Ink set, liquid applying device, liquid applying method, and printed matter

Abstract

To provide an ink set which can obtain a good image density even when a pigment ink is used and can obtain high friction fastness.SOLUTION: An ink set comprising: a pre-processing fluid; an aqueous pigment ink; and a post-processing fluid, wherein the pre-processing fluid contains an organic acid and an amine compound, and the post-processing fluid contains cationic resin particles.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an ink set, a liquid application device, a liquid application method, and a printed matter. [Background technology]

[0002] Inkjet printers are known as an example of a liquid application device. Inkjet printers have advantages such as low noise, low running costs, and ease of color printing, and are widely used in ordinary households as digital signal output devices.

[0003] In recent years, there has been a growing demand for inkjet printing methods to achieve image quality comparable to that of conventional analog printing, not only for home use, but also for low-permeability media such as coated paper, non-absorbent media such as plastic film, and fabrics such as woven and knitted fabrics. In the textile printing field, the market for direct printing using water-based inks on clothing such as T-shirts and pre-sewn fabric substrates is expanding year by year. In addition to the traditional cotton and cotton-polyester blend media, demand for sportswear has skyrocketed, creating a need for compatibility with polyester media as well. This has led to a growing demand for inkjet printers capable of producing images with excellent color development and durability on a variety of materials, including cotton and polyester.

[0004] Dye inks using reactive dyes or acid dyes are widely used in these fields, but dye inks have the disadvantage of placing a heavy burden on the environment because the post-processing involves a washing step using a large amount of water.

[0005] For this reason, expectations are rising for pigment inks. The use of pigment inks has the advantage of being simple, requiring only a heating step for post-processing. Furthermore, as mentioned above, compatibility with a variety of substrates is required, and pigment inks have the advantage of being versatile and can be used on any substrate.

[0006] However, pigment inks have inferior color development compared to dye inks, and therefore, printed matter obtained using pigment inks may have an impression of insufficient image density.Furthermore, because pigment inks leave solid content on fibers, printed matter obtained using pigment inks has the problem that image peeling is easily noticeable when rubbed.

[0007] To address this issue, a technique for solving the color development problem associated with pigment inks is known, in which a pretreatment liquid containing a component that aggregates the ink is applied to the substrate in advance, thereby retaining the ink on the surface and increasing its concentration (see, for example, Patent Document 1). However, particularly in the case of cotton substrates, which readily absorb ink, pigment inks still have inferior color development compared to dye inks. Furthermore, it is known that the use of a pretreatment liquid tends to cause the pigment to remain on the surface, which in turn worsens abrasion resistance.

[0008] In order to solve such problems, methods using a post-processing liquid have been proposed, as in Patent Documents 2 and 3. Summary of the Invention [Problem to be solved by the invention]

[0009] However, in the prior art, it has not yet been possible to obtain good image density and high rub fastness even when using pigment ink.

[0010] An object of the present invention is to provide an ink set that can provide good image density and high abrasion resistance even when pigment inks are used. [Means for solving the problem]

[0011] In order to solve the above-mentioned problems, the ink set of the present invention is an ink set comprising a pre-treatment liquid, an aqueous pigment ink, and a post-treatment liquid, wherein the pre-treatment liquid comprises an organic acid and an amine compound, and the post-treatment liquid comprises cationic resin particles. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide an ink set that can obtain good image density and high abrasion resistance even when pigment inks are used. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 2 is a schematic cross-sectional view showing an example of a liquid deposition apparatus. [Figure 2] FIG. 1 is an example of a functional block diagram. [Figure 3] 1 is an example of a flow. [Figure 4] FIG. 10 is a schematic cross-sectional view showing another example of the liquid deposition device. [Figure 5] FIG. 10 is a schematic perspective view showing another example of the liquid deposition device. [Figure 6] FIG. 2 is a perspective schematic view showing an example of a main tank. [Figure 7] FIG. 10 is a schematic plan view showing another example of the liquid deposition device. [Figure 8] FIG. 2 is a schematic plan view illustrating an example of an inkjet recording module. [Figure 9] FIG. 10 is another example of a functional block diagram. [Figure 10] 10A and 10B are schematic plan views for explaining an example of a maintenance and recovery operation. [Figure 11] 1A and 1C are cross-sectional schematic views for explaining an example of cleaning of a nozzle surface. [Figure 12] 10A to 10D are cross-sectional schematic views illustrating another example of cleaning the nozzle surface. [Figure 13] 10A to 10D are cross-sectional schematic views illustrating another example of cleaning the nozzle surface. [Figure 14] 10 is a cross-sectional observation image of an example of a printed matter. [Figure 15] FIG. 2 is a schematic cross-sectional view of an example of a printed matter. [Figure 16] 1 is a schematic diagram illustrating an example of an electrode manufacturing apparatus according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0014] The ink set, liquid application device, liquid application method, and printed matter according to the present invention will be described below with reference to the drawings. Note that the present invention is not limited to the embodiments shown below, and other modifications, additions, corrections, deletions, and other changes can be made within the scope of what a person skilled in the art can conceive, and any embodiment is within the scope of the present invention as long as it achieves the functions and effects of the present invention.

[0015] (ink set) The ink set of the present invention is an ink set comprising a pre-treatment liquid, an aqueous pigment ink, and a post-treatment liquid, wherein the pre-treatment liquid comprises an organic acid and an amine compound, and the post-treatment liquid comprises cationic resin particles.

[0016] According to the present invention, good image density and high abrasion resistance can be obtained even when using pigment inks. The reasons for the effects of the present invention are thought to be, but are not limited to, the following: A printed matter produced using the ink set of the present invention has a layer (also referred to as a printed layer) containing aqueous pigment ink formed by mixing and agglomerating the aqueous pigment ink and the pretreatment liquid, and a layer (also referred to as a continuous layer) formed by the posttreatment liquid. These layers have different electric charges, allowing each layer to exist independently. In particular, by using a cationic resin in the posttreatment liquid, a pigment-free continuous layer can be formed on the printed layer, as shown in Figure 14 below, for example. This is thought to improve image density due to the reflection intensity of the coating film, and also to protect the printed layer with the resin in the continuous layer. The printed layer containing the aqueous pigment ink, which is formed by mixing and agglomerating the aqueous pigment ink and the pretreatment liquid, may be obtained by removing the liquid component by drying or the like.

[0017] (Pretreatment liquid) First, the pretreatment liquid used in the present invention will be described. The pretreatment liquid used in the present invention contains an organic acid and an amine compound, and may also contain water and other ingredients.

[0018] <Organic acid> The organic acid used in the pretreatment liquid of the present invention is not particularly limited, but it is preferable to contain a carboxylic acid having a carbon number of 6 or less. Carboxylic acids having a carbon number of 6 or less are highly soluble in water, which prevents separation of the carboxylic acid from water during long-term storage and increases the stability of the pretreatment liquid.

[0019] Preferred examples of carboxylic acids having 6 or less carbon atoms include saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, and hexanoic acid, and hydroxy acids such as lactic acid, malic acid, and citric acid. The carbon chain may be linear or branched, and may be saturated or unsaturated. Among these, lactic acid, citric acid, and acetic acid are preferred because they are inexpensive, highly safe, and can efficiently aggregate pigments in the ink.

[0020] The content of the organic acid in the pretreatment liquid is preferably 1% by mass or more, and more preferably 2% by mass or more, based on the total pretreatment liquid. A content of 1% by mass or more causes pigment aggregation and suppresses image bleeding. Furthermore, the content is preferably 50% by mass or less, and more preferably 15% by mass or less, based on the total pretreatment liquid. A content of 50% by mass or less prevents the pigment from remaining on the fabric surface from becoming too effective, making it easier to maintain friction fastness. Furthermore, the content is particularly preferably 10% by mass or more and 15% by mass or less, based on the total pretreatment liquid. In this case, image bleeding is suitably suppressed, and an image with excellent friction fastness can be obtained. The content of the organic acid in the pretreatment liquid may be 1.5% by mass or more and 2.0% by mass or less, based on the total pretreatment liquid. In this case, pigment aggregation occurs and image bleeding can be suppressed.

