Ink, printing device, printing method, and printed matter

Abstract

This invention relates to ink, printing apparatus, printing method, and printed matter. The object of this invention is to provide an ink that exhibits excellent spray stability and substrate concealment when applied to surfaces of buildings (such as roads, exterior or interior finishes), civil structures such as bridges or tunnels, and porous substrates. The ink of this invention comprises solvent, resin, and thickening particles, and operates at a shear rate of 1 second. ‑1 The viscosity at 25°C is 3.00 × 10⁻⁶. 3 Above mPa·s and 2.50 × 10 4 Below mPa·s, at a shear rate of 5000 s ‑1 Under normal conditions, the viscosity at 25°C is below 130 mPa·s.

Description

Technical Field

[0001] This invention relates to ink, printing apparatus, printing method, and printed matter. Background Technology

[0002] Traditionally, solvent-based coatings have been used for applications such as road surfaces, floors, and building walls. While solvent-based inks offer advantages such as short drying times, susceptibility to weather conditions, and flexibility in application, they contain volatile organic compounds (VOCs), posing risks of health hazards, environmental pollution, odor, and flammability.

[0003] Due to these issues, in recent years, water-based paints have gradually replaced those used for road surfaces, floors, and building walls. Compared to solvent-based paints, water-based inks have almost no odor and significantly reduce VOCs, thus having less impact on people and the environment.

[0004] As for the aforementioned water-based inks used for applications such as road surfaces, floors, and building walls, for example, in order to further improve adhesion to substrates, especially adhesion to asphalt when applied to road surfaces, and to further improve the stability of the coating, a water-based coating composition that controls the average particle size and particle size distribution of the water-based dispersion matrix resin has been proposed (see, for example, Patent Document 1).

[0005] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent No. 4623707 Summary of the Invention

[0007] The present invention is proposed in view of the problems existing in the above-mentioned background technology, and its purpose is to provide an ink that has excellent spraying stability and substrate concealment when coating the walls of buildings such as roads, exterior or interior decorations, civil structures such as bridges or tunnels, and porous substrates.

[0008] As a means of solving this problem, the ink of the present invention comprises a solvent, a resin, and thickening particles, and is applied at a shear rate of 1 second. -1 The viscosity at 25°C is 3.00 × 10⁻⁶. 3 Above mPa·s and 2.50 × 10 4 Below mPa·s, at a shear rate of 5000 s -1 Under normal conditions, the viscosity at 25°C is below 130 mPa·s.

[0009] The effects of the present invention are explained below:

[0010] According to the present invention, an ink is provided that exhibits excellent spray stability and substrate concealment when applied to the walls of buildings such as roads, exterior or interior decorations, the walls of civil structures such as bridges or tunnels, and porous substrates. Attached Figure Description

[0011] Figure 1 This is a schematic diagram illustrating an example of the printing apparatus of the present invention.

[0012] Figure 2 This is a three-dimensional illustration showing an example of the main container in a printing apparatus.

[0013] Figure 3 This is a schematic side view showing an example of a liquid discharge device used in a printing apparatus.

[0014] Figure 4 This is a schematic top view showing an example of a liquid discharge device used in a printing apparatus.

[0015] Figure 5 This is a schematic diagram showing an example of an inkjet nozzle, and a diagram showing an example of the nozzle in its closed state.

[0016] Figure 6 This is a schematic diagram showing an example of an inkjet nozzle, and a diagram showing an example of the nozzle in its open state.

[0017] The symbols in the diagram have the following meanings:

[0018] 1. Matrix

[0019] 2 Nozzle orifice

[0020] 3 ink room

[0021] 4 needle valve

[0022] 5 Ink Input Channels

[0023] 6 Ink Output Channels

[0024] 7. Elastomer diaphragm

[0025] 8. Movable iron core

[0026] 9. Storage space for drive mechanism

[0027] 10. Spring Material

[0028] 11. Fixed iron core

[0029] 12 Solenoids

[0030] 13 Pressurization Channel

[0031] 14. Springs for preventing screw loosening

[0032] 15. Adjustment bolts for clearance

[0033] 16 nuts

[0034] 17 Ink Cans

[0035] 18 pumps

[0036] 20. Loop Path

[0037] 400 Image forming apparatus

[0038] 401 External mounting of image forming apparatus

[0039] 401c The cover of the main body of the device

[0040] 404 Ink Cartridge Retainer

[0041] 410 Main Tank

[0042] 410k, 410c, 410m, 410y Various colored master containers for black (K), cyan (C), magenta (M), and yellow (Y).

[0043] 411 Ink Storage Department

[0044] 413 Ink outlet

[0045] 414 Storage container shell

[0046] 420 Department

[0047] 434 Discharge Head

[0048] 436 Supply Management Detailed Implementation

[0049] (ink)

[0050] The ink of the present invention contains solvent, resin, and tackifying particles, and may further contain other components as needed.

[0051] The ink of the present invention is preferably an ink for coating road surfaces, exterior surfaces, and porous substrates.

[0052] The ink of this invention exhibits pseudoplastic flow. Therefore, after the ink is sprayed onto asphalt or similar road surfaces, its viscosity increases, making it difficult to penetrate the road surface, resulting in a thicker coating and improved concealment. Furthermore, when the ink is sprayed from a nozzle using an inkjet method, its viscosity decreases, thus improving spray stability.

[0053] In addition, even on the walls of buildings, bridges, tunnels and other civil structures, the ink viscosity increases after it is sprayed out. Therefore, it is possible to thicken the coating on the wall while suppressing ink dripping, thereby improving the concealment.

[0054] The aforementioned "pseudoplastic flow" refers to flow at a shear rate of 1 second. -1 The viscosity at 25°C is 3.00 × 10⁻⁶. 3 Above mPa·s and 2.50 × 10 4 Below mPa·s, at a shear rate of 5000 s -1 Under normal conditions, the viscosity at 25°C is below 130 mPa·s.

[0055] The ink described in Patent Document 1 is a water-based ink used for applications such as road surfaces, floors, and building walls. However, due to the excessively large particle size in the ink, the ink's fluidity deteriorates, and its viscosity remains high even under high shear rates, resulting in poor ejection stability.

[0056] The ink of this invention exhibits pseudoplastic flow; therefore, after being sprayed onto asphalt or similar surfaces, the ink viscosity increases, making it difficult to penetrate the interior of the surface, resulting in a thicker coating and improved concealment. Furthermore, when the ink is ejected from a nozzle using an inkjet method, the lower ink viscosity improves ejection stability.

[0057] The ink of this invention operates at a shear rate of 1 second. -1 The viscosity at 25°C is 3.00 × 10⁻⁶. 3 Above mPa·s and 2.50 × 10 4 Below mPa·s, considering superior concealment and the ability to suppress ink scattering during ejection, 6.00 × 10⁻⁶ is preferred. 3 Above mPa·s and 2.50 × 10 4 Below mPa·s, more preferably 6.00 × 10⁻⁶ mPa·s. 3 Pa·s or higher and 1.40 × 10⁻⁶ mPa·s or higher 4 Below mPa·s.

[0058] The ink of this invention operates at a shear rate of 5000 s. -1 Under normal conditions, the viscosity at 25°C is below 130 mPa·s. From the perspective of obtaining better discharge stability, it is preferable to have a viscosity above 30 mPa·s and below 80 mPa·s.

[0059] The ink of the present invention is preferably used at a shear rate of 0.1 s. -1 The viscosity at 25°C is 3.00 × 10⁻⁶. 4This results in superior concealment and reduces ink scattering during ejection.

[0060] There are no particular limitations on the method for measuring the viscosity, and it can be appropriately selected according to the purpose. For example, the cone plate (cone radius: 25 mm, cone angle: 1°) of MCR301 (manufactured by Anton Parr) can be used for measurement.

[0061] <Thickening particles>

[0062] The so-called "thickening property" of the aforementioned thickening particles refers to the characteristic that, in solutions containing these particles such as inks, the viscosity increases when the shear rate decreases and decreases when the shear rate increases. When 60g of thickening particles are dispersed in 100mL of water at 25°C, the shear rate is 0.1s. -1 Under the condition that the viscosity is above 100 mPa·s and below 900,000 mPa·s, at a shear rate of 5000 s -1 Under certain conditions, the viscosity is above 1 mPa·s and below 200 mPa·s, and it exhibits the characteristic that the viscosity increases when the shear rate is decreased and decreases when the shear rate is increased.

[0063] The ink of the present invention, by containing the aforementioned thickening particles, allows for control of ink viscosity. Specifically, by controlling the viscosity at a shear rate of 1 second... -1 Under normal conditions, the ink viscosity at 25℃ should be controlled at 3.00×10⁻⁶. 3 Above mPa·s and 2.50 × 10 4 At a shear rate below mPa·s, a thick coating of ink can be formed, exhibiting excellent substrate concealment. Furthermore, by applying a shear rate of 5000 s... -1 Under normal conditions, controlling the ink viscosity at 25℃ to below 130 mPa·s can improve the ink ejection stability.

