0010] As a result of diligent research, the present inventors have found that by using a combination of a processing solution containing a polyvalent metal salt and resin A, and an ink containing a colorant, an organic solvent with a boiling point of 290°C or higher, a silicone-based surfactant, and resin B, wherein the content of the organic solvent with a boiling point of 290°C or higher is 0.5% by mass or more of the total ink amount, the ink discharge stability is excellent, the fixation of the formed image to the substrate is excellent, and the occurrence of blurring and cracking of the image can be suppressed.

[0011] Furthermore, since the processing liquid is applied to the substrate before the ink is applied, the processing liquid may be referred to as a pre-treatment liquid.

[0012] <Processing liquid application process and processing liquid application means> The aforementioned processing solution application step is a step of applying a processing solution containing a polyvalent metal salt and resin A to the substrate. The processing liquid application means is a means for applying a processing liquid contained in a processing liquid container, which contains a processing liquid containing a polyvalent metal salt and resin A, to a substrate. There are no particular restrictions on the processing liquid container, and known inkjet cartridges and the like can be used.

[0013] -Processing liquid- The processing solution contains a polyvalent metal salt and resin A, and may further contain water, an organic solvent, a surfactant, and other components as needed. The organic solvent, the surfactant, and the other components (for example, defoaming agents, pH adjusters, preservatives, antifungal agents, rust inhibitors, and antibacterial agents) can be the same materials used for the ink described later, or other materials used for known processing solutions can be used. Furthermore, as the organic solvent for the processing solution, any organic solvent usable for the ink described later can be appropriately selected without specifying its boiling point.

[0014] --Polyvalent metal salts (coagulants)-- The aforementioned polyvalent metal salt functions as a flocculant. The aforementioned polyvalent metal salt reacts with components in the ink to suppress image blurring and other issues, thereby enabling the formation of high-quality images. Furthermore, the polyvalent metal salt rapidly aggregates the pigment in the ink after it is dropped onto the skin, suppressing color bleeding and improving color development.

[0015] There are no particular restrictions on the polyvalent metal salts mentioned above, and they can be appropriately selected depending on the purpose. Examples include titanium salts, chromium salts, copper salts, cobalt salts, strontium salts, barium salts, iron salts, aluminum salts, calcium salts, potassium salts, and magnesium salts. These may be used individually or in combination of two or more. Among these, divalent metal salts are preferred, and calcium salts, magnesium salts, and the like are more preferred. Examples of the calcium salts mentioned above include calcium carbonate, calcium nitrate, calcium chloride, calcium acetate, calcium sulfate, magnesium chloride, magnesium acetate, and magnesium sulfate. These may be used individually or in combination of two or more.

[0016] As the content of the polyvalent metal salt, it is preferably 0.1% by mass or more and less than 5% by mass, more preferably 0.1% by mass or more and 3% by mass or less, based on the total amount of the treatment liquid. When the content of the polyvalent metal salt is 0.1% by mass or more and less than 5% by mass based on the total amount of the treatment liquid, bleeding suppression and the effect of suppressing cracks in the formed image can be improved. Further, when the content of the polyvalent metal salt is 0.1% by mass or more and 3% by mass or less based on the total amount of the treatment liquid, image formation property (the image is formed without bleeding between colors or cracking of the coating film) can be improved.

[0017] --Resin A-- There are no particular limitations on the resin A, and it can be appropriately selected according to the purpose. For example, urethane resins, acrylic resins, polyester resins, vinyl acetate resins, styrene resins, butadiene resins, styrene-butadiene resins, vinyl chloride resins, acrylic styrene resins, acrylic silicone resins, etc. can be mentioned. Among these, urethane resins and acrylic resins are preferred. When the resin A is a urethane resin or an acrylic resin, the adhesion to the substrate and the adhesion to the image formed by the ink described below and the adhesion to the substrate can be improved.

[0018] There are no particular limitations on the form of the resin A, and it can be appropriately selected according to the purpose. For example, resin particles can be mentioned. It is possible to obtain a treatment liquid by mixing the resin particles in the state of a resin emulsion dispersed with water as a dispersion medium with materials such as a polyvalent metal salt and an organic solvent. As the resin particles, those synthesized appropriately may be used, or commercially available products may be used. As the resin A, one kind may be used alone, or two or more kinds may be used in combination.

[0019] Examples of the aforementioned commercially available resin microparticles include Xw-Um12 (polyurethane resin, manufactured by Mitsui Chemicals, Inc.), Xw-Um3A (polyurethane resin, manufactured by Mitsui Chemicals, Inc.), W6110 (polyurethane resin, manufactured by Mitsui Chemicals, Inc., solid content concentration: 35% by mass), Superflex 300 (polyurethane resin, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid content concentration: 30% by mass), Xw-Um7 (polyurethane resin, manufactured by Mitsui Chemicals, Inc., solid content concentration: 30% by mass), Movinyl 6800 (acrylic resin, manufactured by Japan Coating Resin Co., Ltd., solid content concentration: 45% by mass), Movinyl 6969D (acrylic resin, manufactured by Japan Coating Resin Co., Ltd., solid content concentration: 40% by mass), Movinyl 6750 (acrylic resin, manufactured by Japan Coating Resin Co., Ltd., solid content concentration: 50% by mass), and Movinyl 6810 (acrylic resin, manufactured by Japan Coating Resin Co., Ltd., solid content concentration: 40% by mass). There are no particular restrictions on the volume-average particle size of the resin particles, and they can be appropriately selected depending on the purpose. However, from the standpoint of obtaining good adhesion and high image hardness, a particle size of 10 nm to 1,000 nm is preferred, 10 nm to 500 nm is more preferred, and 10 nm to 300 nm is particularly preferred. The volume-average particle size can be measured, for example, using a particle size analyzer (NanoTrac Wave-UT151, manufactured by MicroTrac-Bell Co., Ltd.).

[0020] There are no particular restrictions on the content of resin A, and it can be appropriately selected depending on the purpose. However, from the viewpoint of scratch resistance of the formed image and storage stability of the processing solution, it is preferable that the content be 2% by mass or more and 10% by mass or less, and more preferably 4% by mass or more and 8% by mass or less, relative to the total amount of processing solution. When the content of resin A is 2% by mass or more and 10% by mass or less, relative to the total amount of processing solution, adhesion to the substrate and adhesion to the formed image can be improved.

[0021] For the resin A, the glass transition temperature Tg is preferably -70°C to 0°C for urethane resins, and more preferably -55°C to -5°C for acrylic resins. For acrylic resins, it is preferably 0°C to 100°C, and more preferably 0°C to 80°C for acrylic resins. When the Tg of the processing liquid is -55°C to -5°C for urethane resins and 0°C to 80°C for acrylic resins, adhesion can be improved while ensuring discharge stability.