[0021] <Amine compounds> The amine compound contained in the pretreatment liquid in the present invention is not particularly limited and can be selected appropriately. The organic amine may be any of primary, secondary, tertiary, and quaternary amines and their salts. Specific examples include tetraalkylammonium, alkylamine, benzalkonium, alkylpyridium, imidazolium, polyamine, and derivatives or salts thereof. Specific examples include amylamine, butylamine, propanolamine, propylamine, ethanolamine, ethylethanolamine, 2-ethylhexylamine, ethylmethylamine, ethylbenzylamine, ethylenediamine, octylamine, oleylamine, cyclooctylamine, cyclobutylamine, cyclopropylamine, cyclohexylamine, diisopropanolamine, diethanolamine, diethylamine, di-2-ethylhexylamine, diethylenetriamine, diphenylamine, dibutylamine, dipropylamine, dihexylamine, dipentylamine, 3-(dimethylamino)propylamine, dimethylethylamine, dimethylethylenediamine, and dimethyloctylamine. Amines, 1,3-dimethylbutylamine, dimethyl-1,3-propanediamine, dimethylhexylamine, amino-butanol, amino-propanol, amino-propanediol, N-acetylaminoethanol, 2-(2-aminoethylamino)-ethanol, 2-amino-2-ethyl-1,3-propanediol, 2-(2-aminoethoxy)ethanol, 2-(3,4-dimethoxyphenyl)ethylamine, cetylamine, triisopropanolamine, triisopentylamine, triethanolamine, trioctylamine, tritylamine, bis(2-aminoethyl)1,3-propanediamine, bis(3-aminopropyl)ethylenediamine, bis(3-aminopropyl)1,Examples of suitable amines include 3-propanediamine, bis(3-aminopropyl)methylamine, bis(2-ethylhexyl)amine, bis(trimethylsilyl)amine, butylamine, butylisopropylamine, propanediamine, propyldiamine, hexylamine, pentylamine, 2-methylcyclohexylamine, methylpropylamine, methylbenzylamine, monoethanolamine, laurylamine, nonylamine, trimethylamine, triethylamine, dimethylpropylamine, propylenediamine, hexamethylenediamine, tetraethylenepentamine, diethylethanolamine, tetramethylammonium chloride, tetraethylammonium bromide, dihydroxyethylstearylamine, 2-heptadecenylhydroxyethylimidazoline, lauryldimethylbenzylammonium chloride, cetylpyridinium chloride, stearamidomethylpyridium chloride, diallyldimethylammonium chloride polymer, diallylamine polymer, and monoallylamine polymer.

[0022] The amount of the amine compound added in the present invention is preferably such that the ratio of the functional group content of the amine group to the functional group content of the acidic functional group contained in the organic acid is 0.05 to 1. By adding the compound in this range, an appropriate cohesive force is maintained when the pretreatment liquid is mixed with the ink, and the optical density of the recorded material can be increased when the pretreatment liquid is used as an ink set for printing. On the other hand, by adding the compound in this range, the pH can be maintained neutral to weakly alkaline, reducing the risk of corrosion of the member onto which the pretreatment liquid is ejected or coated. This allows for stable liquid application for printing and other purposes over a long period of time.

[0023] <Additives> The pretreatment liquid of the present invention may contain organic solvents, surfactants, antifoaming agents, antiseptic and antifungal agents, antirust agents, etc., if necessary.

[0024] <Organic solvents> The organic solvent used in the present invention is not particularly limited, and any water-soluble organic solvent can be used, including, for example, polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds.

[0025] Specific examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, and the like. Polyhydric alcohols such as pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl-1,3-pentanediol, and petriol, ethylene glycol monoethyl ether, and ethylene glycol monobutyl ether. polyhydric alcohol alkyl ethers such as diethylene 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.

[0026] It is preferable to use an organic solvent having a boiling point of 250° C. or less, since it not only functions as a wetting agent but also provides good drying properties.

[0027] The content of the organic solvent in the pretreatment liquid is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of ensuring the stability of the ejection or coating of the pretreatment liquid while maintaining good drying properties of the final printed matter, the content is preferably from 10% by mass to 60% by mass, more preferably from 20% by mass to 60% by mass, and even more preferably from 20% by mass to 26% by mass.

[0028] <Surfactant> As the surfactant, any of silicone surfactants, fluorine surfactants, amphoteric surfactants, nonionic surfactants and anionic surfactants can be used.

[0029] Silicone surfactants are not particularly limited and can be appropriately selected depending on the purpose.Among them, those that do not decompose even at high pH are preferred, such as side-chain modified polydimethylsiloxane, both-end modified polydimethylsiloxane, one-end modified polydimethylsiloxane, and both-end modified polydimethylsiloxane of side chain, and 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.In addition, polyether-modified silicone surfactants can also be used as the silicone surfactant, and examples thereof include compounds in which a polyalkylene oxide structure is introduced into the Si part side chain of dimethylsiloxane.

[0030] As fluorosurfactants, for example, 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 the side chain are particularly preferred due to their low foaming properties. Examples of the perfluoroalkyl sulfonic acid compounds include perfluoroalkyl sulfonic acids and perfluoroalkyl sulfonate salts. Examples of the perfluoroalkyl carboxylic acid compounds include perfluoroalkyl carboxylic acids and perfluoroalkyl carboxylate salts. Examples of the polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in the side chain include sulfate ester salts of polyoxyalkylene ether polymers having perfluoroalkyl ether groups in the side chain, and salts of polyoxyalkylene ether polymers having perfluoroalkyl ether groups in the side chain. Counterions of the salts in these fluorosurfactants include Li, Na, K, NH, NHCHCHOH, NH(CHCHOH), NH(CHCHOH), and the like.

[0031] Examples of amphoteric surfactants include lauryl aminopropionate, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.

[0032] Examples of 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 alcohol.

[0033] Examples of anionic surfactants include polyoxyethylene alkyl ether acetates, dodecylbenzenesulfonates, laurates, and salts of polyoxyethylene alkyl ether sulfates. These may be used alone or in combination of two or more.

[0034] The content of the surfactant in the pretreatment liquid is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of achieving excellent wettability and ejection stability and improving image quality, the content is preferably from 0.001% by mass to 5% by mass, and more preferably from 0.05% by mass to 5% by mass.

[0035] The antifoaming agent is not particularly limited, and examples thereof include silicone-based antifoaming agents, polyether-based antifoaming agents, and fatty acid ester-based antifoaming agents. These may be used alone or in combination of two or more. Among these, silicone-based antifoaming agents are preferred because of their excellent foam-breaking effect.

[0036] <Preservative and fungicide> The antiseptic and antifungal agent is not particularly limited, and examples thereof include 1,2-benzisothiazolin-3-one.

[0037] <Rust inhibitor> The rust inhibitor is not particularly limited, and examples thereof include acid sulfites and sodium thiosulfate.

[0038] (ink) Next, the aqueous pigment ink used in the present invention will be described. The aqueous pigment ink used in the present invention contains at least water, a pigment, and an organic solvent. Hereinafter, the aqueous pigment ink may be simply referred to as ink.

[0039] <Pigments> The pigment may be an inorganic pigment or an organic pigment. These may be used alone or in combination of two or more. Mixed crystals may also be used.

[0040] Examples of pigments that can be used include black pigments, yellow pigments, magenta pigments, cyan pigments, white pigments, green pigments, orange pigments, glossy pigments such as gold and silver pigments, and metallic pigments.

[0041] As inorganic pigments, titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, as well as carbon black produced by known methods such as the contact method, furnace method, and thermal method can be used.

[0042] In addition, examples of organic pigments that can be used include azo pigments, polycyclic pigments (e.g., phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments), dye chelates (e.g., basic dye chelates and acid dye chelates), nitro pigments, nitroso pigments, and aniline black. Of 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.

[0043] Specific examples of pigments for black include carbon blacks (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, metals such as copper, iron (CI Pigment Black 11), and titanium oxide, and organic pigments such as aniline black (CI Pigment Black 1).