[0064] There are no particular limitations on the thickening particles mentioned above, and they can be selected appropriately according to the purpose. Examples include fumed silica, precipitated silica, diatomaceous earth, saponin, sepiolite, talc, calcium carbonate, barium sulfide, and polyethylene oxide. These can be used individually or in combination of two or more. From the viewpoint of ink film adhesion, calcium carbonate and talc are preferred.

[0065] Alternatively, mixed crystals can also be used as the aforementioned thickening particles.

[0066] Alternatively, both the aforementioned thickening particles and non-particle thickeners can be used together. Examples of non-particle thickeners include thickeners that melt into the coating in a resinous form to exert a "thickening" effect.

[0067] There are no particular restrictions on the calcium carbonate used, and it can be selected appropriately according to the purpose; for example, commercially available products can be used.

[0068] There are no particular restrictions on the commercially available products mentioned above; you can choose appropriately according to your purpose. For example, you can list UP-G (manufactured by Immeris Specialites Japan, 100% solid content), luminous (manufactured by Maruo CALCIUM Co., Ltd., 100% solid content), Caltex 5 (manufactured by Maruo CALCIUM Co., Ltd., 100% solid content), Super#2000 (manufactured by Maruo CALCIUM Co., Ltd., 100% solid content), Super SSS (manufactured by Maruo CALCIUM Co., Ltd., 100% solid content), Softon 1500 (manufactured by Bikita Powdering Industry Co., Ltd., 100% solid content), Softon 3200 (manufactured by Bikita Powdering Industry Co., Ltd., 100% solid content), BF100 (manufactured by Bikita Powdering Industry Co., Ltd., 100% solid content), Lighton A-5 (manufactured by Bikita Powdering Industry Co., Ltd., 100% solid content), etc.

[0069] There are no particular restrictions on the type of talc used; it can be selected appropriately according to the purpose, for example, commercially available products can be used.

[0070] There are no particular restrictions on the commercially available products mentioned above, and you can choose appropriately according to your purpose. For example, you can list Nano AceD-600 (Talc Corporation of Japan, 100% solid content), etc.

[0071] There are no particular limitations on the content of the aforementioned thickening particles, which can be appropriately selected according to the purpose, but it is preferable to have a content of 20.0% by mass or more and 55.0% by mass or less relative to the total amount of the ink. This makes it easier to control the viscosity of the ink.

[0072] <Resin>

[0073] There are no particular limitations on the resins mentioned above; they can be selected appropriately according to the purpose. Examples include polyurethane resins, polyester resins, acrylic resins, vinyl acetate resins, styrene resins, butadiene resins, styrene-butadiene resins, vinyl chloride resins, acrylic-styrene resins, and acrylic-silicone resins. One of these can be used alone, or two or more can be used in combination.

[0074] As the aforementioned resin, resin particles composed of these resins can also be used. By dispersing the aforementioned resin particles in water as a dispersion medium to form a resin emulsion, ink can be obtained by mixing with materials such as colorants or organic solvents.

[0075] The resin particles described above can be appropriately synthesized resin particles or commercially available products. These resin particles can be used alone or in combination of two or more.

[0076] There are no particular limitations on the glass transition temperature of the above-mentioned resin, and it can be appropriately selected according to the purpose. Considering the cracking of the coating when it is thick, it is preferably below 15°C, and more preferably below 0°C.

[0077] There are no particular limitations on the method for determining the glass transition temperature mentioned above, and it can be appropriately selected according to the purpose. For example, in the case of resin emulsion, it can be determined by the following method.

[0078] Specifically, 4g of resin emulsion was placed in a petri dish made of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) with a diameter of 50mm, and allowed to spread evenly. The mixture was then dried at 50°C for one week to obtain a resin film. 5.0mg of the obtained resin film was placed in an aluminum sample container, which was then placed on a support unit and placed in an electric furnace.

[0079] Next, under a nitrogen atmosphere, the temperature was increased from 0°C to 150°C at a heating rate of 10°C / min. Then, the temperature was decreased from 150°C to -80°C at a cooling rate of 5°C / min. Finally, the temperature was increased to 150°C again at a heating rate of 10°C / min, and the DSC curve was measured.

[0080] Using the analytical program in the DSC-60 system, the inflection point during the second heating is analyzed by the midpoint method, and the glass transition temperature (also known as the glass transition point) (Tg) is determined from the obtained DSC curve.

[0081] There are no particular restrictions on the content of the aforementioned resin, and it can be appropriately selected according to the purpose. From the viewpoint of the strength of the dried film, it is preferably 5% by mass or more and 30% by mass or less.

[0082] The above content indicates the content of the solid component of the resin.

[0083] The ratio (A / B) of the content of the thickening particles (A) to the content of the solid components of the resin (B) is not particularly limited and can be appropriately selected according to the purpose. It is preferably 0.8 or more, more preferably 1.0 or more, and even more preferably 1.5 or more. When the ratio (A / B) is 0.8 or more, it has excellent spraying stability, and by forming a thick coating film, the substrate has excellent concealment.

[0084] <Solvent>

[0085] There are no particular restrictions on the solvents mentioned above; they can be selected appropriately according to the purpose. For example, organic solvents and water can be listed.

[0086] There are no particular restrictions on the organic solvents used, and they can be selected appropriately according to the purpose. Examples include polyol alkyl ethers, polyol aryl ethers, polyols, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene carbonate, ethylene carbonate, etc.

[0087] There are no particular restrictions on the types of polyols mentioned above. They can be selected appropriately according to the purpose. From the perspective of functioning as a wetting agent and achieving excellent spray stability, diols, triols, etc. can be listed.

[0088] Examples of the aforementioned diols include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, and 1,5-hexanediol.

[0089] Examples of the aforementioned triols include glycerol, 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.

[0090] There are no particular restrictions on the types of polyol alkyl ethers mentioned above, and they can be selected appropriately according to the purpose. For example, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether, etc. can be listed.

[0091] There are no particular restrictions on the polyol aryl ethers mentioned above; they can be selected appropriately according to the purpose. For example, ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether can be listed.

[0092] There are no particular limitations on the nitrogen-containing heterocyclic compounds mentioned above, and they can be appropriately selected according to the purpose. For example, nitrogen-containing heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolium ketone, ε-caprolactam, and γ-butyrolactone can be listed.

[0093] There are no particular restrictions on the amides mentioned above, and they can be selected appropriately according to the purpose. For example, formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, etc. can be listed.

[0094] There are no particular restrictions on the amines mentioned above; they can be selected appropriately according to the purpose. For example, monoethanolamine, diethanolamine, triethylamine, etc. can be listed.

[0095] There are no particular restrictions on the sulfur-containing compounds mentioned above; they can be appropriately selected according to the purpose. Examples include dimethyl sulfoxide, sulfolane, and thiodiethanol.

[0096] The content of the above-mentioned organic solvent is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of excellent drying properties, it is preferably 7.0% by mass or less, and more preferably 5.0% by mass or less.

[0097] There are no particular restrictions on the water content mentioned above, and it can be appropriately selected according to the purpose. However, from the viewpoint of ink drying and spraying reliability, it is preferable to be 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 60% by mass or less, relative to the total amount of ink.

[0098] <Other Ingredients>

[0099] There are no particular restrictions on the other components mentioned above, and they can be selected appropriately according to the purpose. For example, surfactants, colorants, defoamers, preservatives and mildew inhibitors, rust inhibitors, pH adjusters, film-forming aids, etc. can be listed.

[0100] -surfactant-

[0101] There are no particular restrictions on the surfactants mentioned above; they can be selected appropriately according to the purpose. Examples include silicone surfactants, fluorinated surfactants, amphoteric surfactants, nonionic surfactants, and anionic surfactants. One of these can be used alone, or two or more can be used in combination.

[0102] As the aforementioned silicon-based surfactant, a silicon-based surfactant that does not decompose even at high pH is preferred.

[0103] There are no particular limitations on the aforementioned silicone-based surfactants; they can be selected appropriately according to the purpose. Examples include silicone-based surfactants with modified groups such as polyether-modified silicone surfactants, side-chain modified polydimethylsiloxanes, two-terminal modified polydimethylsiloxanes, single-terminal modified polydimethylsiloxanes, and side-chain two-terminal modified polydimethylsiloxanes. These can be used individually or in combination of two or more.

[0104] There are no particular restrictions on the modified groups mentioned above, and they can be appropriately selected according to the purpose. From the perspective of exhibiting good properties as a water-based surfactant, modified groups having polyoxyethylene groups, polyoxyethylene polyoxypropylene groups are preferred.