[0022] --Other ingredients-- The other components mentioned above are not particularly limited and can be selected as appropriate depending on the purpose.

[0023] Any known method can be used to apply the processing solution without any particular limitations. Examples include the inkjet method, blade coating method, gravure coating method, gravure offset coating method, bar coating method, roll coating method, knife coating method, air knife coating method, comma coating method, U-comma coating method, AKKU coating method, smoothing coating method, microgravure coating method, reverse roll coating method, 4-roll coating method, 5-roll coating method, dip coating method, curtain coating method, slide coating method, die coating method, and the like. The aforementioned processing solution can be used as a pre-treatment solution before applying the color ink.

[0024] The aforementioned substrate is not particularly limited as long as it is one that has been conventionally used as a recording medium, and can be appropriately selected according to the purpose.

[0025] [Recording medium] There are no particular restrictions on the recording medium; plain paper, glossy paper, specialty paper, cloth, etc., can be used, but good image formation is also possible with non-permeable substrates. The aforementioned non-permeable substrate is a substrate having a surface with low water permeability and absorption, and includes materials that have numerous internal cavities but do not open to the outside. More quantitatively, in the Bristow method, from the start of contact for 30 msec 1 / 2Up to 10 mL / m² of water absorption capacity 2 The following refers to the base material. As the non-permeable substrate, plastic films such as polyvinyl chloride resin film, polyethylene terephthalate (PET) film, polypropylene, polyethylene, and polycarbonate film can be suitably used. In addition to materials commonly used as recording media, other materials such as wallpaper, flooring, tiles, fabrics for clothing like T-shirts, textiles, and leather can be used as appropriate. Furthermore, by adjusting the configuration of the transport path for the recording media, ceramics, glass, and metals can also be used.

[0026] <Ink application process and ink application means> The ink application step is a step of applying an ink onto the processing liquid, the ink containing a colorant, an organic solvent with a boiling point of 290°C or higher, a silicone-based surfactant, and resin B, wherein the content of the organic solvent with a boiling point of 290°C or higher is 0.5% by mass or more of the total amount of ink. The ink application means is a means for applying the ink, which is contained in an ink container, onto the processing liquid. The ink contains a colorant, an organic solvent with a boiling point of 290°C or higher, a silicone-based surfactant, and resin B, and the content of the organic solvent with a boiling point of 290°C or higher is 0.5% by mass or more of the total amount of ink. There are no particular restrictions on the ink container, and it can be appropriately selected according to the purpose.

[0027] -ink- The following describes the colorants used in the ink, organic solvents with a boiling point of 290°C or higher, silicone-based surfactants, resin B, water, and other components.

[0028] --Colorants-- The aforementioned coloring material is not particularly limited, and pigments and dyes can be used. The aforementioned pigments can be inorganic or organic pigments. These may be used individually or in combination of two or more. Mixed crystals may also be used. Examples of the aforementioned pigments include black pigment, yellow pigment, magenta pigment, cyan pigment, white pigment, green pigment, orange pigment, glossy pigments such as gold and silver, and metallic pigments. As the inorganic pigments mentioned above, titanium dioxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chromium yellow can be used, as well as carbon black produced by known methods such as the contact method, furnace method, and thermal method. Furthermore, as the organic pigment, 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 chelates, etc.), nitro pigments, nitroso pigments, aniline black, etc. can be used. Among these pigments, those with good affinity for the solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used. Specific examples of the aforementioned pigments include carbon blacks (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, or metals such as copper, iron (CI Pigment Black 11), and titanium dioxide, and organic pigments such as aniline black (CI Pigment Black 1). Furthermore, for color applications, we have 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 O Range 5, 13, 16, 17, 36, 43, 51, CI Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48:2, 48:2 (Permanent Red 2B(Ca)), 48:3, 48:4, 49:1, 52:2, 53:1, 57:1 (Brilliant Carmine 6B), 60:1, 63:1, 63:2, 64:1, 81, 83, 88 , 101 (Bengara), 104, 105, 106, 108 (Cadmium Red), 112, 114, 122 (Quinacridone Magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 184, 185, 190, 193, 202, 207, 208, 209, 213, 219, 224, 254, 264, CI Pigment Violet 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; CI Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, etc. are available. The aforementioned dyes are not particularly limited and can include acid dyes, direct dyes, reactive dyes, and basic dyes. They may be used individually or in combination of two or more. Examples of the aforementioned dyes include 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, 173; CI Direct Red 1, 4, 9, 80, 81, 225, 227; CI Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202; CI Direct Black 19, 38, 51, 71, 154, 168, 171, 195; and CI Reactive Red. Examples include 14, 32, 55, 79, 249, and CI Reactive Black 3, 4, 35.

[0029] The content of the colorant in the ink is preferably 0.1% by mass or more and 15% by mass or less, and more preferably 1% by mass or more and 10% by mass or less, from the viewpoint of improving image density, good fixation and ejection stability.

[0030] Methods for obtaining ink by dispersing the aforementioned pigments include introducing hydrophilic functional groups into the pigment to make it a self-dispersible pigment, coating the surface of the pigment with a resin and dispersing it, and using a dispersant to disperse it. One method for introducing hydrophilic functional groups into the aforementioned pigment to create the self-dispersible pigment is to add functional groups such as sulfone groups or carboxyl groups to the pigment (e.g., carbon) to make it dispersible in water. One method for coating and dispersing the surface of the aforementioned pigment with a resin is to encapsulate the pigment in microcapsules so that it can be dispersed in water. This can be rephrased as resin-coated pigment. In this case, it is not necessary for all pigments incorporated into the ink to be coated with resin; as long as the effects of the present invention are not impaired, uncoated pigments or partially coated pigments may be dispersed in the ink. Resin-coated pigments are preferred from the viewpoint of ejection reliability and coating film durability. Methods for dispersion using the aforementioned dispersant include methods using known low-molecular-weight dispersants, such as surfactants, and high-molecular-weight dispersants. Depending on the pigment, the dispersant can be, for example, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc. RT-100 (nonionic surfactant) manufactured by Takemoto Oil & Fat Co., Ltd., and sodium naphthalene sulfonate formalin condensate can also be suitably used as dispersants. The aforementioned dispersing agent may be used alone or in combination of two or more types.