[0044] In addition, for color, 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, CI Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48:2 (Permanent Red 2B (Ca)), 48:3, 48:4, 49:1, 52:2, 53:1, 57:1 (Brilliant Carmine 6B), 60:1, 63:1, 63:2, 64:1, 81, 83, 88, 10 1 (Red Iron), 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 Pi 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.

[0045] The content of the pigment in the ink is preferably from 0.1% to 15% by mass, more preferably from 1% to 10% by mass, from the viewpoints of improving image density, good fixability, and ejection stability.

[0046] Methods for dispersing a pigment in ink include introducing a hydrophilic functional group into the pigment to make it a self-dispersing pigment, coating the surface of the pigment with a resin to disperse the pigment, and using a dispersant to disperse the pigment. As a method for introducing a hydrophilic functional group into a pigment to make it a self-dispersing pigment, for example, a self-dispersing pigment can be obtained by adding a functional group such as a sulfone group or a carboxyl group to a pigment (e.g., carbon) to make it dispersible in water.

[0047] As a method for coating the surface of a pigment with a resin and dispersing it, a pigment can be encapsulated in microcapsules that can be dispersed in water. This can also be called a resin-coated pigment. In this case, it is not necessary for all of the pigments blended into the ink to be coated with resin; uncoated or partially coated pigments may be dispersed in the ink as long as the effects of the present invention are not impaired.

[0048] Examples of the method for dispersing using a dispersant include a method for dispersing using a known low molecular weight dispersant or a high molecular weight dispersant, such as a surfactant. As the dispersant, for example, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc. can be used depending on the pigment. RT-100 (nonionic surfactant) manufactured by Takemoto Yushi Co., Ltd. and sodium naphthalenesulfonate formalin condensate can also be suitably used as the dispersant. One dispersant may be used alone, or two or more dispersants may be used in combination.

[0049] <Pigment dispersion> Ink can be obtained by mixing a colorant with water, an organic solvent, or other materials. Alternatively, ink can be produced by mixing a pigment with other materials such as water and a dispersant to form a pigment dispersion, and then mixing the pigment with other materials such as water and an organic solvent. The pigment dispersion is obtained by dispersing water, a pigment, a pigment dispersant, and optionally other components, and adjusting the particle size. Dispersion is preferably performed using a disperser.

[0050] Although there are no particular restrictions on the particle size of the pigment in the pigment dispersion, the maximum frequency, calculated as the maximum number, is preferably 20 nm or more and 500 nm or less, and more preferably 20 nm or more and 150 nm or less, in order to improve the dispersion stability of the pigment and image quality such as ejection stability and image density. The particle size of the pigment can be measured using a particle size analyzer (Nanotrac Wave-UT151, manufactured by Microtrac Bell Co., Ltd.).

[0051] The content of the pigment in the pigment dispersion is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of obtaining good ejection stability and increasing image density, the content 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.

[0052] It is preferable that the pigment dispersion is degassed, if necessary, by filtering coarse particles using a filter, a centrifugal separator, or the like.

[0053] <Organic solvents> The ink of the present invention contains an organic solvent, and the organic solvent contained in the ink may have the same composition as the organic solvent contained in the pretreatment liquid. For example, the type and amount of the organic solvent contained in the ink are the same as the type and amount of the organic solvent contained in the pretreatment liquid.

[0054] <Resin> The ink of the present invention preferably contains a resin in order to ensure high abrasion resistance. The resin in the present invention may be added to the ink in any state, but the resin particles are contained in a dispersed state in the ink composition, and the resin particles generally bond together when water, which is the main solvent of aqueous inks, or the water-soluble organic solvent in the ink evaporates or penetrates, thereby facilitating the fixation of the pigment to the recording medium.

[0055] The type of resin contained in the ink is not particularly limited and can be selected appropriately 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.

[0056] Resin particles made of these resins may be used as the resin. The resin particles may be dispersed in water as a dispersion medium to form a resin emulsion, which may be mixed with materials such as coloring materials and organic solvents to obtain an ink. The resin particles may be appropriately synthesized or commercially available. These may be used alone or in combination of two or more types of resin particles.

[0057] The volume-average particle size of the resin particles is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of obtaining good fixation and high image hardness, it is preferably 10 nm to 1,000 nm, more preferably 10 nm to 200 nm, and particularly preferably 10 nm to 100 nm. The volume-average particle size can be measured, for example, using a particle size analyzer (Nanotrac Wave-UT151, manufactured by Microtrac Bell Co., Ltd.).

[0058] The resin content is not particularly limited and can be selected appropriately depending on the purpose. From the viewpoint of fixability and ink storage stability, however, it is preferably from 1% by mass to 30% by mass, and more preferably from 5% by mass to 20% by mass, of the total amount of ink.

[0059] <Additives> As with the pretreatment liquid, the ink of the present invention may contain surfactants, antifoaming agents, antiseptics, antifungals, antirust agents, etc., as needed, and the types and amounts that can be used are the same as those for the pretreatment liquid described above, so further explanation will be omitted here.

[0060] <Ink properties> The physical properties of the ink are not particularly limited and can be appropriately selected depending on the purpose. For example, it is preferable that the viscosity, surface tension, pH, etc. are within the following ranges. The ink viscosity at 25°C is preferably 5 mPa·s or more and 30 mPa·s or less, and more preferably 5 mPa·s or more and 25 mPa·s or less, in order to improve print density and character quality and obtain good ejection properties. Here, viscosity can be measured using, for example, a rotational viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.). Measurement conditions include 25°C, a standard cone rotor (1°34' x R24), a sample liquid volume of 1.2 mL, a rotation speed of 50 rpm, and 3 minutes. The surface tension of the ink is preferably 35 mN / m or less, and more preferably 32 mN / m or less at 25° C., in order to ensure that the ink is properly leveled on the recording medium and the drying time of the ink is shortened. The pH of the ink is preferably 7 to 12, and more preferably 8 to 11, from the viewpoint of preventing corrosion of metal members that come into contact with the ink.

[0061] (Post-processing liquid) Next, the post-treatment liquid will be described. In the present invention, after applying the ink, a post-treatment liquid is used for the purpose of improving color development and rubbing fastness. The post-treatment liquid used in the present invention contains cationic resin particles and may also contain water and the like.

[0062] <Cationic resin particles> Cationic resin particles quickly aggregate when applied onto previously applied ink and remain on the surface, forming a coating layer, which contributes to improved color development and abrasion resistance.

[0063] The cationic resin particles contained in the post-treatment liquid are preferably added in the form of a resin emulsion in which the resin particles are dispersed in water as a dispersion medium, and are preferably of a self-emulsifying type.

[0064] The cationic component of the cationic resin is not particularly limited, but is preferably a quaternary ammonium salt.

[0065] The cationic resin particles are preferably acrylic resin or urethane resin. The resin particles may be appropriately synthesized or commercially available. These may be used alone or in combination of two or more types of resin particles.

[0066] The method for synthesizing the cationic resin particles is not particularly limited, and any known synthesis method can be used, for example, the following method.

[0067] <<Cationic urethane resin particles>> An example of the preparation of cationic urethane resin particles will be described. Cationic urethane resin particles can be prepared from a polyol, a polyisocyanate, and a tertiary amino group-containing polyol. For example, a polyol, a polyisocyanate, and a separately prepared tertiary amino group-containing polyol are reacted in a solvent or without solvent to prepare a urethane prepolymer with isocyanate groups at the ends. The urethane prepolymer is then chain-extended using a polyamine to prepare a urethane resin particle dispersion. The tertiary amino groups in the urethane resin particle dispersion are then neutralized with an acid or quaternized with a quaternizing agent. This process allows the preparation of urethane resin cationic resin particles.

[0068] Another example of a production method is to produce polyurethane by reacting a polyol, a polyisocyanate, and a tertiary amino group-containing polyol in a solvent or without a solvent, and then neutralizing the tertiary amino groups in the polyurethane with an acid or quaternizing them with a quaternizing agent.

[0069] The tertiary amino group-containing polyol can be prepared by the following method. First, a compound having two epoxy groups per molecule (described later) and a secondary amine are mixed so that one equivalent of epoxy groups corresponds to one equivalent of NH groups. Then, these are subjected to a ring-opening addition reaction at about 20°C or while heating, to produce a tertiary amino group-containing polyol.