[0105] As the aforementioned silicone-based surfactants, appropriate synthesizers or commercially available products can be used.

[0106] As for the aforementioned commercially available products, there are no particular restrictions, and appropriate choices can be made according to the purpose. For example, they can be obtained from companies such as BYK CHEMIE, Shin-Etsu Chemical Co., Ltd., Silicon Dow Corning Toray, Japan Latex Co., Ltd., and KYOEISHA CHEMICAL.

[0107] There are no particular limitations on the polyether-modified silicone surfactants mentioned above; they can be appropriately selected according to the purpose. Examples include compounds that introduce a polyepoxide structure into the Si side chain of a dimethylsiloxane.

[0108] There are no particular limitations on the polyether-modified silicone surfactants mentioned above, and they can be appropriately selected according to the purpose. Examples include compounds represented by the following general formula (S-1) that introduce a polyepoxide structure into the Si side chain of a dimethylpolysiloxane.

[0109] General formula (S-1):

[0110]

[0111] X = -R(C2H4O) a (C3H6O) b R'

[0112] In the above general formula (S-1), m, n, a, and b are independent and represent integers, R represents alkylene, and R' represents alkyl.

[0113] Commercially available products can be used as the aforementioned polyether-modified silicone surfactants.

[0114] There are no particular restrictions on the commercially available products mentioned above. You can choose the appropriate one according to your purpose. Examples include KF-618, KF-642, KF-643 (Shin-Etsu Chemical Co., Ltd.), EMLEX-SS-5602, SS-1906EX (Japan Latex Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2163, FZ-2164 (Silicon Dow Corning Toray Co., Ltd.), BYK-33, BYK-387 (BYK CHEMIE Co., Ltd.), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.), etc.

[0115] There are no particular limitations on the aforementioned fluorinated surfactants; they can be appropriately selected according to the purpose. From the perspective of low foaming performance, preferred surfactants include, for example, perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate compounds, adducts of perfluoroalkyl ethylene oxide, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups on the side chains. These can be used alone or in combination of two or more.

[0116] There are no particular limitations on the perfluoroalkyl sulfonic acid compounds mentioned above; they can be appropriately selected according to the purpose. Examples include perfluoroalkyl sulfonic acids and perfluoroalkyl sulfonates.

[0117] There are no particular limitations on the perfluoroalkyl carboxylic acid compounds mentioned above; they can be appropriately selected according to the purpose. Examples include perfluoroalkyl carboxylic acids and perfluoroalkyl carboxylate salts.

[0118] There are no particular limitations on the polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in the side chains mentioned above. They can be appropriately selected according to the purpose. Examples include sulfate salts of polyoxyalkylene ether polymers having perfluoroalkyl ether groups in the side chains and salts of polyoxyalkylene ether polymers having perfluoroalkyl ether groups in the side chains.

[0119] There are no particular restrictions on the counterions that serve as salts for these fluorinated surfactants; they can be selected appropriately according to the purpose. Examples include Li, Na, K, NH4, NH3CH2CH2OH, NH2(CH2CH2OH)2, and NH(CH2CH2OH)3.

[0120] There are no particular limitations on the fluorinated surfactants mentioned above, and they can be appropriately selected according to the purpose. However, compounds with fluorinated carbon atoms numbering 2 to 16 are preferred, and compounds with fluorinated carbon atoms numbering 4 to 16 are more preferred.

[0121] Examples of fluorinated surfactants include perfluoroalkyl phosphate compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in their side chains. Among these, polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in their side chains are preferred due to their low foaming properties, and fluorinated surfactants represented by general formulas (F-1) and (F-2) are particularly preferred.

[0122] General formula (F-1):

[0123] CF3CF2(CF2CF2) m -CH2CH2O(CH2CH2O) n H

[0124] In compounds represented by the above general formula (F-1), in order to impart water solubility, m is preferably an integer from 0 to 10, and n is preferably an integer from 0 to 40.

[0125] General formula (F-2):

[0126] C n F 2n+1 -CH2CH(OH)CH2-O-(CH2CH2O) a -Y

[0127] In compounds represented by the above general formula (F-2), Y is H or C. m F 2m+1 (m is an integer from 1 to 6), or CH2CH(OH)CH2-C m F 2m+1 (m is an integer from 4 to 6), or CpF 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.

[0128] Commercially available products can also be used as the aforementioned fluorinated surfactants.

[0129] As products sold in this city, there are no special restrictions; appropriate choices can be made according to the purpose. Examples include: SURFLONS-111, S-112, S-113, S-121, S-131, S-132, S-141, S-145 (all manufactured by ASAHI GLASS); FLUORAD FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (all manufactured by Sumitomo 3M); MEGAFACE F-470, F-1405, F-474 (all manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.); ZONYL TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR, CAPSTONE. FS-30, FS31, FS-3100, FS-34, FS-35 (all manufactured by Chemours); FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW (all manufactured by NEOS); POLY FOX PF-136A, PF-156A, PF-151N, PF-154, PF-159 (manufactured by OMNOVA); Unidyne DSN-403N (manufactured by Daikin Industries), etc. Among them, considering the improvement of print quality, especially the significant improvement of color development, paper penetration, wettability and uniform dyeing, Chemours FS-3100, FS-34, FS-300, NEOS FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW, OMNOVA POLY FOX PF-151N and Daikin Industries Unidyne DSN-403N are particularly preferred.

[0130] There are no particular limitations on the amphoteric surfactants mentioned above; they can be appropriately selected according to the purpose. Examples include lauryl aminopropionate, lauryl dimethyl betaine, stearoyl dimethyl betaine, and lauryl dihydroxyethyl betaine. These can be used alone or in combination of two or more.

[0131] There are no particular limitations on the aforementioned nonionic surfactants; they can be appropriately selected according to the purpose. Examples include polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene propylene block polymers, sorbitan aliphatic esters, polyoxyethylene sorbitan aliphatic esters, and ethylene oxide adducts of ethynyl alcohol. These can be used individually or in combination of two or more.

[0132] There are no particular limitations on the anionic surfactants mentioned above; they can be appropriately selected according to the purpose. Examples include polyoxyethylene alkyl ether acetates, dodecylbenzene sulfonates, laurates, and polyoxyethylene alkyl ether sulfates. One of these can be used alone, or two or more can be used in combination.

[0133] There are no particular restrictions on the content of the aforementioned surfactants, and they can be appropriately selected according to the purpose. Considering excellent wettability, discharge stability, and image quality improvement, it is preferable to have a content of 0.001% by mass or more and 5% by mass or less, and more preferably 0.05% by mass or more and 5% by mass or less.

[0134] -Color material-

[0135] There are no particular restrictions on the aforementioned coloring materials. They can be appropriately selected according to the purpose; for example, pigments and dyes can be listed. Among the aforementioned pigments, examples include inorganic pigments and organic pigments. These can be used alone or in combination of two or more. Furthermore, mixed crystals can also be used.

[0136] There are no particular restrictions on the pigments mentioned above. Appropriate choices can be made according to the intended purpose. For example, black pigments, yellow pigments, magenta pigments, cyan pigments, white pigments, green pigments, orange pigments, and glossy or metallic pigments such as gold or silver can be listed.

[0137] There are no particular restrictions on the aforementioned inorganic pigments. Appropriate selections can be made according to the intended purpose. Examples include titanium dioxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black manufactured by known methods such as the contact process, furnace process, and thermal process.

[0138] There are no particular limitations on the organic pigments mentioned above. Appropriate selection can be made according to the purpose. For example, azo pigments, polycyclic pigments (e.g., phthalocyanine pigments, perylene pigments, perynone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindolinone pigments, isoindolineone pigments, quinolineone pigments, etc.), dye chelates (e.g., basic dye-type chelates, acid dye-type chelates, etc.), nitro pigments, nitroso pigments, aniline black, resin hollow particles, inorganic hollow particles, etc., are preferred among the pigments listed above. Those with good solvent affinity are preferred.

[0139] Specifically, examples of organic pigments include carbon black (CI Pigment Black 7) used for black purposes such as furnace black, lamp black, acetylene black, and channel black; metallic pigments such as copper, iron (CI Pigment Black 11), and titanium oxide; and organic pigments such as aniline black (CI Pigment Black 1). Furthermore, examples of organic pigments used for color purposes include CI Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 138, 150, 153, 155, 180, 185, 213; CI Pigment Orange 5, 13, 16, 17, 36, 43, 51; and CI Pigment Red 1, 2, 3, 5, 17, 22.

[0140] 23, 31, 38, 48:2, 48:2 (Long-lasting 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,

[0141] 101 (Carmine), 104, 105, 106, 108 (Cadmium Red), 112, 114, 122 (Nagoridon 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 Green 1, 4, 7, 8, 10, 17, 18, 36, etc.

[0142] As the aforementioned pigment, it is preferable to disperse it in the aforementioned ink for use.