[0031] [Pigment dispersion] It is possible to obtain ink by mixing the aforementioned pigment with materials such as water or organic solvents. Alternatively, ink can be manufactured by mixing the pigment with other materials such as water or dispersants to form a pigment dispersion, and then mixing this dispersion with materials such as water or organic solvents. The aforementioned pigment dispersion is obtained by mixing and dispersing water, pigment, pigment dispersant, and other components as needed, and adjusting the particle size. Dispersion is preferably performed using a disperser. There are no particular restrictions on the particle size of the pigment in the aforementioned pigment dispersion, but from the standpoint of improving the dispersion stability of the pigment and enhancing image quality such as ejection stability and image density, it is preferable that the maximum frequency is between 20 nm and 500 nm, and more preferably between 20 nm and 150 nm, in terms of maximum number. The particle size of the pigment can be measured using a particle size analyzer (NanoTrac Wave-UT151, manufactured by MicroTrac-Bell Co., Ltd.). The pigment content in the pigment dispersion is not particularly limited and can be appropriately selected depending on the purpose, but from the standpoint of obtaining good discharge stability and increasing image density, it is preferably 0.1% by mass or more and 50% by mass or less, and more preferably 0.1% by mass or more and 30% by mass or less. The pigment dispersion is preferably filtered to remove coarse particles and degassed using a filter, centrifuge, or the like, if necessary.

[0032] --Organic solvents with a boiling point of 290°C or higher-- There are no particular restrictions on the organic solvent having a boiling point of 290°C or higher, and it can be appropriately selected depending on the purpose. Examples include benzyl benzoate, glycerin (glycerol), and triethanolamine. By including an organic solvent with a boiling point of 290°C or higher, the continuous ejection stability of the ink can be improved. The content of the organic solvent having a boiling point of 290°C or higher is 0.5% by mass or more, preferably 0.5% by mass or more and 5% by mass or less, relative to the total amount of ink. When the content of the organic solvent having a boiling point of 290°C or higher is 0.5% by mass or more relative to the total amount of ink, the initial ejection performance of the ink and the scratch resistance of the formed image can be improved, and when it is 0.5% by mass or more and 5% by mass or less, the continuous ejection stability of the ink and the drying performance of the ink can be improved.

[0033] Furthermore, the aforementioned ink may also contain other organic solvents.

[0034] ---Other Organic Solvents--- The aforementioned other organic solvents are not particularly limited and can be appropriately selected depending on the purpose; for example, water-soluble organic solvents can be used. Examples of the water-soluble organic solvents include polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds. Specific examples of the aforementioned water-soluble organic solvents include, for example, 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, Polyhydric alcohols such as 5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl-1,3-pentanediol, petriol, etc., ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, di Examples 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. It is preferable to use an organic solvent with a boiling point of 250°C or lower, as it not only functions as a wetting agent but also provides good drying properties.

[0035] Furthermore, polyol compounds having 8 or more carbon atoms and glycol ether compounds are also suitably used. Specific examples of polyol compounds having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol. Specific examples of glycol ether compounds include polyhydric alcohol alkyl ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether; and polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether. Polyol compounds with 8 or more carbon atoms, and glycol ether compounds, can improve ink penetration when paper is used as a recording medium.

[0036] There are no particular restrictions on the content of the other organic solvents mentioned above, and they can be appropriately selected depending on the purpose. However, from the viewpoint of ink drying properties and ejection reliability, it is preferable that the content be 10% by mass or more and 60% by mass or less, and more preferably 20% by mass or more and 60% by mass or less, based on the total amount of ink.

[0037] --Silicone-based surfactants-- There are no particular restrictions on the silicone-based surfactant, and it can be appropriately selected depending on the purpose. There are no particular limitations on the silicone-based surfactant, and it can be appropriately selected depending on the purpose. Examples include side-chain modified polydimethylsiloxane, both-end modified polydimethylsiloxane, one-end modified polydimethylsiloxane, and both-end modified polydimethylsiloxane. Polyether-modified silicone-based surfactants having a polyoxyethylene group or a polyoxyethylene-polyoxypropylene group as a modifying group are particularly preferred as they exhibit good properties as aqueous surfactants.

[0038] Among the silicone-based surfactants, those that do not decompose even at high pH are preferred. Examples include side-chain modified polydimethylsiloxane, both-end modified polydimethylsiloxane, one-end modified polydimethylsiloxane, and both-end modified polydimethylsiloxane. Those having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group are particularly preferred because they exhibit good properties as aqueous surfactants.

[0039] Furthermore, a polyether-modified silicone surfactant can also be used as the silicone surfactant. Examples include compounds in which a polyalkylene oxide structure is introduced into the Si side chain of dimethylsiloxane.

[0040] Such surfactants may be synthesized as appropriate, or commercially available products may be used. Commercially available products include, for example, those from BIC Chemie Inc., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., and Kyoeisha Chemical Co., Ltd.

[0041] There are no particular limitations on the polyether-modified silicone surfactants mentioned above, and they can be appropriately selected depending on the purpose. For example, one example is a polyalkylene oxide structure represented by the general formula (S-1), in which a polyalkylene oxide structure is introduced into the Si side chain of dimethylpolysiloxane. JPEG0007830921000001.jpg66151 General formula (S-1) (However, in general formula (S-1), m, n, a, and b each independently represent integers, R represents an alkylene group, and R' represents an alkyl group.)

[0042] Commercially available polyether-modified silicone surfactants can be used, such as KF-618, KF-642, KF-643 (Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5602, SS-1906EX (Nippon Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (Toray Dow Corning Silicone Co., Ltd.), BYK-33, BYK-387 (BIC Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (Toshiba Silicone Co., Ltd.).

[0043] The content of the silicone-based surfactant is preferably 0.001% to 5% by mass, more preferably 0.05% to 5% by mass, and even more preferably 0.1% to 3% by mass, relative to the total amount of ink. When the content of the silicone-based surfactant is 0.001% to 5% by mass relative to the total amount of ink, wettability and ejection stability can be improved, and image quality can be improved. Furthermore, when the content of the silicone-based surfactant is 0.1% to 3% by mass relative to the total amount of ink, the initial ejection stability of the ink and the scratch resistance of the formed image can be improved.

[0044] Furthermore, the ink may also contain other surfactants besides the silicone surfactant.