[0070] Examples of the compound having two epoxy groups per molecule include ethanediol 1,2-diglycidyl ether, propanediol 1,2-diglycidyl ether, propanediol 1,3-diglycidyl ether, butanediol 1,4-diglycidyl ether, pentanediol 1,5-diglycidyl ether, 3-methyl-pentanediol 1,5-diglycidyl ether, neopentyl glycol diglycidyl ether, hexanediol 1,6-diglycidyl ether, polybutadiene glycol diglycidyl ether, cyclohexanediol 1,4-diglycidyl ether, diglycidyl ether of 2,2-bis(4-hydroxycyclohexyl)-propane (hydrogenated bisphenol A), and diglycidyl ether of a mixture of isomers of hydrogenated dihydroxydiphenylmethane (hydrogenated bisphenol F).

[0071] Examples of acids for neutralizing tertiary amino groups in urethane resin particle dispersions or tertiary amino groups in polyurethane include aliphatic di- or tricarboxylic acids such as malonic acid, succinic acid, tartaric acid, oxalic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, alkylsuccinic acid, linolenic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, citric acid, and isocitric acid; organic acids such as phthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and tetrahydrophthalic acid; organic sulfonic acids such as sulfonic acid, paratoluenesulfonic acid, and methanesulfonic acid; and inorganic acids such as phosphoric acid, boric acid, phosphorous acid, hydrochloric acid, sulfuric acid, and nitric acid; and at least one of these may be used.

[0072] Examples of quaternizing agents for quaternizing tertiary amino groups in urethane resin particle dispersions or tertiary amino groups in polyurethane include dialkyl sulfates such as dimethyl sulfate and diethyl sulfate, alkyl or aryl methyl sulfonates such as methyl methanesulfonate and methyl paratoluenesulfonate, epoxies such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether, and alkyl halides such as methyl chloride, ethyl chloride, benzyl chloride, methyl bromide, ethyl bromide, benzyl bromide, methyl iodide, ethyl iodide, and benzyl iodide, and at least one of these can be used.

[0073] <<Cationic acrylic resin particles>> An example of the preparation of cationic acrylic resin particles will be described. Cationic acrylic resin particles are prepared from materials such as (meth)acrylic monomers, styrene, and α-methylstyrene by emulsion polymerization of vinyl monomers using a cationic emulsifier, emulsion polymerization of vinyl monomers using a polymer having cationic groups as a protective colloid, or reverse emulsion polymerization of cationic water-soluble monomers. In this specification, (meth)acrylic means either acrylic or its corresponding methacrylic.

[0074] The cationic acrylic resin particles may also be prepared from the above materials using a cationic surfactant as an emulsion stabilizer, such as laurylamine salt, stearyltrimethylenediamine salt, octadecylamine salt, laurylpyridinium chloride, stearylammonium chloride, dioleylammonium chloride, or octylbenzyltrimethylammonium chloride.

[0075] The cationic acrylic resin particles may be prepared by emulsion polymerization of the above-mentioned materials using a nonionic surfactant, followed by the post-addition of a cationic substance, such as a cationic surfactant, polyoxyethylene alkylamine, or polyethyleneimine.

[0076] The cationic acrylic resin particles may be prepared by radical copolymerizing an N-substituted aminoalkyl (meth)acrylate such as dimethylaminoethyl (meth)acrylate or diethylaminoethyl (meth)acrylate, or an N-substituted aminoalkyl (meth)acrylamide such as dimethylaminopropyl (meth)acrylamide with another (meth)acrylic monomer, styrene, α-methylstyrene, or the like, followed by quaternization with an alkylating agent.

[0077] Generally, cationic acrylic resin particles are produced from the above materials by solution polymerization using a solvent or emulsion polymerization using an emulsifier. Examples of alkylating agents used in the solution polymerization or emulsion polymerization include octyl chloride, octyl bromide, dodecyl chloride, dodecyl bromide, tetradecyl chloride, tetradecyl bromide, hexadecyl chloride, and hexadecyl bromide.

[0078] As mentioned above, commercially available cationic resin particles can also be used, such as Superflex 620 and 650 from Dai-ichi Kogyo Seiyaku Co., Ltd., Hydran CP-7520 and CP-7610 from DIC Corporation, Permarin UC-20 from Sanyo Chemical Industries, Ltd., Vinyblan 2687 from Nissin Chemical Industry Co., Ltd., and Movinyl M-9410 from Japan Coating Resins Co., Ltd.

[0079] The average particle size of the cationic resin particles is preferably 10 nm or more and 300 nm or less, and more preferably 20 nm or more and 200 nm or less, which inhibits penetration into the printed layer and improves the smoothness of the finally formed coating layer, making it easy to particularly improve color development and abrasion resistance.

[0080] <Solid content> The solid content of the post-treatment liquid is preferably 1.0% by mass or more and 20.0% by mass or less, and more preferably 5.0% by mass or more and 20.0% by mass or less, relative to the total mass of the post-treatment liquid. Within this range, sufficient color development is obtained, rub fastness can be improved, and loss of ejection reliability can be suppressed. The amount of solid content contained in the post-treatment liquid can be calculated from the weight change before and after volatilizing volatile components by dropping 1 g of the post-treatment liquid into an aluminum cup and drying at 120°C for 5 hours. Drying is sufficient as long as it removes volatile components, and reduced-pressure drying is preferred to improve measurement accuracy. The degree of vacuum when drying under reduced pressure is preferably -0.1 MPa.

[0081] <Physical properties of post-processing liquid> The physical properties of the post-treatment liquid can be appropriately selected depending on the purpose. In order to achieve the effects of the present invention at a higher level, it is effective to sufficiently suppress the penetration of the post-treatment liquid into the printing layer, and from that perspective, the viscosity of the post-treatment liquid at 25°C is preferably 8.0 cP or more, and from the perspective of easily achieving good ejection, it is preferably 25.0 cP or less, more preferably 15.0 cP or less. From the perspective of improving ejection properties, the viscosity of the post-treatment liquid at 25°C is preferably 8.0 cP or more and 11.0 cP or less. Note that 1 cP = 1 mPa s. Other physical properties such as surface tension are not particularly limited and can be adjusted appropriately.

[0082] (Liquid application device and liquid application method) The liquid application device of the present invention has the ink set of the present invention, and is characterized by comprising: a pretreatment liquid application unit that applies the pretreatment liquid to a substrate; an ink application unit that applies the aqueous pigment ink to the substrate; and a posttreatment liquid application unit that applies the posttreatment liquid to the substrate.

[0083] The liquid application method of the present invention is a liquid application method that uses the ink set of the present invention, and is characterized by including: a pre-treatment liquid application step of applying the pre-treatment liquid to a substrate; an ink application step of applying the aqueous pigment ink to the substrate after the pre-treatment liquid application step; and a post-treatment liquid application step of applying the post-treatment liquid to the substrate after the ink application step.

[0084] The liquid application device of the present invention is a device capable of applying a pre-treatment liquid, an ink, a post-treatment liquid, and, if necessary, various other treatment liquids, etc. to a substrate, and the liquid application method of the present invention is a method of printing using the device. The liquid application device and liquid application method of the present invention provide good image density and high rub fastness. The liquid-applying apparatus of the present invention may be, for example, a printing apparatus, an image-forming apparatus, a recording apparatus, a printing apparatus, a printer, etc. The liquid-applying method of the present invention may be, for example, a printing method, an image-forming method, a recording method, a printing method, a printing method, etc. The liquid-applying method of the present invention can be suitably carried out by the liquid-applying apparatus of the present invention.

[0085] In the liquid application method of the present invention, a pretreatment liquid, an aqueous pigment ink, and a posttreatment liquid are applied to a substrate in this order. The pretreatment liquid application step may be referred to as the first step, the ink application step as the second step, and the posttreatment liquid application step as the third step. The aqueous pigment ink may also be referred to simply as ink.

[0086] The substrate refers to a material to which the pre-treatment liquid, ink, post-treatment liquid, and, if necessary, other various treatment liquids can be attached even temporarily. The substrate can be selected appropriately, and fabric is preferred.