[0143] Examples of methods for dispersing the aforementioned pigments in ink include introducing hydrophilic functional groups into the pigment to make it a self-dispersible pigment, coating the pigment surface with resin to disperse it, and using a dispersant to disperse it.

[0144] Examples of self-dispersible pigments that incorporate hydrophilic functional groups include pigments with added sulfone or carboxyl groups that are dispersible in water (e.g., carbon).

[0145] Examples of pigments with resin-coated surfaces include pigments contained in microcapsules that are dispersible in water. This can also be referred to as resin-coated pigments. In this case, the pigment added to the ink does not need to be completely covered by resin; without impairing the effects of the invention, it may contain uncovered pigment, and partially coated pigment may be dispersed in the ink.

[0146] As a method of dispersing pigments using dispersants, examples include well-known low-molecular-weight dispersants, such as interfacial activators, and high-molecular-weight dispersants. Depending on the pigment, dispersants may include anionic, cationic, amphoteric, and nonionic interfacial activators. Suitable dispersants may also include RT-100 (a nonionic interfacial activator) or naphthalenesulfonic acid sodium formaldehyde condensate manufactured by Takemoto Oils Co., Ltd. Dispersants can be used alone or in combination of two or more.

[0147] There are no particular restrictions on the dyes mentioned above. Appropriate selection can be made according to the purpose; for example, acid dyes, direct dyes, reactive dyes, and basic dyes can be listed. These can be used alone or in combination of two or more.

[0148] Examples of the aforementioned dyes include CI Acid Yellow 17, 23, 42, 44, 79, and 142.

[0149] 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

[0150] 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; CI Reactive Red 14, 32, 55, 79, 249; CI Reactive Black 3, 4, 35, etc.

[0151] There are no particular restrictions on the content of the aforementioned colorant, and it can be appropriately selected according to the purpose. However, it is preferred to be 1.0% by mass or more and 15.0% by mass or less relative to the total amount of ink, and more preferably 1.0% by mass or more and 10.0% by mass or less.

[0152] The P99 particle size distribution, which serves as the ISO Max Distance (maximum distance) benchmark for the aforementioned ink, falls within the range of 0.1 μm to 100 μm. There are no particular limitations on this P99; it can be appropriately selected depending on the purpose, but preferably below 9 μm. This allows for further control of the shear rate in the aforementioned ink to be 5000 s. -1 The viscosity at 25°C. Furthermore, when P99 is 9 μm or less, in the printing apparatus, when there is a flow path with a width of tens to hundreds of μm in the flow path from ink supply to nozzle ejection, the ink flow in the flow path becomes smoother, which can improve ejection stability.

[0153] There are no particular limitations on the method for determining the particle size distribution P99 of the aforementioned ISO Max Distance. It can be appropriately selected according to the purpose. For example, the IF-3200 injection-type image resolution particle size analyzer can be used for the determination.

[0154] Specifically, ink can be diluted with water to allow observation of particles within the ink. Using an injection-type image resolution particle size analyzer IF-3200, the number of particles in the ink can be measured within the range of 0.1 μm to 100 μm, based on the ISO MaxDistance particle size distribution (P99). Since the dilution amount varies depending on the amount or size of the particle components in the ink, the dilution ratio needs to be adjusted to allow observation of individual particle sizes. In cases where the ink condenses in water, it can also be diluted using a non-condensing solvent (such as cyclohexane).

[0155] There are no particular limitations on the glass transition temperature of the dried film (hereinafter sometimes referred to as "coating") of the above ink, which can be appropriately selected according to the purpose, but it is preferably below 15°C.

[0156] There are no particular limitations on the method for determining the glass transition temperature mentioned above. It can be appropriately selected according to the purpose, and a differential scanning calorimeter (TA-60WS and DSC-60, manufactured by Shimadzu Corporation) can be used for the determination.

[0157] Specifically, 4g of ink was placed in a petri dish made of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) with a diameter of 50mm, and allowed to spread evenly. The mixture was then dried at 50°C for one week to obtain a dried ink film. 5.0mg of the dried ink film was taken and placed in an aluminum sample container. The sample container was then placed on a support unit and set up in an electric furnace.

[0158] Next, under a nitrogen atmosphere, the temperature was increased from 0°C to 150°C at a heating rate of 10°C / min. Then, the temperature was decreased from 150°C to -80°C at a cooling rate of 5°C / min. Finally, the temperature was increased to 150°C again at a heating rate of 10°C / min, and the DSC curve was measured.

[0159] Using the analytical program in the DSC-60 system, the inflection point during the second heating was analyzed by the midpoint method, and the glass transition point (Tg) was determined from the obtained DSC curve.

[0160] The resin content in the drying film of the above-mentioned ink is not particularly limited and can be appropriately selected according to the purpose, preferably 10% by mass or more and 60% by mass or less.

[0161] The above content indicates the content of the solid component of the resin.

[0162] There are no particular restrictions on the content of solid components in the above-mentioned ink, and it can be appropriately selected according to the purpose. From the viewpoint of good drying properties and excellent concealment, it is preferably 45% by mass or more, and more preferably 55% by mass or more.

[0163] The solid components are the solid components contained in the ink, such as thickening particles, resin, and pigments.

[0164] There are no particular limitations on the static surface tension of the ink, and it can be appropriately selected according to the purpose. From the viewpoint of ensuring that the ink flows properly on the substrate and shortening the ink drying time, it is preferably 35 mN / m or less at 25°C, and more preferably 30 mN / m or less.

[0165] There are no particular limitations on the pH of the ink, and it can be appropriately selected according to the purpose. From the viewpoint of preventing corrosion of metal parts in contact with the liquid, it is preferably 7 or more and 12 or less, and more preferably 8 or more and 11 or less.

[0166] <Ink Manufacturing Method>

[0167] There are no particular limitations on the manufacturing method of the above-mentioned ink, and it can be appropriately selected according to the purpose. For example, it can be obtained by dispersing or dissolving the constituent components in an aqueous medium and then stirring and mixing them as needed.

[0168] The mixing process described above can be performed using, for example, a mixer with stirring blades, a magnetic stirrer, or a high-speed disperser.

[0169] (Printing methods and printing apparatus)

[0170] The ink of this invention can be used in various recording devices based on inkjet recording, such as printers, fax machines, copiers, printer / fax / copier multifunction printers, stereoscopic modeling devices, etc.

[0171] In this invention, the term "printing apparatus and printing method" refers to an apparatus capable of dispensing ink or various processing liquids onto a workpiece, and a method of printing using the apparatus.

[0172] The aforementioned printing apparatus may include not only the ink ejection head but also means (mechanisms) related to the feeding, conveying, and paper output of the printed material, as well as devices referred to as pre-processing devices and post-processing devices.

[0173] Printing apparatus and printing method may include heating means (mechanisms) for the heating process and drying means (mechanisms) for the drying process. The heating and drying means (mechanisms) may include, for example, means (mechanisms) for heating and drying the printed surface or back of the workpiece. There are no particular limitations on the heating and drying means (mechanisms); for example, hot air heaters and infrared heaters may be used. Heating and drying may be performed before printing, during printing, or after printing.

[0174] Furthermore, printing apparatus and printing methods are not limited to those that visualize meaningful images such as text and graphics using ink. For example, they also include those that form patterns such as geometric designs and three-dimensional images.

[0175] In addition, unless otherwise specified, printing apparatus includes either a serial device that moves the printhead or a linear device that does not move the printhead.

[0176] Furthermore, this printing apparatus includes not only desktop models, but also wide-format printing apparatuses capable of printing on AO-sized recording media, or continuous bill printers that can use continuous paper wound into a roll as a recording medium.

[0177] As a form of pre-processing device and post-processing device, similar to the cases of black (K), cyan (C), magenta (M), yellow (Y) inks, it has an additional liquid storage section and liquid nozzle with pre-processing liquid and post-processing liquid, and discharges the pre-processing liquid and post-processing liquid by inkjet recording.

[0178] Other forms of pre-processing and post-processing devices include those that employ methods other than inkjet recording, such as blade coating, roller coating, and spray coating.

[0179] <Storage Containers>

[0180] The ink of the present invention is stored in the container as described above, and may also include other components as needed.

[0181] There are no particular restrictions on the material used for the aforementioned containers; they can be selected appropriately according to their purpose. For example, polyethylene terephthalate (PET) can be listed.

[0182] There are no particular restrictions on the shape, structure, and size of the containers mentioned above; they can be appropriately selected according to the purpose.