[0045] ---Other surfactants--- The aforementioned other surfactants are not particularly limited and can be appropriately selected depending on the purpose. For example, fluorinated surfactants, amphoteric surfactants, nonionic surfactants, and anionic surfactants can all be used. Examples of the fluorinated surfactants include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in their side chains, as they exhibit low foaming properties. Examples of the perfluoroalkyl sulfonic acid compounds include perfluoroalkyl sulfonic acid and perfluoroalkyl sulfonate salts. Examples of the perfluoroalkyl carboxylic acid compounds include perfluoroalkyl carboxylic acid and perfluoroalkyl carboxylic acid salts. Examples of the polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in their side chains include sulfate ester salts of polyoxyalkylene ether polymers having perfluoroalkyl ether groups in their side chains and salts of polyoxyalkylene ether polymers having perfluoroalkyl ether groups in their side chains. Examples of counterions for the salts of these fluorinated surfactants include Li, Na, K, NH4, NH3CH2CH2OH, NH2(CH2CH2OH)2, and NH(CH2CH2OH)3. Examples of the aforementioned amphoteric surfactants include laurylaminopropionate, lauryldimethylbetaine, stearyldimethylbetaine, and lauryldihydroxyethylbetaine. Examples of the nonionic surfactants 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 alcohols. Examples of the anionic surfactants include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl salt, and salts of polyoxyethylene alkyl ether sulfate. These can be used individually or in combination of two or more types.

[0046] --Resin B-- There are no particular restrictions on the resin B, and it can be appropriately selected depending on the purpose. Examples 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. Furthermore, resin particles made from these resins may be used as the resin B. It is possible to obtain ink by mixing the resin particles, which are dispersed in water as a dispersion medium in a resin emulsion, with materials such as colorants and organic solvents. The aforementioned resin particles may be synthesized as appropriate, or commercially available products may be used. Furthermore, these may be used individually or in combination of two or more types of resin particles. From the viewpoint of adhesion to the substrate, it is preferable that the substrate contains urethane resin or acrylic resin.

[0047] The content of resin B is preferably 1% to 30% by mass, more preferably 2% to 10% by mass, and even more preferably 2% to 6% by mass, relative to the total amount of ink. When the content of resin B is 1% to 30% by mass relative to the total amount of ink, the storage stability of the ink and the fixation of the formed image can be improved. Furthermore, when the content of resin B is 2% to 10% by mass relative to the total amount of ink, the ejection stability and the fixation of the formed image can be improved. Moreover, when the content of resin B is 2% to 6% by mass relative to the total amount of ink, the viscosity of the ink can be kept within an appropriate range, and the ejection stability can be improved.

[0048] The resin B may be in the form of resin particles. The resin particles, dispersed in water as a dispersion medium, can be mixed with materials such as colorants and organic solvents to obtain ink. The resin particles may be synthesized as appropriate, or commercially available products may be used. Furthermore, one type of resin particle may be used alone, or two or more types of resin particles may be used in combination.

[0049] There are no particular restrictions on the volume-average particle size of the resin particles, and they can be appropriately selected depending on the purpose. However, from the standpoint of obtaining good adhesion and high image hardness, a particle size of 10 nm to 1,000 nm is preferred, 10 nm to 200 nm is more preferred, and 10 nm to 100 nm is particularly preferred. The volume-average particle size can be measured, for example, using a particle size analyzer (NanoTrac Wave-UT151, manufactured by MicroTrac-Bell Co., Ltd.).

[0050] There are no particular restrictions on the particle size of the solids in the ink, and they can be appropriately selected depending on the purpose. However, from the standpoint of improving ejection stability and image quality such as image density, it is preferable that the maximum frequency in terms of maximum number is between 20 nm and 1000 nm, and more preferably between 20 nm and 150 nm. The solids include resin particles, pigment particles, etc. The particle size can be measured using a particle size analyzer (NanoTrac Wave-UT151, manufactured by MicroTrac-Bell Co., Ltd.).

[0051] --water-- There are no particular restrictions on the water content, and it can be appropriately selected depending on the purpose. For example, 10% by mass or more and 90% by mass or less is preferred, and 20% by mass or more and 60% by mass or less is more preferred.

[0052] --Other ingredients-- The aforementioned other components are not particularly limited and can be appropriately selected depending on the purpose. Examples include defoaming agents, antiseptics and antifungal agents, rust inhibitors, and pH adjusters.

[0053] ---Antifoaming agent--- There are no particular limitations on the aforementioned defoaming agent; examples include silicone-based defoaming agents, polyether-based defoaming agents, and fatty acid ester-based defoaming agents. These may be used individually or in combination of two or more. Among these, silicone-based defoaming agents are preferred due to their superior foam-breaking effect.

[0054] ---Preservative and fungicide--- There are no particular restrictions on the aforementioned preservative and antifungal agent; for example, 1,2-benzisothiazolin-3-one is one such example.

[0055] ---Rust Inhibitor--- There are no particular restrictions on the rust inhibitor, and examples include acidic sulfites and sodium thiosulfate.

[0056] ---pH adjuster--- The pH adjusting agent is not particularly limited as long as it can adjust the pH to 7 or higher, and examples include amines such as diethanolamine and triethanolamine.

[0057] The physical properties of the ink are not particularly limited and can be appropriately selected according to 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 between 5 mPa·s and 30 mPa·s, and more preferably between 5 mPa·s and 25 mPa·s, as this improves print density and character quality and ensures good ejection. Here, viscosity can be measured using, for example, a rotational viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.). Measurement conditions are 25°C, standard cone rotor (1°34' × R24), sample volume of 1.2 mL, rotation speed of 50 rpm, and measurement can be performed in 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 levels well on the recording medium and shorten the ink drying time. The pH of the ink is preferably 7 to 12, and more preferably 8 to 11, from the viewpoint of preventing corrosion of the metal components that come into contact with the ink.

[0058] <Other processes and other means> The aforementioned other processes are not particularly limited and can be selected as appropriate depending on the purpose, for example, a drying process. The aforementioned other means are not particularly limited and can be appropriately selected depending on the purpose, and examples include drying methods.

[0059] <<Drying process and drying means>> The drying step is a step of drying the processing liquid and the ink. The drying means is a means for drying the processing liquid and the ink. In the drying process described above, especially when the recording medium is a non-permeable substrate, the drying temperature during recording is preferably 50°C or higher in order to improve fixation to the non-permeable substrate and suppress the occurrence of bleeding. There is no particular upper limit to the drying temperature during recording, and it can be appropriately selected according to the purpose, but 120°C or lower is preferred from the viewpoint of ejection reliability and thermal deformation of the substrate. Furthermore, 90°C or lower is more preferable from the viewpoint of the wettability of the ink to the substrate. There is no particular limit to the drying temperature before and after recording, and it can be appropriately selected according to the purpose, but 100°C or lower is preferred from the viewpoint of thermal deformation of the substrate in terms of ejection reliability and thermal deformation of the substrate.