[0087] The fabric used in the present invention may be a woven fabric, a knitted fabric, a nonwoven fabric, etc. The fibers forming the fabric may be natural fibers such as cotton, rayon, hemp, silk, wool, etc., semi-synthetic fibers such as acetate, triacetate, etc., and synthetic fibers such as polyester, polyamide, acrylic, etc.

[0088] In the present invention, the terms image formation, recording, printing, printing, etc. are all synonymous. Furthermore, the terms recording medium, media, printed material, and substrate are all synonymous.

[0089] The liquid application device and liquid application method of the present invention are not limited to those that visualize meaningful images such as letters and figures using ink. For example, they also include those that form patterns such as geometric designs and those that create three-dimensional images.

[0090] <Pretreatment Liquid Application Step and Pretreatment Liquid Application Unit> The pretreatment liquid application step is a step of applying a pretreatment liquid to a substrate. The pretreatment liquid applying means is a means for applying the pretreatment liquid to the substrate. The pretreatment liquid application step is suitably carried out by a pretreatment liquid application unit.

[0091] The method for applying the pretreatment liquid is not particularly limited and can be appropriately selected depending on the purpose, and for example, a known method can be used. Examples of the method for applying the pretreatment liquid include immersion, spraying, inkjet printing, 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.

[0092] The immersion method is a method in which the substrate is immersed in the pretreatment liquid and the pretreatment liquid is applied. The spray method is a method in which the pretreatment liquid is sprayed onto the substrate using a spray device or the like. The inkjet method is a method in which the pretreatment liquid is ejected onto the substrate using an inkjet system. The roll coating method is a method in which the pretreatment liquid is applied to the substrate using a roll coater or the like.

[0093] Among these, the immersion method, roll coating method, and spray method are preferred because they have a simple device configuration and can quickly apply the pretreatment liquid. Furthermore, the inkjet method is preferred because it can apply the pretreatment liquid only to the area where the ink is to be applied, can apply a small amount uniformly, and can reduce costs. In the case of the inkjet method, either a serial type or a line type may be used.

[0094] The amount of the pretreatment liquid applied per unit area of ​​the substrate (which may also be referred to as the coating amount) is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of achieving both sufficient color development and drying properties of the ink on the substrate, it is preferred to apply an amount of 5 g / m 2 More than 500g / m 2 Preferably, it is 5 g / m or less. 2 More than 300g / m 2 It is more preferable that the density is 5 g / m or less. 2 When the density is 500 g / m or more, the ink aggregation function is exhibited, the penetration of the ink into the substrate is suppressed, and a high-quality image without bleeding can be obtained, which is preferable. 2 If the amount is less than this, the amount of volatile components applied will not be too large, so drying properties can be improved, and for example, the pressing time when drying the printed material can be prevented from becoming too long.

[0095] <Ink application process and ink application means> The ink application step is a step of applying ink to the substrate, and may be a step of applying ink to the region to which the pretreatment liquid has been applied. The ink applying means is a means for applying ink to the substrate, and may be a means for applying ink to the region to which the pretreatment liquid has been applied. The ink application step is preferably carried out by an ink application means.

[0096] The ink application method can be selected as appropriate, but an inkjet method is preferred. Inkjet method ejection has a simple device configuration, allows ink to be applied quickly, and allows the ink to be applied precisely to a target location, resulting in cost savings.

[0097] The aqueous pigment ink (ink) and post-treatment liquid are preferably ejected by an inkjet method and applied to the substrate. That is, the ink application means is preferably an ejection means that ejects the aqueous pigment ink, and the post-treatment liquid application means is preferably an ejection means that ejects the post-treatment liquid. Furthermore, the ink application step preferably ejects the aqueous pigment ink by an inkjet method, and the post-treatment liquid application step preferably ejects the post-treatment liquid by an inkjet method. In this case, a good image can be formed, and the post-treatment liquid can be applied by confining it to the area where the ink is applied, allowing a small amount to be applied uniformly, resulting in cost reduction.

[0098] The type of ink to be applied is not particularly limited and can be selected appropriately. One type or multiple types may be used.

[0099] The amount of ink applied per unit area to the substrate is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of achieving both sufficient color development and drying speed of the ink on the fabric, a coating amount of 5 g / m 2 More than 50g / m 2 Preferably, it is 5 g / m or less. 2 More than 30g / m 2 It is more preferable that the density is 5 g / m or less. 2 A density of 50 g / m or more is preferable because it provides image color development that can withstand practical use. 2 If the amount is less than this, the amount of volatile components applied will not be too large, so that drying properties can be improved, and for example, the pressing time when drying the printed matter will not be too long, which is preferable.

[0100] <Post-treatment liquid application step and post-treatment liquid application unit> The post-treatment liquid application step is a step of applying a post-treatment liquid, and may be a step of applying a post-treatment liquid to an area where ink has been applied. The post-treatment liquid applying unit is a unit that applies a post-treatment liquid, and may be a unit that applies a post-treatment liquid to an area where ink has been applied. The post-treatment liquid application step is suitably carried out by a post-treatment liquid application means.

[0101] The method for applying the post-treatment liquid is not particularly limited and can be appropriately selected depending on the purpose, and the same methods as those for applying the pre-treatment liquid can be used. Therefore, although explanations will be omitted here, the immersion method, roll coating method, and spray method are preferred, and the inkjet method is more preferred.

[0102] The amount of post-treatment liquid applied per unit area to the substrate is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of achieving both sufficient color development and drying properties of the ink on the substrate, it is preferred to apply an amount of 5 g / m 2 More than 50g / m 2 Preferably, it is 5 g / m or less. 2 More than 30g / m 2 It is more preferable that the density is 5 g / m or less. 2 A density of 50 g / m or more is preferable because it is easy to form a continuous film of transparent resin without permeating into the printed layer. 2 If the amount is less than this, the texture of the printed matter is less likely to deteriorate, which is preferable.

[0103] In the printing method of the present invention, the ink application process and the post-treatment liquid application process are performed separately, so the ratio between the amount of ink applied and the amount of post-treatment liquid applied can be freely varied. By varying the ratio between the amount of ink applied and the amount of post-treatment liquid applied, it is possible to adjust the effect of the ink and the effect of the post-treatment liquid, and, for example, to adjust the balance between robustness and image quality (density and saturation). Furthermore, by adjusting the ratio between the amount of ink applied and the amount of post-treatment liquid applied, the post-treatment liquid can be used as a treatment liquid regardless of the mixing stability of the components contained in the ink and the components contained in the post-treatment liquid.

[0104] For these reasons, the post-treatment liquid application step preferably includes an application amount adjustment step of adjusting the application amount of the post-treatment liquid. By performing the application amount adjustment step and applying the post-treatment liquid in an adjusted application amount, it is possible to adjust the ratio between the application amount of the ink and the application amount of the post-treatment liquid, and to obtain the above-mentioned effects, such as being able to adjust the balance between robustness and image quality (density and saturation).

[0105] In the application amount adjustment step, for example, the control unit 160 selects the application amount, and the post-treatment liquid application control unit 163 controls the post-treatment liquid application unit 130 so that the selected application amount is achieved. There are no particular limitations on the adjustment of the application amount of the post-treatment liquid, and the adjustment may be performed for each job or for each substrate. The application amount may also be determined by the control unit based on information input by the user.

[0106] The ratio between the amount of ink applied and the amount of post-treatment liquid applied can be selected appropriately. Although not particularly limited, for example, if it is desired to improve fixation, the amount of post-treatment liquid is adjusted to be increased. Adjustments may be made to increase the amount of post-treatment liquid applied to improve the fixation of the ink and thereby improve the scratch resistance of the printed matter. Furthermore, if it is desired to maintain the image due to the color of the aqueous pigment ink, adjustments may be made to decrease the amount of post-treatment liquid applied.

[0107] <Heat drying process and heat drying means> The liquid application method of the present invention may include a heat drying step, and it is preferable to carry out the heat drying step after the post-treatment liquid application step. When the heat drying step is carried out after the post-treatment liquid application step, it is possible to improve the rub fastness. The liquid application device of the present invention may have a heating and drying means, and it is preferable to carry out heating and drying by the heating and drying means after application of the post-treatment liquid. When heating and drying is carried out after application of the post-treatment liquid, it is possible to improve the rub fastness. The heat drying step is a step of heating and drying one or more selected from the pre-treatment liquid, ink, and post-treatment liquid applied to the substrate, and is carried out by a heat drying means.