[0183] Reference Figure 1 and Figure 2 An example illustrating a printing apparatus. Figure 1 It is a three-dimensional diagram illustrating the printing apparatus. Figure 2 This is a perspective view of the main ink cartridges in a printing apparatus. The image forming apparatus 400, an example of a printing apparatus, is a serial image forming apparatus. A mechanism 420 is provided within the outer casing 401 of the image forming apparatus 400. The ink storage sections 411 of the main ink cartridges 410 (410k, 410c, 410m, and 410y) for black (K), cyan (C), magenta (M), and yellow (Y) are formed from packaging components such as aluminum laminate. The ink storage sections 411 are, for example, housed within a plastic storage container housing 414. Thus, the main ink cartridges 410 are used as ink cartridges for each color.

[0184] On the other hand, when the cover 401c of the main body of the device is opened, the ink cartridge holder 404 is located inside the opening. The main tank 410 is detachably mounted on the ink cartridge holder 404. Thus, each ink outlet 413 of the main tank 410 and each color discharge head 434 are connected via the color supply pipe 436, and ink can be discharged to the recording medium from the discharge head 434.

[0185] In this specification, "inkjet printing apparatus" refers to a liquid discharge device capable of discharging the ink of the present invention, the processing liquid, etc., from the printed material.

[0186] Hereinafter, an example of a liquid discharge device as an inkjet printing apparatus will be described with reference to the accompanying drawings. The present invention is not limited to the embodiments shown below.

[0187] Figure 3 This is a diagram showing the liquid discharge device from the side. Figure 4 This is a diagram showing the liquid discharge device as viewed from the front.

[0188] The liquid discharge device 1000 is arranged opposite to the printed object 100. The carriage 1 is equipped with a head 300 for discharging ink, such as liquid, toward the printed object 100. The Z-axis guide rail 103 holds the carriage 1 so that the carriage 1 can move in the Z-axis direction.

[0189] X-axis guide rail 101 holds Z-axis guide rail 103 so that Z-axis guide rail 103 holding carriage 1 can move in the X-axis direction. Furthermore, Y-axis guide rail 102 holds X-axis guide rail 101 so that X-axis guide rail 101 can move in the Y-axis direction. Here, X-axis is an example of a "first axis", Y-axis is an example of a "second axis intersecting the first axis", and Z-axis is an example of a "third axis intersecting the first and second axes". Additionally, carriage 1 is an example of a "liquid discharge unit", and head 300 is an example of a "liquid discharge head".

[0190] The liquid discharge device 1000 includes a Z-direction drive unit 92 that moves the carriage 1 along the Z-axis guide rail 103 in the Z-axis direction, and an X-direction drive unit 72 that moves the Z-axis guide rail 103 along the X-axis guide rail 101 in the X-axis direction. Furthermore, the liquid discharge device 1000 includes a Y-direction drive unit 82 that moves the X-axis guide rail 101 along the Y-axis guide rail 102 in the Y-axis direction. The Z-direction drive unit 92 is an example of a "first drive means (mechanism)" that moves the carriage 1 in the Z-axis direction, which intersects the X and Y axes. The movement of the carriage 1 and the head 300 in the Z-axis direction may not be parallel to the Z-axis direction, as long as it includes at least a Z-axis component; it may also be an oblique movement.

[0191] The carriage 1 further includes another Z-direction drive unit 93. The Z-direction drive unit 93 is an example of a "second drive means (mechanism)" that moves the head 300 relative to the carriage 1 in the Z-axis direction.

[0192] The liquid dispensing device 1000, configured as described above, dispenses ink from the head 300 to the object 100 while moving the carriage 1 in the X, Y, and Z directions, thus drawing on the object 100. The object 100 is represented in the form of a flat plate, but it can also be a surface that is close to vertical or has a large radius of curvature, such as a car, truck, or aircraft.

[0193] --Ink ejection mechanism--

[0194] The ink discharge means (mechanism) of the present invention can be any means (mechanism) that discharges ink from an inkjet nozzle, and there is no particular limitation. For example, as an ink discharge means (mechanism), it is provided with a nozzle orifice for dispensing ink, an ink chamber for supplying pressurized ink to the nozzle orifice, and a needle valve provided in the ink chamber for controlling the discharge by opening and closing the nozzle orifice.

[0195] As an inkjet nozzle that implements this discharge means (mechanism), for example, there is the inkjet nozzle described in Japanese Patent No. 4123897. Examples of such inkjet nozzles include... Figure 5 and Figure 6 The inkjet nozzles shown are examples of this.

[0196] --Printed materials--

[0197] The printed matter of the present invention has a printable material and a printed layer formed on the printable material by the printing apparatus of the present invention.

[0198] In addition, the terms image formation, recording, printing, and printing used in this invention are all synonyms.

[0199] Recording medium, medium, and printed matter are all synonyms.

[0200] <Substrate>

[0201] The aforementioned substrate (hereinafter sometimes referred to as "the object to be printed") refers to the object to which the ink of the present invention is printed, and refers to the object to which the ink or processing liquid can adhere even temporarily.

[0202] There are no particular restrictions on the aforementioned substrates; they can be selected appropriately according to the purpose, with preferred substrates being those for road surfaces, exterior finishes, and porous materials.

[0203] There are no particular restrictions on the shape, structure, and material of the aforementioned substrates. They can be appropriately selected according to the purpose. For example, substrates that have undergone metal coating treatment by methods such as vapor deposition on wall panels (kiln-made, resin-made, wood-made, metal-made), asphalt, asphalt felt, concrete, glass, cloth, paper, plastic, wood, metal (brass, iron, aluminum, SUS (stainless steel), copper, etc.), or non-metallic substrates can be listed.

[0204] Examples of porous substrates include asphalt, sponges, and other substrates with high ink permeability.

[0205] <Printed Layer>

[0206] The aforementioned printing layer contains resin and tackifying particles, and may contain other components as needed.

[0207] There are no particular limitations on the resins used, and appropriate resins can be selected according to the purpose. For example, the same resins used in the inks described above can be listed.

[0208] There are no particular restrictions on the content of the above-mentioned resin, and it can be appropriately selected according to the purpose, but it is preferred to be 10% by mass or more and 60% by mass or less.

[0209] The above content indicates the content of the solid component of the resin.

[0210] There are no particular restrictions on the aforementioned tackifying particles; they can be selected appropriately according to the purpose. For example, the same tackifying particles used in the aforementioned inks can be listed.

[0211] There are no particular restrictions on the content of the aforementioned thickening particles, which can be appropriately selected according to the purpose, preferably 3% by mass or more and 60% by mass or less.

[0212] There are no particular restrictions on the other components mentioned above, and they can be selected appropriately according to the purpose. For example, the same components as those used in the inks mentioned above can be listed.

[0213] [Example]

[0214] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments.

[0215] <Example 1 of pigment dispersion preparation>

[0216] The mixture of 200 parts by weight of CI pigment white 6 (manufactured by TAYCA, product name "JR-403", number average primary particle size 250nm, aspect ratio 2, surface treatment: Al, Si), 56 parts by weight of pigment dispersant (trade name: TEGO Dispers 651, manufactured by Evonik), and 744 parts by weight of distilled water was premixed.

[0217] Subsequently, using a bead mill disperser (UAM-015, manufactured by Kosuke Industries), at a liquid temperature of 30°C, zirconia beads with a diameter of 0.03 mm (density 6.03 × 10⁻⁶) were dispersed at a circumferential speed of 10 m / s, using zirconia beads at a diameter of 0.03 mm. -6 g / m 2 Disperse for 15 minutes, then centrifuge using a centrifuge (Model-3600, manufactured by Kubota Corporation) to separate coarse particles, obtaining a white pigment dispersion with an average particle size of 250 nm (solid content of 20.0% by mass).

[0218] <Example 2 of pigment dispersion preparation>

[0219] In an automated polymerization reactor (manufactured by Hōsei Sangyo Co., Ltd., polymerization test machine DSL-2AS type) equipped with a reaction vessel containing a stirring device, a dropping device, a temperature sensor, and a reflux device with a nitrogen introduction device at the top, 550g of butanone is added, and nitrogen is purged into the reaction vessel while stirring.

[0220] Then, while maintaining the reaction vessel under a nitrogen atmosphere, the temperature was raised to 80°C, and a mixed solution of 75.0 g of 2-hydroxyethyl methacrylate, 77.0 g of methacrylic acid, 80.0 g of styrene, 150.0 g of butyl methacrylate, 98.0 g of butyl acrylate, 20.0 g of methyl methacrylate, and 40.0 g of "Perbutyl (registered trademark) O" (manufactured by Nippon Oils & Fats Co., Ltd.) was added dropwise over 4 hours.

[0221] After the addition was complete, the reaction was continued for another 15 hours at the same temperature to obtain a butanone solution of a styrene-acrylic acid copolymer containing anionic groups, with an acid value of 100, a weight-average molecular weight of 21,000, and a calculated Tg of 31°C. After the reaction was completed, a portion of the butanone was removed by vacuum distillation to obtain a copolymer solution with the non-volatile content adjusted to 50%.