[0060] [Records] The ink recording material of the present invention has an image formed on a recording medium using the ink of the present invention. The data can be recorded and produced as a record using an inkjet recording device and an inkjet recording method.

[0061] [Recording device, recording method] The ink of the present invention can be suitably used in various recording devices using the inkjet recording method, such as printers, facsimile machines, copying machines, printer / fax / copier combination machines, and 3D modeling devices. In the present invention, a recording device and a recording method refer to a device capable of ejecting ink, various processing liquids, etc., onto a recording medium, and a method of recording using said device. A recording medium refers to a material to which ink or various processing liquids can be temporarily attached. This recording device may include not only the ink ejection head, but also means for feeding, transporting, and ejecting the recording medium, as well as other devices referred to as pre-processing devices and post-processing devices. The recording device and recording method may include heating means for the heating process and drying means for the drying process. The heating means and drying means include, for example, means for heating and drying the printing surface and the back surface of the recording medium. The heating means and drying means are not particularly limited, but for example, a hot air heater and an infrared heater can be used. Heating and drying can be performed before printing, during printing, or after printing. The heating temperature is preferably 40°C to 120°C, more preferably 50°C to 120°C from the viewpoint of fixation, and even more preferably 50°C to 90°C from the viewpoint of not impairing the flexibility of the leather. Furthermore, recording devices and recording methods are not limited to those that visualize meaningful images such as characters and figures using ink. For example, they also include those that form patterns such as geometric designs, and those that create three-dimensional images. Furthermore, unless otherwise specified, recording devices include both serial type devices that move the ejection head and line type devices that do not move the ejection head. Furthermore, this recording device includes not only desktop models, but also wide-format recording devices capable of printing on A0-sized recording media, and continuous-feed printers that can use, for example, continuous paper wound in a roll as a recording medium. An example of a recording device will be described with reference to Figures 1 and 2. Figure 1 is a perspective view of the device. Figure 2 is a perspective view of the main tank. The image forming apparatus 400, as an example of a recording device, is a serial-type image forming apparatus. A mechanism 420 is provided inside the exterior 401 of the image forming apparatus 400. The ink storage sections 411 of the main tanks 410 (410k, 410c, 410m, 410y) for each color, black (K), cyan (C), magenta (M), and yellow (Y), are formed from packaging materials such as aluminum laminate film. The ink storage sections 411 are housed in, for example, plastic storage container cases 414. Thus, the main tanks 410 are used as ink cartridges for each color. Meanwhile, a cartridge holder 404 is provided at the back of the opening when the cover 401c of the main body of the device is opened. The main tank 410 is detachably mounted on the cartridge holder 404. As a result, the ink outlets 413 of the main tank 410 and the ejection heads 434 for each color are connected via supply tubes 436 for each color, enabling ink to be ejected from the ejection heads 434 to the recording medium.

[0062] This recording device may include not only an ink ejection unit, but also devices referred to as pre-treatment devices and post-treatment devices. As one embodiment of the pre-treatment device and post-treatment device, a liquid storage unit and a liquid ejection head are added, similar to the case of black (K), cyan (C), magenta (M), and yellow (Y) inks, to contain pre-treatment liquid and post-treatment liquid, and the pre-treatment liquid and post-treatment liquid are ejected using an inkjet recording method. Other embodiments of the pre-processing and post-processing devices include those that utilize methods other than inkjet recording, such as blade coating, roll coating, or spray coating.

[0063] Examples of methods for applying the ink include inkjet, blade coating, gravure coating, gravure offset coating, bar coating, roll coating, knife coating, air knife coating, comma coating, U-comma coating, AKKU coating, smoothing coating, microgravure coating, reverse roll coating, four-roll coating, five-roll coating, dip coating, curtain coating, slide coating, and die coating.

[0064] Figure 3 is a schematic diagram showing an example of an image forming apparatus used in the image forming method of the present invention. The image forming apparatus 100 in Figure 3 includes means for applying processing liquid (processing liquid coating device 21), ejection means for ejecting ink (ink ejection head 22), and a conveyor belt 23. The image forming apparatus 100 performs printing on the recording medium 11.

[0065] (Processing solution and ink set) The present invention provides a set of processing solution and ink, comprising a processing solution containing a polyvalent metal salt and a resin, The present invention comprises an ink containing a colorant, an organic solvent with a boiling point of 290°C or higher, a silicone-based surfactant, and a resin, wherein the content of the organic solvent with a boiling point of 290°C or higher is 0.5% by mass or more of the total amount of ink. The processing solution and ink in the set of processing solution and ink of the present invention are the same as the processing solution and ink in the printing method of the present invention.

[0066] (Manufacturing method and apparatus for manufacturing printed materials) The present invention provides a method for manufacturing printed materials, comprising: a processing solution application step of applying a processing solution containing a polyvalent metal salt and a resin to a substrate; and an ink application step of applying an ink containing a colorant, an organic solvent with a boiling point of 290°C or higher, a silicone-based surfactant, and a resin, wherein the content of the organic solvent with a boiling point of 290°C or higher is 0.5% by mass or more of the total amount of ink, onto the processing solution, and further including other steps as necessary. Furthermore, the printing apparatus for the printing method of the present invention comprises: a processing liquid containment section containing a processing liquid containing a polyvalent metal salt and resin A; a processing liquid application means for applying the processing liquid contained in the processing liquid containment section to a substrate; an ink containment section containing ink containing a colorant, an organic solvent having a boiling point of 290°C or higher, a silicone-based surfactant, and resin B, wherein the content of the organic solvent having a boiling point of 290°C or higher is 0.5% by mass or more with respect to the total amount of ink; and an ink application means for applying the ink contained in the ink containment section onto the processing liquid, and further comprising other means as necessary. The method for manufacturing printed materials according to the present invention is the same as the printing method according to the present invention. The apparatus for manufacturing the printed material is the same as the printing apparatus.

[0067] Furthermore, in the terminology of this invention, image formation, recording, printing, etc., are all synonymous.

[0068] Recording media, media, and printed material are all considered synonyms. [Examples]

[0069] The following describes embodiments of the present invention, but the present invention is not limited in any way to these embodiments. In the following embodiments, unless otherwise specified, the preparation and evaluation of the inks were carried out under conditions of room temperature of 25°C and relative humidity of 60%RH. In the embodiments, "parts" refers to "parts by mass," and "%" refers to "mass%" except in the evaluation criteria.