[0108] The heat drying method is not particularly limited and can be appropriately selected depending on the purpose. Examples include hot air heating, radiant heating, conduction heating, high-frequency drying, microwave drying, heat pressing, and fixing roller methods. These methods may be used alone or in combination of two or more. They may be contact or non-contact. Hot air drying and heat pressing are preferred from the viewpoint of improving fastness and shortening heating time. In the case of hot air drying and heat pressing, after the pretreatment liquid, ink, and posttreatment liquid are applied to the substrate, the volatile components in the ink can be efficiently volatilized, thereby improving the fastness of the printed matter.

[0109] The term "heat drying process" and "heat drying means" are used because these processes and means include both heating and drying. Heat drying of a substrate at a temperature exceeding the natural drying conditions is considered heat drying. Temperatures exceeding the natural drying conditions vary depending on the environment in which the device is used, but examples include temperatures of 35°C or higher.

[0110] The temperature for heat drying is not particularly limited, but is preferably from 100° C. to 200° C., and more preferably from 100° C. to 180° C. Depending on the substrate, heat shrinkage, yellowing, color migration, etc. may occur, so it is preferable to select the heat drying temperature appropriately. The heating and drying time is not particularly limited, and may be, for example, 1 minute or more.

[0111] The liquid application method of the present invention preferably does not include a heat drying step between the pre-treatment liquid application step and the post-treatment liquid application step. That is, after the application of the pre-treatment liquid, heat drying is not performed before the application of the ink, and after the application of the ink, heat drying is not performed before the application of the post-treatment liquid. In other words, a heat drying step may be included between the first step and the second step, or between the second step and the third step, but from the viewpoint of promoting the reactivity between the pre-treatment liquid and the ink, or the reactivity between the ink and the post-treatment liquid, it is preferable not to include a heat drying step between these steps.

[0112] By not including a heat drying step between the pre-treatment liquid application step and the post-treatment liquid application step, it is possible to improve image density and also improve rub fastness. The reactivity between the pre-treatment liquid and the ink is enhanced, which not only increases image density but also produces images without bleeding. Furthermore, by not including a heat drying step after the ink application step, it is possible to prevent the generation of voids between the printing layer and the post-treatment liquid layer, which makes it easier to obtain higher fastness.

[0113] The liquid application method of the present invention does not need to include a heat drying step, and the liquid application apparatus of the present invention does not need to include a heat drying means. If the liquid application apparatus of the present invention does not include a heat drying means, and the liquid application method of the present invention does not include a heat drying step, there is an advantage in that the apparatus can be made smaller.

[0114] <Pressing means and pressing step> In the liquid application method of the present invention, it is preferable to carry out a pressurizing step of pressurizing the area to which the pretreatment liquid has been applied after the pretreatment liquid application step and before the ink application step. The liquid application device of the present invention preferably has a pressurizing unit between the pretreatment liquid application unit and the ink application unit 120. The pressurizing unit applies pressure to the area where the pretreatment liquid has been applied after the pretreatment liquid has been applied to the substrate and before the ink is applied.

[0115] By performing the pressurizing step using a pressurizing device, the pretreatment liquid can be evenly spread, preventing the pretreatment liquid from becoming mottled. Furthermore, by performing the pressurizing step using a pressurizing device, when the substrate is a fabric, the fiber fluff on the fabric surface can be laid down and smoothed. This allows for uniform ink landing position and penetration, improving image quality.

[0116] <Means of Containment> The liquid application device of the present invention may have a storage means for storing each liquid. The storage means can be, for example, a pre-treatment liquid storage means, an ink storage means, or a post-treatment liquid storage means. Examples of the storage means include an ink cartridge.

[0117] <Example of Liquid Application Device and Liquid Application Method> Next, an example of the liquid application device and liquid application method of the present invention will be described with reference to the drawings. Fig. 1 is a schematic explanatory diagram showing an example of a liquid deposition apparatus of the present invention. Fig. 2 is a schematic explanatory diagram showing an example of a control means of the liquid deposition apparatus of Fig. 1. Fig. 3 is a flowchart showing an example of the operation of the liquid deposition apparatus of Fig. 1. Here, a printing apparatus and a printing method will be taken as examples of the liquid deposition apparatus and liquid deposition method.

[0118] In the printing method of the present invention, the pretreatment liquid application step, ink application step, and posttreatment liquid application step may be performed in the same printing apparatus, or may be performed in independent apparatuses (for example, printing machines).

[0119] The printing apparatus 100 includes a pretreatment liquid applying unit 110, an ink applying unit 120, a posttreatment liquid applying unit 130, and a control unit 160, and further includes a heating and drying unit 140, a conveying unit 150, a memory unit 170, etc., as required.

[0120] The pretreatment liquid application unit 110 applies the pretreatment liquid to the substrate M. The method for applying the pretreatment liquid is not particularly limited, and the methods described above can be used. The pretreatment liquid application unit 110 in this example is an example in which a roll coating method is used.

[0121] The ink applying means 120 applies the aqueous pigment ink to the substrate M. The method of applying the ink is not particularly limited, and the methods described above can be used. The ink applying means 120 in this example is an example in which an inkjet method is used.

[0122] The post-treatment liquid applying unit 130 applies the post-treatment liquid to the substrate M. The method for applying the post-treatment liquid is not particularly limited, and the methods described above can be used. The post-treatment liquid applying unit 130 in this example is an example in which an inkjet method is used.

[0123] The control means 160 is, for example, a CPU, and issues instructions to the storage unit 170 and each control unit. The storage unit 170 is, for example, a hard disk drive (HDD) and stores data such as images to be printed.

[0124] The control unit 160 has, for example, a pretreatment liquid application control unit 161, an ink application control unit 162, and a posttreatment liquid application control unit 163. The pretreatment liquid application control unit 161 controls the driving of the pretreatment liquid application unit 110. The ink application control unit 162 controls the driving of the ink application unit 120. The posttreatment liquid application control unit 163 controls the driving of the posttreatment liquid application unit 130.

[0125] The printing device 100 may have a means for applying ink other than aqueous pigment ink. In this case, the ink application control unit 162 also controls the driving of the means for applying ink other than aqueous pigment ink. The ink other than aqueous pigment ink is not particularly limited, but examples thereof include clear ink.

[0126] The printing apparatus 100 may include a heating and drying means 140 that heats and dries the printing surface (front surface) and back surface of the substrate M to which the pretreatment liquid, ink, and posttreatment liquid have been applied. The heating and drying means 140 may be omitted. Furthermore, if necessary, the printing apparatus 100 may include a step of heating and drying the substrate M after other liquids, including the posttreatment liquid, have been applied, or before and after the application of each liquid.

[0127] The conveying means 150 conveys the substrate M. The conveying means 150 is not particularly limited as long as it is capable of conveying the substrate M, and examples thereof include a conveying belt and a platen. The conveying means 150 may be omitted as necessary.

[0128] The printing apparatus 100 may optionally include a fixing unit that heats and fixes the image formed on the substrate M. The fixing unit is not particularly limited, but examples thereof include a fixing roller and a heat press device.

[0129] The liquid application device of the present invention can also be used as a desktop printer. When used as a desktop printer, for example, a preferred embodiment is one in which the pretreatment liquid, ink, and posttreatment liquid are ejected by an inkjet recording method. One embodiment of the pretreatment liquid application unit and the posttreatment liquid application unit is one in which they are ejected by an inkjet recording method, as in the case of common color inks such as black (K), cyan (C), magenta (M), and yellow (Y). When using such an embodiment in which ink is ejected by an inkjet recording method, for example, a liquid storage unit containing the pretreatment liquid, ink, and posttreatment liquid, and a liquid ejection head are added.

[0130] An example of liquid application will be described with reference to Fig. 3. Here, an example of image formation will be described as an example of liquid application, and an image forming apparatus will be taken as an example of the liquid application apparatus.