[0222] In a mixing tank equipped with a cooling jacket, 1000g of copper phthalocyanine (manufactured by Daihatsu Seika Co., Ltd., SEIKALIGHT BLUE A612), 800g of the above copolymer solution, 143g of 10% sodium hydroxide aqueous solution, 100g of butanone, and 1957g of water were added and stirred to obtain a mixed solution.

[0223] The resulting mixed solution was dispersed in a dispersion device (manufactured by Mitsui Mining Co., Ltd., SC mill, SC100) filled with zirconia beads of 0.3 mm in diameter, by circulation (the dispersion from the dispersion device was returned to the mixing tank), at a speed of 2700 rpm, below 40°C (achieved by circulating cold water in the cooling jacket), for 6 hours.

[0224] After dispersion is complete, the original dispersion solution is removed from the mixing tank. Then, the mixing tank and the flow path of the dispersion device are cleaned with 10,000g of water and combined with the original dispersion solution to obtain a diluted dispersion solution.

[0225] The obtained diluted dispersion was placed in a glass distillation apparatus to distill away all the butanone and some of the water. After cooling to room temperature, 10% hydrochloric acid was added dropwise while stirring to adjust the pH to 4.5. Then, the solid components were filtered using a suction filter (a pressure filter manufactured by Nippon Chemical Machinery Co., Ltd.), and washed with water. The filter cake was placed in a container, 200g of a 20% potassium hydroxide aqueous solution was added, and the mixture was dispersed using a disperser (a TK homogenizer manufactured by Special Machinery Chemical Industry Co., Ltd.). Water was then added to adjust the non-volatile components. Thus, a cyan pigment dispersion (pigment content concentration: 20.0% by mass) was obtained, which contained copper phthalocyanine composite particles (pigment content) coated with carboxyl-containing styrene-acrylic copolymer neutralized in potassium hydroxide.

[0226] <Example 1 of resin emulsion preparation>

[0227] A monomer preemulsion was prepared by emulsifying 55.4 parts by weight of methyl methacrylate as a monomer, 44.6 parts by weight of 2-ethylhexyl acrylate, 1.5 parts by weight of Aqualon KH-20 (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) as an emulsifier, and 53.1 parts by weight of deionized water using an intermittent homogenizer.

[0228] Add 89.4 parts by mass of ion-exchange water to a 2L four-necked flask equipped with a stirrer, nitrogen inlet pipe, reflux condenser, thermometer, and raw material inlet. While introducing nitrogen gas, stir and heat the liquid to 60°C.

[0229] Add 0.5 parts by mass of Aqualon KH-20 as an emulsifier and 6 parts by mass of 5% ammonium persulfate aqueous solution (0.3 parts by mass of ammonium persulfate) to the above reaction vessel.

[0230] Then, after adding a 5% ammonium persulfate aqueous solution to the above reaction vessel for 10 minutes, the above monomer pre-emulsion was continuously added dropwise from a dropping tank for 5 hours, and 6 parts of a 5% ammonium persulfate aqueous solution (0.3 parts as ammonium persulfate) were intermittently added dropwise from another dropping tank at 70°C for 5 hours.

[0231] After the addition is complete, maintain the temperature at 70°C for 3 hours to allow it to mature.

[0232] Then, cool to 50°C, add ammonia, and filter with 180-mesh polyester filter cloth to obtain resin emulsion A.

[0233] A portion of the obtained resin emulsion A was dried at 150°C for 30 minutes, and the solid content was determined according to JIS K5601-1-2, yielding a result of 50.0%. Additionally, the glass transition temperature of resin emulsion A was determined using the following method, yielding a result of 0°C.

[0234] <Determination of the glass transition temperature (Tg) of resin emulsions>

[0235] Specifically, 4g of resin emulsion was placed in a petri dish made of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) with a diameter of 50mm, and allowed to spread evenly. The mixture was then dried at 50°C for one week to obtain a resin film. 5.0mg of the obtained resin film was placed in an aluminum sample container, which was then placed on a support unit and placed in an electric furnace.

[0236] Next, under a nitrogen atmosphere, the temperature was increased from 0°C to 150°C at a heating rate of 10°C / min. Then, the temperature was decreased from 150°C to -80°C at a cooling rate of 5°C / min. Finally, the temperature was increased to 150°C again at a heating rate of 10°C / min, and the DSC curve was measured.

[0237] Using the analytical program in the DSC-60 system, the inflection point during the second heating was analyzed by the midpoint method, and the glass transition point (Tg) was determined from the obtained DSC curve.

[0238] <Example 2 of resin emulsion preparation>

[0239] In Example 1 of resin emulsion preparation, the monomers "55.4 parts by mass of methyl methacrylate" and "44.6 parts by mass of 2-ethylhexyl acrylate" were changed to "66.3 parts by mass of methyl methacrylate" and "33.7 parts by mass of 2-ethylhexyl acrylate," respectively. Otherwise, the preparation was the same as in Example 1, yielding resin emulsion B. The solids concentration and glass transition temperature were measured similarly to those of resin emulsion A. The results showed a solids concentration of 50.0% and a glass transition temperature of 20°C.

[0240] <Example 3 of resin emulsion preparation>

[0241] In Example 1 of resin emulsion preparation, the monomers "55.4 parts by mass of methyl methacrylate" and "44.6 parts by mass of 2-ethylhexyl acrylate" were changed to "63.8 parts by mass of methyl methacrylate" and "36.3 parts by mass of 2-ethylhexyl acrylate," respectively. Otherwise, the preparation was the same as in Example 1, yielding resin emulsion C. The solids concentration and glass transition temperature were measured similarly to those of resin emulsion A. The results showed a solids concentration of 50.0% and a glass transition temperature of 15°C.

[0242] <Example 4 of resin emulsion preparation>

[0243] In Example 1 of resin emulsion preparation, the monomers "55.4 parts by mass of methyl methacrylate" and "44.6 parts by mass of 2-ethylhexyl acrylate" were changed to "49.3 parts by mass of methyl methacrylate" and "50.7 parts by mass of 2-ethylhexyl acrylate," respectively. Otherwise, the preparation was the same as in Example 1, yielding resin emulsion D. The solids concentration and glass transition temperature were measured in the same manner as in resin emulsion A. The results showed a solids concentration of 50.0% and a glass transition temperature of -10°C.

[0244] <Example 5 of resin emulsion preparation>

[0245] In Example 1 of resin emulsion preparation, the monomers "55.4 parts by mass of methyl methacrylate" and "44.6 parts by mass of 2-ethylhexyl acrylate" were changed to "35.6 parts by mass of methyl methacrylate" and "64.4 parts by mass of 2-ethylhexyl acrylate," respectively. Otherwise, the preparation was the same as in Example 1, yielding resin emulsion E. The solids concentration and glass transition temperature were measured in the same manner as in resin emulsion A. The results showed a solids concentration of 50.0% and a glass transition temperature of -30°C.

[0246] <Example 6 of resin emulsion preparation>

[0247] In Example 1 of resin emulsion preparation, the monomers "55.4 parts by mass of methyl methacrylate" and "44.6 parts by mass of 2-ethylhexyl acrylate" were changed to "7.5 parts by mass of Silaace 210 (vinyltrimethoxysilane, manufactured by Chisso)," "56.4 parts by mass of methyl methacrylate," and "36.1 parts by mass of 2-ethylhexyl acrylate," respectively. Otherwise, the preparation was the same as in Example 1, yielding resin emulsion F. The solids concentration and glass transition temperature were measured in the same manner as in resin emulsion A. The results showed a solids concentration of 50.0% and a glass transition temperature of 20°C.

[0248] <Example 7 of resin emulsion preparation>

[0249] In Example 1 of resin emulsion preparation, the monomers "55.4 parts by mass of methyl methacrylate" and "44.6 parts by mass of 2-ethylhexyl acrylate" were changed to "7.5 parts by mass of Silaace 210 (vinyltrimethoxysilane, manufactured by Chisso)," "53.8 parts by mass of methyl methacrylate," and "38.7 parts by mass of 2-ethylhexyl acrylate," respectively. Otherwise, the preparation was the same as in Example 1, yielding resin emulsion G. The solids concentration and glass transition temperature were measured similarly to those of resin emulsion A. The results showed a solids concentration of 50.0% and a glass transition temperature of 15°C.

[0250] <Example 8 of resin emulsion preparation>

[0251] In Example 1 of resin emulsion preparation, the monomers "55.4 parts by mass of methyl methacrylate" and "44.6 parts by mass of 2-ethylhexyl acrylate" were changed to "7.5 parts by mass of Silaace 210 (vinyltrimethoxysilane, manufactured by Chisso)," "45.4 parts by mass of methyl methacrylate," and "47.1 parts by mass of 2-ethylhexyl acrylate," respectively. Otherwise, the preparation was the same as in Example 1, yielding resin emulsion H. The solids concentration and glass transition temperature were measured similarly to those of resin emulsion A. The results showed a solids concentration of 50.0% and a glass transition temperature of 0°C.