[0070] <Example of preparation of treatment solution a> The materials for the following formulation were mixed, and the total volume was reduced to 100 parts by mass using deionized water, after which the mixture was mixed and stirred. Then, the mixture was filtered through a filter with an average pore size of 5 μm (Sartorius, product name: Minisart) to obtain treated solution a. [Prescription] • 1,2-Propanediol (Product name: Propylene Glycol, manufactured by ADEKA Corporation) :35 parts by mass • 3-Methoxy-3-methyl-1-butanol (product name: Solfit, manufactured by Kuraray Co., Ltd.): 30 parts by mass • Polyurethane resin (1) (Product name: Xw-Um12, manufactured by Mitsui Chemicals, Inc.) :6.0 parts by mass • SAG-503A (silicone surfactant, manufactured by Nisshin Chemical Industry Co., Ltd.): 0.5 parts by mass Magnesium acetate hydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): 0.5 parts by mass • Ion-exchanged water: Remaining amount (Total: 100 parts by mass)

[0071] <Examples of preparation of treatment solutions b to r> Except for the change in the formulation shown in Tables 1 to 3 in the preparation example of treatment solution a, treatment solutions b to r were prepared in the same manner as in the preparation example of treatment solution a. Note that the resin content in the tables indicates the solid content.

[0072] [Table 1]

[0073] [Table 2]

[0074] [Table 3]

[0075] Next, we will describe an example of preparing a pigment dispersion used in ink.

[0076] [Example of preparation of black pigment dispersion] 11.2g of styrene, 2.8g of acrylic acid, 12g of lauryl methacrylate, 4g of polyethylene glycol methacrylate, 4g of styrene macromer, and 0.4g of mercaptoethanol were mixed and heated to 65°C. Next, a mixed solution of 100.8 g of styrene, 25.2 g of acrylic acid, 108 g of lauryl methacrylate, 36 g of polyethylene glycol methacrylate, 60 g of hydroxylethyl methacrylate, 36 g of styrene macromer, 3.6 g of mercaptoethanol, 2.4 g of azobismethylvaleronitrile, and 18 g of methyl ethyl ketone was added dropwise to the flask over 2.5 hours. After the initial addition, a mixed solution of 0.8 g of azobismethylvaleronitrile and 18 g of methyl ethyl ketone was added dropwise to the flask over 0.5 hours. After aging at 65°C for 1 hour, 0.8g of azobismethylvaleronitrile was added, and the mixture was aged for another hour. After the reaction was complete, 364 g of methyl ethyl ketone was added to the flask to obtain 800 g of polymer solution A with a solid content of 50%. Next, 28 g of polymer solution A, 42 g of carbon black (Cabot Corporation, Black Pearls 1000), 13.6 g of 1 mol / L potassium hydroxide aqueous solution, 20 g of methyl ethyl ketone, and 13.6 g of water were thoroughly stirred and then kneaded in a roll mill. The obtained paste was added to 200 g of pure water and thoroughly stirred. Methyl ethyl ketone was removed using an evaporator, and the mixture was pressure filtered through a polyvinylidene fluoride membrane filter with an average pore size of 5 μm. The water content was then adjusted to achieve a solid content of 20%, yielding a styrene-acrylic resin-coated black pigment dispersion with a solid content of 20%.

[0077] [Example of preparation of cyanide pigment dispersion] In the example of preparing a black pigment dispersion, a styrene-acrylic resin-coated cyan pigment dispersion with a solid content of 20% was obtained in the same manner as the example of preparing a black pigment dispersion, except that pigment blue 15:4 (SMART Cyan 3154BA, manufactured by SENSIENT) was used instead of carbon black.

[0078] [Example of magenta pigment dispersion preparation] In the example of preparing a black pigment dispersion, a styrene-acrylic resin-coated magenta pigment dispersion with a solid content of 20% was obtained in the same manner as the example of preparing a black pigment dispersion, except that Pigment Red 122 (manufactured by Sun Chemical Co., Ltd.) was used instead of carbon black.

[0079] [Example of preparation of yellow pigment dispersion] In the example of preparing a black pigment dispersion, a styrene-acrylic resin-coated yellow pigment dispersion with a solid content of 20% was obtained in the same manner as the example of preparing a black pigment dispersion, except that Pigment Yellow 74 (SMART Yellow 3074BA, manufactured by SENSIENT) was used instead of carbon black.

[0080] <Example of Ink A preparation> The ingredients for the following formulation were mixed, and the total volume was reduced to 100 parts by mass using deionized water, after which the mixture was mixed and stirred. Then, the mixture was filtered through a filter with an average pore size of 5 μm (Sartorius, product name: Minisart) to obtain ink A. [Ink formulation] • Black pigment dispersion: 20 parts by mass • 1,2-Propanediol (Product name: Propylene Glycol, manufactured by ADEKA Corporation) :15 parts by mass • 1,3-Butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.): 4 parts by mass • 2-Ethyl-1,3-Hexanediol (Trade name: EHD, manufactured by Kuraray Co., Ltd.) :1 part by mass • 3-Methoxy-3-methyl-1-butanol (product name: Solfit, manufactured by Kuraray Co., Ltd.): 5 parts by mass • 3-Methoxy-N,N-dimethylpropionamide (Trade name: M100, manufactured by Idemitsu Kosan Co., Ltd.): 10 parts by mass • Polyurethane resin (2) (Product name: Xw-Um3A, manufactured by Mitsui Chemicals, Inc.) :4.0 parts by mass • Polyurethane resin (3) (Product name: W6110, manufactured by Mitsui Chemicals, Inc., polyurethane resin, solid content concentration: 35% by mass): 6.0 parts by mass Triton HW1000, poly(oxyethylene) alkyl ether (manufactured by Dow Chemical, non-silicone surfactant): 0.2 parts by mass • SAG-503A (manufactured by Nisshin Chemical Industry Co., Ltd., silicone surfactant): 1.0 part by mass • Ion-exchanged water: Remaining amount (Total: 100 parts by mass)

[0081] <Examples of ink preparation (B-R)> Ink B to R were prepared in the same manner as in the preparation example of ink A, except that the formulation was changed as shown in Tables 4 to 6. Note that the resin content in the tables indicates the solid content. The polyurethane resin (5) used in inks C, H, M, and Q was prepared by the following method.