[0131] When the image forming apparatus receives the instruction to start image formation, the image forming apparatus starts the image forming operation. In step S1, the image forming apparatus conveys the substrate M by the conveying means 150, and the pretreatment liquid applying means 110 applies the pretreatment liquid to the substrate M.

[0132] In this case, the pretreatment liquid applying unit 110 may apply the pretreatment liquid only to the portion where an image is to be formed, or may apply the pretreatment liquid to the entire surface of the substrate. When applying the pretreatment liquid only to the portion where an image is to be formed, the application area is determined in accordance with, for example, an instruction from the pretreatment liquid application control unit 161, and the pretreatment liquid applying unit 110 applies the pretreatment liquid to that application area. When applying the pretreatment liquid to the entire surface of the substrate, the pretreatment liquid applying unit 110 applies the pretreatment liquid to the entire surface of the substrate in accordance with, for example, an instruction from the pretreatment liquid application control unit 161.

[0133] In step S2, the ink applying unit 120 applies ink to the substrate M that has been transported by the transport unit 150 and to which the pretreatment liquid has been applied. At this time, the ink applying unit 120 may apply ink only to the portion to which the pretreatment liquid has been applied, or may apply ink to the entire surface of the substrate. However, in the present invention, it is preferable that the ink applying unit 120 applies ink to the portion to which the pretreatment liquid has been applied.

[0134] When applying ink only to the portion to which the pretreatment liquid has been applied, the application range is determined in accordance with, for example, an instruction from the ink application control unit 162, and the ink application unit 120 applies ink to that application range. When applying ink to the entire surface of the substrate, the ink application unit 120 applies ink to the entire surface of the substrate in accordance with, for example, an instruction from the ink application control unit 162.

[0135] In step S3, the post-treatment liquid applying unit 130 applies the post-treatment liquid to the substrate M that has been transported by the transport unit 150 and to which the pre-treatment liquid and ink have been applied. At this time, the post-treatment liquid applying unit 130 may apply the post-treatment liquid only to the areas to which the pre-treatment liquid and ink have been applied, or may apply the post-treatment liquid to the entire surface of the substrate. However, in the present invention, it is preferable that the post-treatment liquid applying unit 130 applies the post-treatment liquid to the areas to which the pre-treatment liquid and ink have been applied.

[0136] When the post-treatment liquid is applied only to the portion where an image is to be formed, the discharge range is determined in accordance with, for example, an instruction from the post-treatment liquid application control unit 163, and the post-treatment liquid application unit 130 applies the post-treatment liquid to the discharge range. When the post-treatment liquid is applied to the entire surface of the substrate, the post-treatment liquid application unit 130 applies the post-treatment liquid to the entire surface of the substrate in accordance with, for example, an instruction from the post-treatment liquid application control unit 163.

[0137] In step S3, an application amount adjustment step of adjusting the application amount of the post-treatment liquid may be performed. By performing the application amount adjustment step, it is possible to adjust the ratio between the application amount of the ink and the application amount of the post-treatment liquid.

[0138] The image forming apparatus may be provided with a sensor that recognizes the position and location of the substrate. By providing a sensor that recognizes the position and location of the substrate, the pre-treatment liquid applying unit 110, the ink applying unit 120, and the post-treatment liquid applying unit 130 can apply the pre-treatment liquid, the ink, and the post-treatment liquid to the substrate more efficiently in steps S1, S2, and S3.

[0139] After step S3, the substrate to which the pre-treatment liquid, ink, and post-treatment liquid have been applied may be transported by transport means 150 to heating and drying means 140, where a drying step of drying may be carried out. The heating and drying means 140 and the heating and drying step are not essential and are optional in the liquid application apparatus and liquid application method of the present invention.

[0140] When the heat drying step is not performed, the user may manually perform heat drying using a separate heat drying device. When the heat drying step is performed, the heat drying time and heat drying temperature may be constant or may be adjusted depending on the amounts of the pre-treatment liquid, ink, and post-treatment liquid applied. It is more preferable to adjust them depending on the amounts of the pre-treatment liquid, ink, and post-treatment liquid applied.

[0141] The image forming apparatus may have a sensor for detecting the amount of pre-treatment liquid, ink, and post-treatment liquid applied to the substrate. The sensor enables the heat-drying time and heat-drying temperature to be set and adjusted according to the amount of pre-treatment liquid, ink, and post-treatment liquid applied to the recording medium. This allows the heat-drying unit 140 to heat-dry the substrate more efficiently.

[0142] The sensor that recognizes the amount of the pre-treatment liquid, ink, and post-treatment liquid applied may be a sensor that recognizes the amount of liquid actually attached to the substrate, or a sensor that measures and recognizes the amount applied to the substrate by each application means.

[0143] The image forming process using the image forming apparatus is completed after the substrate is heated and dried as needed. In addition, the process may include steps of removing the substrate from the image forming apparatus and transporting the substrate.

[0144] <Other Examples of Liquid Application Apparatus and Liquid Application Method> Next, another example of the liquid deposition apparatus and liquid deposition method of the present invention will be described. 4 is a schematic diagram illustrating another example of a liquid application device of the present invention. A printing device and a printing method will be described as an example of the liquid application device and the liquid application method. The printing device 100 of this example has a pressurizing unit 180 between a pretreatment liquid application unit 110 and an ink application unit 120. The pressurizing unit 180 pressurizes the area where the pretreatment liquid has been applied after the pretreatment liquid has been applied to the substrate and before the ink is applied. In the printing method of this example, after the pretreatment liquid application step and before the ink application step, a pressurizing step is performed in which pressure is applied to the area where the pretreatment liquid has been applied.

[0145] The pressure means 180 may be a cylindrical or columnar pressure roller or the like, or may be a flat plate whose pressure application area is a flat surface. By performing the pressurizing step using the pressurizing unit 180, the pretreatment liquid is evenly spread, and mottling of the pretreatment liquid can be prevented. Furthermore, by performing the pressurizing step using the pressurizing unit 180, when the substrate is fabric, the fiber fluff on the fabric surface can be laid down and smoothed. This makes it possible to make the ink landing position and penetration uniform, thereby improving image quality.

[0146] Next, still another example of the liquid deposition apparatus and liquid deposition method of the present invention will be described. The ink set of the present invention can be suitably used in various recording devices using the inkjet recording method, such as printing devices, printers, facsimile machines, copying machines, printer / fax / copier combination machines, and three-dimensional modeling devices.

[0147] The liquid application device can include not only a head portion that ejects ink, but also means related to feeding, transporting, and discharging the recording medium, as well as other devices called pre-processing devices and post-processing devices.

[0148] Furthermore, unless otherwise specified, the liquid deposition device includes both a serial type device in which the discharge head moves and a line type device in which the discharge head does not move. Furthermore, this liquid deposition device includes not only desktop types, but also wide-width printing devices that can print on A0-sized recording media, and continuous feed printers that can use continuous paper wound into a roll as a substrate, for example.

[0149] The liquid deposition device of this example will be described with reference to FIGS. 5 and 6. FIG. 5 is a perspective view of the device. FIG. 6 is a perspective view of the main tank. The printing device 400 of this example is a serial-type image forming device. A mechanism unit 420 is provided within an exterior 401 of the printing device 400. Each ink storage unit 411 of the main tanks 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is formed from a packaging material such as aluminum laminate film. The ink storage unit 411 is housed in a storage container case 414 made of, for example, plastic. As a result, the main tanks 410 are used as ink cartridges for each color.

[0150] On the other hand, a cartridge holder 404 is provided at the back of the opening when the cover 401c of the device body is opened. A main tank 410 is detachably attached to the cartridge holder 404. This allows each ink outlet 413 of the main tank 410 to communicate with the ejection head 434 for each color via the supply tube 436 for each color, making it possible to eject ink from the ejection head 434 onto a recording medium.