[0252] (Example 1)

[0253] 5.0% by mass of propylene glycol and 9.0% by mass of ion-exchanged water as solvent, 30.0% by mass of the above-mentioned resin emulsion A as resin, and 36.0% by mass of pigment dispersion A as colorant are mixed and stirred for 30 minutes to make it uniform. Then, 36.0% by mass of calcium carbonate (UP-G, manufactured by Immeris Specialites Japan) as thickening particles are added and stirred at high speed for 1 hour to make it uniform, thus obtaining ink 1.

[0254] For the obtained ink 1, the particle size (P99 in the particle size distribution of ISO Max Distance) and the glass transition temperature of the dried film were determined by the following methods. The particle size of ink 1 was 5.0, and the glass transition temperature of the dried film was 0℃.

[0255] <Ink viscosity>

[0256] For the viscosity of the above ink, the shear rate was measured to be 1 second using an MCR301 (Anton Parr) cone plate (cone radius: 25 mm, cone angle: 1°). -1 The viscosity (mPa·s) at 25℃ and the shear rate are 5000 s. -1 The viscosity (mPa·s) at 25℃ and the shear rate are 0.1 s. -1 Viscosity (mPa·s) at 25℃ under certain conditions.

[0257] <Determination of the glass transition point (Tg) of the dried film of ink>

[0258] 4g of ink was placed in a petri dish made of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) with a diameter of 50mm, and allowed to spread evenly. The mixture was then dried at 50°C for one week to obtain a dried ink film. 5.0mg of the dried ink film was taken and placed in an aluminum sample container. The sample container was then placed on a support unit and set up in an electric furnace.

[0259] Next, under a nitrogen atmosphere, the temperature was increased from 0°C to 150°C at a heating rate of 10°C / min. Then, the temperature was decreased from 150°C to -80°C at a cooling rate of 5°C / min. Finally, the temperature was increased to 150°C again at a heating rate of 10°C / min, and the DSC curve was measured.

[0260] Using the analytical program in the DSC-60 system, the inflection point during the second heating was analyzed by the midpoint method, and the glass transition point (Tg) was determined from the obtained DSC curve.

[0261] <Determination of the number of inks based on ISO Max Distance P99>

[0262] 0.1g of ink was diluted with 100mL of water. Using an IF-3200 injection-type image resolution particle size analyzer, set to observe the size of each particle in the ink, the P99 value was measured in the ISO Max Distance range from 0.1μm to 100μm, based on the number of particles in the ink. Since the dilution amount varies depending on the amount or size of the particle components in the ink, the dilution ratio needs to be adjusted to observe the size of each particle. In cases where the ink condenses in water, it can also be diluted using a solvent that does not condense ink (such as cyclohexane).

[0263] (Examples 2-32 and Comparative Examples 1-3)

[0264] In Example 1, the types and contents of solvent, resin, colorant, and thickening particles were changed to the compositions shown in Tables 1 to 5 below. Otherwise, the composition remained the same as in Example 1, and inks 2 to 35 were obtained. The units of the numbers in Tables 1 to 5 represent "mass %".

[0265] Table 1

[0266]

[0267] Table 2

[0268]

[0269] Table 3

[0270]

[0271] Table 4

[0272]

[0273] Table 5

[0274]

[0275] The detailed information of each component in Tables 1 to 5 is as follows:

[0276] -Thickening particles-

[0277] ·UP-G (manufactured by Immeris Specialites Japan, 100% solids)

[0278] ·luminous (manufactured by Maruo Calcium Co., Ltd., solid content 100%)

[0279] ·Caltex 5 (manufactured by Maruo Calcium Co., Ltd., solid content 100%)

[0280] ·Super#2000 (manufactured by Maruo Calcium Co., Ltd., solid content 100%)

[0281] ·Super SSS (manufactured by Maruo Calcium Co., Ltd., solid content 100%)

[0282] ·Super SS (manufactured by Maruo Calcium Co., Ltd., solid content 100%)

[0283] ·Nano Ace D-600 (Japan Talc Co., Ltd., solid content 100%)

[0284] -Resin-

[0285] • TAKERACK W6110 (Made by Mitsui Chemicals, Ltd., polycarbonate-based polyurethane resin particles, Tg: -20℃, solids content 32%)

[0286] • TAKERACK W6061 (Made by Mitsui Chemicals, Ltd., polycarbonate-based polyurethane resin particles, Tg: 25℃, solids content 30%)

[0287] For inks 1-35 in Examples 1-32 and Comparative Examples 1-3, "discharge stability", "concealment", "coating cracking", "coating drying", "coating adhesion" and "ink scattering" were evaluated. The results are shown in Table 6.

[0288] <Excretion Stability>

[0289] Ink 1 to 35 from Examples 1 to 32 and Comparative Examples 1 to 3 were placed in a Retarobo (registered trademark) ink head (a Retarobo ink head manufactured by Ricoh Digital Painting Co., Ltd.), and ink was dispensed. Dispensing stability was evaluated based on the following evaluation criteria. A dispensing stability evaluation result of "B" or higher indicates that the ink is within the scope of applicability.

[0290] [Evaluation Criteria]

[0291] A: It will not bend or shake during discharge and can be discharged stably.

[0292] B: Although there may be slight bending or shaking during discharge, it can be discharged stably.

[0293] C: Sometimes the discharge may bend or shake, and it cannot be discharged stably.

[0294] D: Cannot be excreted.

[0295] <Concealment>

[0296] The inks 1-35 from Examples 1-32 and Comparative Examples 1-3 were placed on a Retarobo (registered trademark) head (a Retarobo head, manufactured by Ricoh Digital Painting Co., Ltd.). Figure 3 and Figure 4 In the printing apparatus shown, ink is dispensed, and a solid image is printed on a glass plate. After confirming that the film thickness upon drying is 300 μm, a solid image is printed on porous asphalt in the same manner as on the glass plate. Then, the image is placed at 23°C and 50% humidity for 24 hours, and its concealment is evaluated based on the following evaluation criteria. A concealment evaluation result of "C" or higher indicates a usable range.

[0297] [Evaluation Criteria]

[0298] A: The flat parts of the asphalt surface, as well as the substrate in the porous pores visible from the surface, can be concealed very well.

[0299] B: The flat parts of the asphalt surface, as well as the substrate in the porous pores visible from the surface, can be well concealed.

[0300] C: The substrate in the flat part of the asphalt surface can be well concealed, but the substrate in the porous pores visible from the surface cannot be concealed.

[0301] D: The flat parts of the asphalt surface, as well as the substrate in the porous pores visible from the surface, cannot be concealed.

[0302] <Coating Breakage>

[0303] The inks 1-35 from Examples 1-32 and Comparative Examples 1-3 were placed on a Retarobo (registered trademark) head (a Retarobo head, manufactured by Ricoh Digital Painting Co., Ltd.). Figure 3 and Figure 4 In the printing apparatus shown, ink is dispensed to form a solid image coating with a dry thickness of 100 μm, 200 μm, and 300 μm on a glass plate. After the solid image is placed at a temperature of 23°C and a humidity of 50% for 24 hours, the coating is visually inspected under diffused sunlight for cracks, and the cracks are evaluated based on the following evaluation criteria.

[0304] [Evaluation Criteria]

[0305] A: The coatings at 100μm, 200μm, and 300μm showed no cracking.

[0306] B: The 100μm and 200μm coatings showed no cracking, but the 300μm coating showed cracking.

[0307] C: The 100μm coating showed no cracking, but the 200μm and 300μm coatings showed cracking.

[0308] <Drying properties of the coating>

[0309] The inks 1-35 from Examples 1-32 and Comparative Examples 1-3 were placed on a Retarobo (registered trademark) head (a Retarobo head, manufactured by Ricoh Digital Painting Co., Ltd.). Figure 3 and Figure 4 In the printing apparatus shown, ink is discharged to form a coating on a glass plate with a solid image thickness of 200 μm when dry.

[0310] After that, hot air was blown at a temperature of 40℃ and a wind speed of 5m / s to dry it.

[0311] Subsequently, a test roller weighing 15.8 kg with a smooth tire made of synthetic rubber, namely a no-pickup time tester (manufactured by TP Giken Co., Ltd.), was rolled on the solid image coating, and the drying time until the coating no longer adhered to the tire was measured. The drying performance of the coating was evaluated based on the following evaluation criteria.

[0312] [Evaluation Criteria]

[0313] A: The drying time is less than 5 minutes.

[0314] B: Drying time exceeds 5 minutes but is less than 10 minutes.

[0315] C: Drying time is more than 10 minutes but less than 15 minutes.