[0082] [Example of preparation of polyurethane resin (5)] In a nitrogen-purged container equipped with a thermometer, nitrogen gas inlet tube, and stirrer, 200.4 g of polyester polyol (product name: Polylight OD-X-2251, manufactured by DIC Corporation, average molecular weight 2,000), 15.7 g of 2,2-dimethylolpropionic acid, 48.0 g of isophorone diisocyanate, and 77.1 g of methyl ethyl ketone as an organic solvent were reacted using 0.06 g of DMTDL (dibutyltin dilaurate) as a catalyst. After continuing the reaction for 4 hours, 30.7 g of methyl ethyl ketone was supplied as a diluent, and the reaction was continued. When the average molecular weight of the reactants reached a range of 20,000 to 60,000, 1.4 g of methanol was added to terminate the reaction, thereby obtaining an organic solvent solution of urethane resin. Next, 13.4 g of a 48% by mass potassium hydroxide aqueous solution was added to the organic solvent solution of the urethane resin to neutralize the carboxyl groups present in the urethane resin. Then, 715.3 g of water was added and thoroughly stirred, followed by aging and desolventing to obtain a polyester-based urethane resin emulsion (polyurethane resin (5)) with a solid content concentration of 30% by mass. The lowest film formation temperature (MFT) of the obtained polyurethane resin (5), measured using a "film formation temperature test device" (manufactured by Imoto Seisakusho Co., Ltd.), was 74°C.

[0083] [Table 4]

[0084] [Table 5]

[0085] [Table 6]

[0086] The detailed information regarding the materials used in the processing solution and ink is as follows: [resin] • Polyurethane resin (1) (Product name: Xw-Um12, manufactured by Mitsui Chemicals, Inc.) • Polyurethane resin (2) (Product name: Xw-Um3A, manufactured by Mitsui Chemicals, Inc.) • Polyurethane resin (3) (Product name: W6110, manufactured by Mitsui Chemicals, Inc., solid content concentration: 35% by mass) • Polyurethane resin (4) (Product name: Superflex 300, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid content concentration: 30% by mass) • Polyurethane resin (6) (Product name: Xw-Um7, manufactured by Mitsui Chemicals, Inc., solids content: 30% by mass) • Acrylic resin (1) (Product name: Movinyl 6800, manufactured by Japan Coating Resin Co., Ltd., solid content concentration: 45% by mass) • Acrylic resin (2) (Product name: Movinyl 6969D, manufactured by Japan Coating Resin Co., Ltd., solid content concentration: 40% by mass) • Acrylic resin (3) (Product name: Movinyl 6750, manufactured by Japan Coating Resin Co., Ltd., solid content concentration: 50% by mass) • Acrylic resin (4) (Product name: Movinyl 6810, manufactured by Japan Coating Resin Co., Ltd., solid content concentration: 40% by mass) [Organic solvents] • 1,2-Propanediol (Product name: Propylene Glycol, manufactured by ADEKA Corporation) • 1,3-Propanediol (manufactured by ADEKA Corporation) • 1,3-Butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) • 2-Ethyl-1,3-Hexanediol (Trade name: EHD, manufactured by Kuraray Co., Ltd.) • 3-methyl-1,5-pentanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) • 3-Methoxy-1-butanol (Trade name: MB, manufactured by Daicel Corporation) • 3-Methoxy-3-methyl-1-butanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) • 3-Methoxy-N,N-dimethylpropionamide (Trade name: Equamid M100, manufactured by Idemitsu Kosan Co., Ltd.) • 3-Butoxy N,N-dimethylpropionamide (manufactured by Tokyo Chemical Industry Co., Ltd.) [Organic solvents with a boiling point of 290°C or higher] • Triethanolamine (manufactured by Sigma-Aldrich) Glycerin (manufactured by Sakamoto Pharmaceutical Co., Ltd.) [Surfactants] Triton HW1000 (poly(oxyethylene) alkyl ether, manufactured by Dow Chemical, non-silicone surfactant) • BYK348 (manufactured by Big Chemie Japan Co., Ltd., silicone-based surfactant) • SAG-503A (manufactured by Nisshin Chemical Industry Co., Ltd., silicone-based surfactant) [Flocculants (metal salts)] • Calcium acetate hydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) • Magnesium acetate hydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) • Aluminum chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) • Sodium chloride (manufactured by Fuso Pharmaceuticals Ltd.)

[0087] (Examples 1-11 and Comparative Examples 1-8) Using the combinations shown in Tables 7 and 8, the "initial ink ejection stability" of the prepared inks, and the "image scratch resistance," "image blurring," and "image cracking" of the images formed using the processing solution and inks were evaluated as follows.

[0088] <Initial ink ejection stability> The inkjet ejection head installed in the ejection evaluation device (EV2500, manufactured by Genesis) is filled with the prepared ink, and after maintenance operations are performed, ejection is started. The evaluation device's camera was used to observe ink droplet ejection. Nozzles that did not eject ink droplets (total: 320, in a single row) were designated as non-ejecting nozzles, and the number of non-ejecting nozzles was counted. The initial ink ejection stability was evaluated based on the following evaluation criteria. ○ and ◎ indicate levels suitable for practical use. [Evaluation Criteria] ◎: Number of non-discharging nozzles is between 0 and 5 (discharge rate: between 97% and 100%) ○: Number of non-discharging nozzles is 6 or more but 10 or less (discharging rate: 94.5% or more but less than 97%) ×: Number of non-discharging nozzles is 11 or more (discharging rate: less than 94.5%)

[0089] [Image Formation] In Examples 1-11 and Comparative Examples 1-8, the ink was filled into the black section of an inkjet printer (device name: Ri100, manufactured by Ricoh Co., Ltd.), and the processing solution was filled into the magenta section. For the substrates used were polyester felt (average thickness 2 mm), nonwoven fabric (average thickness 0.3 mm), and PET (average thickness 0.2 mm). The processing solution was applied using the T-shirt cleaning mode, with an adhesion amount of approximately 3.7 g / m². 2 I printed out a solid image. Next, the ink coverage is approximately 13.0 g / m². 2 The solid color image was printed, and the printed material was dried in an 80°C hot air dryer to fix the image.

[0090] <Image scratch resistance> The image obtained on polyester felt was cut to a size of 2.5 cm x 20 cm and placed in a dyed fabric rubbing fastness tester (model: AR-2, manufactured by Intec Co., Ltd.). A load of 200 g was applied, white cloth (Kanakin No. 3) was used, and the test was performed at a reciprocating speed of 30 cycles / minute. After 25 cycles for dry rubbing and 5 cycles for wet rubbing, the condition of the image and white cloth was observed and evaluated according to the following criteria. If the evaluation result is "○" or "◎", it is at a level that is actually usable. In the evaluation criteria, "image abnormality" refers to a condition where the image is scratched or the image (coating) has peeled off from the recording medium. [Evaluation Criteria] ◎: No abnormalities found in either the cotton fabric or the image. ○: Although the cotton fabric is discolored, there are no noticeable image abnormalities. △: The cotton fabric is colored, making the image anomaly immediately visible (the base material is not exposed). ×: The cotton fabric is colored, and the base material is exposed.