[0316] <Strength>

[0317] The inks 1-35 from Examples 1-32 and Comparative Examples 1-3 were placed on a Retarobo (registered trademark) head (a Retarobo head, manufactured by Ricoh Digital Painting Co., Ltd.). Figure 3 and Figure 4 In the printing apparatus shown, ink is discharged to form a solid image coating with a drying thickness of 100 μm on a glass plate. Subsequently, it is dried by blowing hot air at 40°C and a wind speed of 5 m / s for 15 minutes.

[0318] Then, quickly and repeatedly rub the center of the dried solid image coating surface with your fingernail, and evaluate the adhesion based on the following evaluation criteria.

[0319] [Evaluation Criteria]

[0320] A: The coating surface was not scraped at all.

[0321] B: The coating surface was almost completely scraped.

[0322] C: The coating surface has been slightly scraped, but the substrate has not been exposed.

[0323] D: The coating surface peels off, exposing the substrate.

[0324] <The Scattering of Ink>

[0325] The inks 1-35 from Examples 1-32 and Comparative Examples 1-3 were placed on a Retarobo (registered trademark) head (a Retarobo head, manufactured by Ricoh Digital Painting Co., Ltd.). Figure 3 and Figure 4 In the printing apparatus shown, ink is ejected and a solid image coating is formed on a glass plate at distances of 10 mm, 50 mm, and 100 mm between the nozzle of the printing head and the glass, resulting in a film thickness of 200 μm upon drying. Ink dispersion at each distance is visually observed, and the ink dispersion is evaluated based on the following evaluation criteria.

[0326] [Evaluation Criteria]

[0327] A: No ink scattering occurs at distances of 10mm, 50mm, and 100mm.

[0328] B: No ink scattering occurred at distances of 10mm and 50mm, but slight ink scattering occurred at a distance of 100mm.

[0329] C: No ink scattering occurred at a distance of 10mm, but slight ink scattering occurred at a distance of 50mm.

[0330] Table 6

[0331]

[0332] Examples of embodiments of the present invention include the following:

[0333] <1>

[0334] An ink, characterized in that:

[0335] Contains solvents, resins, and thickening particles.

[0336] At a shear rate of 1 second -1 The viscosity at 25°C is 3.00 × 10⁻⁶. 3 Above mPa·s and 2.50 × 10 4 Below mPa·s

[0337] At a shearing rate of 5000 s -1 Under normal conditions, the viscosity at 25°C is below 130 mPa·s.

[0338] <2>

[0339] According to the ink described in <1> above, at a shearing speed of 1 second...-1 The viscosity at 25°C is 6.00 × 10⁻⁶. 3 Above mPa·s and 2.50 × 10 4 Below mPa·s.

[0340] <3>

[0341] According to the ink described in <1> or <2> above, at a shearing speed of 0.1 s... -1 The viscosity at 25°C is 3.00 × 10⁻⁶. 4 Above mPa·s.

[0342] <4>

[0343] According to the ink described in <1> or <2> above, at a shearing speed of 5000 s... -1 Under these conditions, the viscosity at 25°C is 30 mPa·s and below 80 mPa·s.

[0344] <5>

[0345] According to the ink described in <1> or <2> above, the P99 of the particle size distribution in the range of 0.1μm to 100μm based on the number of particles is 9μm or less.

[0346] <6>

[0347] According to the ink described in <1> or <2> above, the solid content in the ink is 45% by mass or more.

[0348] <7>

[0349] According to the ink described in <1> or <2> above, the glass transition temperature (Tg) of the resin is below 15°C, or the glass transition temperature (Tg) of the dried film of the ink is below 15°C.

[0350] <8>

[0351] According to the ink described in <1> or <2> above, the solvent comprises at least one of diols and triols.

[0352] <9>

[0353] According to the ink described in <1> or <2> above, the content of the thickening particles is 20.0% by mass or more and 55.0% by mass or less relative to the ink.

[0354] <10>

[0355] According to the ink described in <1> or <2> above, the ratio (A / B) of the content of the thickening particles (A) to the content of the solid components of the resin is 0.8 or more.

[0356] <11>

[0357] According to the ink described in <1> or <2> above, the thickening particles are at least one of calcium carbonate and talc.

[0358] <12>

[0359] The ink described in <1> or <2> above is used for coating the walls of buildings such as roads, exterior or interior surfaces, the walls of civil structures such as bridges or tunnels, and porous substrates.

[0360] <13>

[0361] A printing apparatus, characterized in that:

[0362] It has a discharge mechanism that discharges the ink from any one of the above <1> to <12> from the inkjet nozzle.

[0363] <14>

[0364] According to the printing apparatus described in <13> above, the discharge mechanism includes:

[0365] The ink chamber is used to store the ink described in any one of <1> to <12> above.

[0366] The nozzle orifice discharges pressurized ink supplied from the ink chamber; and

[0367] A needle valve, located in the ink chamber, controls the ink discharge by opening and closing the nozzle orifice.

[0368] <15>

[0369] A printing method, characterized in that:

[0370] The process includes the discharge step of discharging the ink from any one of <1> to <12> above from the inkjet nozzle.

[0371] <16>

[0372] According to the printing method described in <15> above, in the discharge process, pressurized ink is supplied from the ink chamber containing the ink to the nozzle orifice, and the discharge of the ink is controlled by opening and closing the nozzle orifice by a needle valve.

[0373] <17>

[0374] According to the printing method described in <16> above, in the discharge process, when the ink is discharged from the nozzle orifice to the printed object, the distance between the discharge outlet of the nozzle orifice and the printed object is 50 mm or more.

[0375] <18>

[0376] A printed matter, characterized in that it comprises:

[0377] Printed objects; and

[0378] The printed layer, formed on the object to be printed using the printing apparatus described in <13> or <14> above, contains resin and thickening particles.

[0379] The ink described in any one of <1> to <12> above, the printing apparatus described in <13> or <14> above, the printing method described in any one of <15> to <17> above, and the printed matter described in <18> above can solve the problems that have existed in the past and achieve the above-mentioned objectives of the present invention.

[0380] The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the above embodiments. Various modifications can be made within the scope of the technical concept of the present invention, and all of them fall within the protection scope of the present invention.

Claims

1. An ink, characterized in that... : Contains solvents, resins, and thickening particles. At a shear rate of 1 second -1 The viscosity at 25°C is 3.00 × 10⁻⁶. 3 Above mPa·s and 2.50 × 10 4 Below mPa·s At a shearing rate of 5000 s -1 Under normal conditions, the viscosity at 25°C is below 130 mPa·s. At a shear rate of 0.1 s -1 The viscosity at 25°C is 3.00 × 10⁻⁶. 4 Above mPa·s The content of the thickening particles relative to the ink is 36.0% by mass or more and 55.0% by mass or less. The thickening particles are at least one of calcium carbonate and talc; The solvent includes water and an organic solvent, wherein the organic solvent comprises at least one of diols and triols, and the content of the organic solvent is less than 7.0% by mass relative to the total amount of the ink; The ratio (A / B) of the content of the thickening particles (A) to the content of the solid components of the resin is 0.8 or more.

2. The ink according to claim 1, characterized in that... : At a shear rate of 1 second -1 The viscosity at 25°C is 6.00 × 10⁻⁶. 3 Above mPa·s and 2.50 × 10 4 Below mPa·s.

3. The ink according to claim 1 or 2, characterized in that... : At a shearing rate of 5000 s -1 Under these conditions, the viscosity at 25°C is 30 mPa·s and below 80 mPa·s.

4. The ink according to claim 1 or 2, characterized in that... : The P99 for the range of particle size distribution above 0.1 μm and below 100 μm in the ISO Max Distance based on the number of particles is below 9 μm.

5. The ink according to claim 1 or 2, characterized in that... : The solid content in the ink is 45% by mass or more.

6. The ink according to claim 1 or 2, characterized in that... : The glass transition temperature (Tg) of the resin is below 15°C, or the glass transition temperature (Tg) of the dried film of the ink is below 15°C.

7. The ink according to claim 1 or 2, characterized in that... : Coatings used for road surfaces, exterior or interior building walls, civil structures such as bridges or tunnels, and porous substrates.

8. A printing method, characterized in that... : The process includes the discharge step of discharging the ink from the inkjet nozzle according to any one of claims 1 to 7.

9. The printing method according to claim 8, characterized in that... : In the discharge process, pressurized ink is supplied from the ink chamber containing the ink to the nozzle orifice, and the discharge of the ink is controlled by opening and closing the nozzle orifice by a needle valve.

10. The printing method according to claim 9, characterized in that... : In the discharge process, when the ink is discharged from the nozzle orifice onto the printed object, the distance between the discharge outlet of the nozzle orifice and the printed object is 50 mm or more.

11. A printed matter, characterized in that... ,include: Printed objects; and The printing layer is formed on the printed object using the ink according to any one of claims 1 to 7, and contains resin and thickening particles.

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