[0091] <Image blurring (color boundary blurring)> After applying the pretreatment solution to the substrate, an image was printed with each color adjacent to the others, and the degree of color bleeding at the color boundaries was visually inspected. Evaluation results of "○" and "◎" indicate a level suitable for practical use. [Evaluation Criteria] ◎: No bleeding at all ○: There is some jaggedness at the color boundaries and slight variations in color intensity that can be seen upon close inspection (the width of the jaggedness and color variation is 1.0 mm or less). △: The jaggedness at the color boundaries and the difference in color intensity are immediately apparent.

[0092] <Image crack> After applying the pretreatment solution to the substrate, an ink film is formed, and the image quality after the drying process is checked and evaluated based on the following evaluation criteria. A "○" result indicates that the image is at a level suitable for practical use. [Evaluation Criteria] ○: No cracks are visible in the image. ×: Cracks have appeared in the image.

[0093] [Table 7]

[0094] [Table 8]

[0095] Examples of the present invention are as follows: <1> A treatment solution application step in which a treatment solution containing a polyvalent metal salt and resin A is applied to the substrate, An ink application step of applying an ink containing a colorant, an organic solvent with a boiling point of 290°C or higher, a silicone-based surfactant, and resin B, wherein the content of the organic solvent with a boiling point of 290°C or higher is 0.5% by mass or more relative to the total amount of ink, onto the processing liquid; This printing method is characterized by including [a specific element]. <2> The content of the organic solvent having a boiling point of 290°C or higher is 0.5% by mass or more and 5% by mass or less relative to the total amount of ink. <1> This is the printing method described. <3> The content of the silicone-based surfactant is 0.1% by mass or more and 3% by mass or less relative to the total amount of ink. <1> from <2> This is the printing method described in one of the following. <4> The resin A comprises at least one of urethane resin and acrylic resin. <1> from <3> This is the printing method described in one of the following. <5> The content of resin A is 2% by mass or more and 10% by mass or less relative to the total amount of processing liquid. <1> from <4> This is the printing method described in one of the following. <6> The polyvalent metal salt comprises at least one of a calcium salt and a magnesium salt. <1> from <5> This is the printing method described in one of the following. <7> The content of the polyvalent metal salt is 0.1% by mass or more and 3% by mass or less relative to the total volume of the treatment liquid. <1> from <6> This is the printing method described in one of the following. <8> A treatment solution containing polyvalent metal salts and resins, This is a set of processing liquid and ink characterized by comprising a colorant, an organic solvent with a boiling point of 290°C or higher, a silicone-based surfactant, and a resin, wherein the content of the organic solvent with a boiling point of 290°C or higher is 0.5% by mass or more of the total amount of ink. <9> The content of the organic solvent having a boiling point of 290°C or higher is 0.5% by mass or more and 5% by mass or less relative to the total amount of ink. <8> This is a set of processing solution and ink as described. <10> A treatment solution application step in which a treatment solution containing a polyvalent metal salt and a resin is applied to the substrate, An ink application step of applying an ink containing a colorant, an organic solvent with a boiling point of 290°C or higher, a silicone-based surfactant, and a resin, wherein the content of the organic solvent with a boiling point of 290°C or higher is 0.5% by mass or more of the total amount of ink, onto the processing liquid; A method for manufacturing printed materials, characterized by including [a specific element].

[0096] The aforementioned <1> from <7> The printing method described in any of the above <8> from <9> A set of processing liquid and ink as described in any of the above, and the <10> The method for manufacturing printed materials described herein can solve the problems of the past and achieve the objectives of the present invention. [Explanation of symbols]

[0097] 400 Image forming apparatus 401 Exterior of the image forming apparatus 401c Cover of the main unit of the device 404 Cartridge Holder 410 Main Tank Main tanks for each color: 410k, 410c, 410m, 410y (Black (K), Cyan (C), Magenta (M), Yellow (Y)) 411 Ink reservoir 413 Ink outlet 414 Storage container case 420 Mechanism Department 434 Discharge head 436 Supply Tube [Prior art documents] [Patent Documents]

[0098] [Patent Document 1] Japanese Patent Publication No. 2019-019187

Claims

1. A treatment solution application step in which a treatment solution containing a polyvalent metal salt and resin A is applied to the substrate, An ink application step of applying an ink containing a colorant, an organic solvent with a boiling point of 360°C or higher, a silicone-based surfactant, and resin B, wherein the content of the organic solvent with a boiling point of 360°C or higher is 0.5% by mass or more relative to the total amount of ink, onto the processing liquid; A printing method characterized by including the following.

2. The printing method according to claim 1, wherein the content of the organic solvent having a boiling point of 360°C or higher is 0.5% by mass or more and 5% by mass or less with respect to the total amount of ink.

3. The printing method according to any one of claims 1 to 2, wherein the content of the silicone-based surfactant is 0.1% by mass or more and 3% by mass or less with respect to the total amount of ink.

4. The printing method according to any one of claims 1 to 3, wherein the resin A includes at least one of urethane resin and acrylic resin.

5. The printing method according to any one of claims 1 to 4, wherein the content of resin A is 2% by mass or more and 10% by mass or less with respect to the total amount of processing liquid.

6. The printing method according to any one of claims 1 to 5, wherein the polyvalent metal salt comprises at least one of a calcium salt and a magnesium salt.

7. The printing method according to any one of claims 1 to 6, wherein the content of the polyvalent metal salt is 0.1% by mass or more and 3% by mass or less with respect to the total amount of the processing liquid.

8. A treatment solution containing polyvalent metal salts and resins, A set of processing liquid and ink, characterized by comprising a colorant, an organic solvent having a boiling point of 360°C or higher, a silicone-based surfactant, and a resin, wherein the content of the organic solvent having a boiling point of 360°C or higher is 0.5% by mass or more of the total amount of ink.

9. The set of processing liquid and ink according to claim 8, wherein the content of the organic solvent having a boiling point of 360°C or higher is 0.5% by mass or more and 5% by mass or less with respect to the total amount of ink.

10. A treatment solution application step in which a treatment solution containing a polyvalent metal salt and a resin is applied to the substrate, An ink application step of applying an ink containing a colorant, an organic solvent with a boiling point of 360°C or higher, a silicone-based surfactant, and a resin, wherein the content of the organic solvent with a boiling point of 360°C or higher is 0.5% by mass or more of the total amount of ink, onto the processing liquid; A method for manufacturing printed materials, characterized by including the following:

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