[0151] The liquid application device of this example can be provided with a pretreatment liquid ejection head that ejects a pretreatment liquid and a posttreatment liquid ejection head that ejects a posttreatment liquid, in addition to the ejection head 434 that ejects ink. The liquid application device of this example can also be provided with a pretreatment liquid storage unit that stores the pretreatment liquid, and the pretreatment liquid is supplied from the pretreatment liquid storage unit to the pretreatment liquid ejection head. The liquid application device of this example can also be provided with a posttreatment liquid storage unit that stores the posttreatment liquid, and the posttreatment liquid is supplied from the posttreatment liquid storage unit to the posttreatment liquid ejection head. In this way, the liquid application device of this example can also apply the pretreatment liquid, ink, and posttreatment liquid to a substrate.

[0152] <Electrode manufacturing equipment> The "liquid application device" according to the present invention also includes a manufacturing device for an electrode and an electrochemical element. An electrode manufacturing device will be described below.

[0153] 16 is a schematic diagram showing an example of an electrode manufacturing apparatus according to an embodiment of the present invention. The electrode manufacturing apparatus is an apparatus for manufacturing an electrode including a layer having an electrode material by ejecting liquid compositions such as a pretreatment liquid, an aqueous pigment ink, and a posttreatment liquid using a head module including a liquid ejection head.

[0154] <Means for forming layer containing electrode material, and process for forming layer containing electrode material> The discharge means provided in the electrode manufacturing apparatus shown in FIG. 16 is a head module according to the embodiment of the present invention. A liquid composition is applied to a target object by being discharged from a discharge head included in the head module, thereby forming a liquid composition layer. The target object (hereinafter, sometimes referred to as a "discharge target") is not particularly limited as long as it is an object on which a layer containing an electrode material is to be formed, and can be appropriately selected depending on the purpose. For example, the target object may be an electrode substrate (current collector), an active material layer, a layer containing a solid electrode material, or the like. The target object may also be an electrode mixture layer containing an active material on an electrode substrate (current collector). The discharge means and discharge step may also be a means and step for forming a layer containing an electrode material by directly discharging the liquid composition, as long as it is possible to form a layer containing an electrode material on the discharge target object. The discharge means and discharge step may also be a means and step for forming a layer containing an electrode material by indirectly discharging the liquid composition.

[0155] <Other components and processes> Other components included in the manufacturing apparatus for an electrode mixture layer are not particularly limited and can be selected appropriately depending on the purpose. Furthermore, other steps included in the manufacturing method for an electrode mixture layer are also not particularly limited and can be selected appropriately depending on the purpose. For example, components and steps included in the manufacturing apparatus and manufacturing method for an electrode mixture layer include a heating means and a heating step.

[0156] <Heating means, heating process> The heating means included in the manufacturing device for the electrode mixture layer is a means for heating the liquid composition ejected by the ejection means. Also, the heating step included in the manufacturing method for the electrode mixture layer is a step of heating the liquid composition ejected in the ejection step. By heating the liquid composition, the liquid composition layer can be dried.

[0157] <Configuration for forming a layer containing an electrode material by directly ejecting a liquid composition> Here, as an example of an electrode manufacturing apparatus, an electrode manufacturing apparatus that forms an electrode mixture layer containing an active material on an electrode substrate (current collector) will be described. As shown in Fig. 16, the electrode manufacturing apparatus includes a discharge process unit 110 that includes a step of applying a liquid composition to a printing substrate 704 having an object to be discharged to form a liquid composition layer, and a heating process unit 130 that includes a heating step of heating the liquid composition layer to obtain an electrode mixture layer.

[0158] The electrode manufacturing apparatus includes a conveying unit 705 that conveys the printing substrate 704. The conveying unit 705 conveys the printing substrate 704 at a preset speed through the discharging process unit 110 and the heating process unit 130 in that order. There are no particular limitations on the method for manufacturing the printing substrate 704 having a discharge target such as an active material layer, and any known method can be selected as appropriate. The discharging process unit 110 includes a liquid discharge head 281a that performs the application step of applying a liquid composition onto the printing substrate 704, a storage container 281b that stores the liquid composition 707, and a supply tube 281c that supplies the liquid composition 707 stored in the storage container 281b to the liquid discharge head 281a.

[0159] In the discharge process unit 110, the liquid composition 707 is discharged from the liquid discharge head 281a and applied to the printing substrate 704, thereby forming a thin film of the liquid composition layer. The storage container 281b may be configured as an integral part of the manufacturing apparatus for the electrode mixture layer, or may be configured as a removable part from the manufacturing apparatus for the electrode mixture layer. The storage container 281b may be a container used for adding the liquid to a storage container that is integrated with the manufacturing apparatus for the electrode mixture layer, or a storage container that is removable from the manufacturing apparatus for the electrode mixture layer.

[0160] The storage container 281b and the supply tube 281c can be arbitrarily selected as long as they can stably store and supply the liquid composition 707.

[0161] In the heating process section 130, a solvent removal step is carried out in which the solvent remaining in the liquid composition layer is heated and removed. Specifically, the solvent remaining in the liquid composition layer is heated and dried by the heating device 703 in the heating process section 130, thereby removing the solvent from the liquid composition layer. This results in the formation of an electrode mixture layer. The solvent removal step in the heating process section 130 may also be carried out under reduced pressure.

[0162] The heating device 703 is not particularly limited and can be appropriately selected depending on the purpose. For example, the heating device 703 can be a substrate heater, an IR heater, a hot air heater, or the like. The heating device 703 may also be a combination of at least two of the substrate heater, the IR heater, and the hot air heater. The heating temperature and heating time can be appropriately selected depending on the boiling point of the solvent contained in the liquid composition 707 or the thickness of the formed film.

[0163] By using the electrode manufacturing apparatus according to an embodiment of the present invention, a liquid composition can be ejected onto a target object. The electrode mixture layer can be suitably used, for example, as part of the configuration of an electrochemical element. The components other than the electrode mixture layer in the electrochemical element are not particularly limited, and known components can be appropriately selected. For example, components other than the electrode mixture layer include a positive electrode, a negative electrode, a separator, and the like.

[0164] <Example of cleaning the nozzle surface> Next, another example of the liquid deposition apparatus and liquid deposition method of the present invention will be described. The liquid deposition apparatus of this example is equipped with a nozzle surface cleaning device, and the liquid deposition method of this example includes a nozzle surface cleaning step.

[0165] In this example, the ink application means has a nozzle surface on which nozzles for ejecting the aqueous pigment ink are provided, the post-treatment liquid application means has a nozzle surface on which nozzles for ejecting the post-treatment liquid are provided, and the liquid application device is equipped with a nozzle surface cleaning device that cleans at least one of the nozzle surfaces of the ink application means and the post-treatment liquid application means, and the nozzle surface cleaning device has a wiping member that wipes away liquid from the nozzle surface.

[0166] By providing the liquid application device with a nozzle surface cleaning device, the nozzle surface can be cleaned, making it easier to maintain good ejection properties. By including the nozzle surface cleaning step in the printing method, the nozzle surface can be cleaned, making it easier to maintain good ejection properties.

[0167] FIG. 7 is a schematic diagram illustrating a liquid deposition apparatus according to this embodiment. Here, a printing apparatus will be used as an example of the liquid deposition apparatus. The printing apparatus 100 according to this embodiment is a serial inkjet recording apparatus. The printing apparatus 100 according to this embodiment includes inkjet recording modules 1a, 1b, and 1c, and a substrate holding member 3.

[0168] The inkjet recording modules 1a, 1b, and 1c each have a recording head that ejects liquid. In this example, the inkjet recording module 1a ejects a pre-treatment liquid, the inkjet recording module 1b ejects ink, and the inkjet recording module 1c ejects a post-treatment liquid. When the inkjet recording modules 1a, 1b, and 1c are described without distinction, they will also be referred to as inkjet recording module 1.

[0169] The substrate holding member 3 holds the substrate 39 and moves and scans in the direction indicated by arrow D2. The substrate holding member 3 moves and scans below the recording heads of the inkjet recording modules 1a, 1b, and 1c. The inkjet recording modules eject liquid onto the substrate 39 held by the substrate holding member 3 to perform printing.

[0170] FIG. 8 is a schematic diagram showing an example of the inkjet recording module 1. As shown in FIG. The inkjet recording module 1 is a liquid ejection device that includes a recording head 34 that is a liquid ejection head that ejects liquid droplets from nozzles, and a maintenance and recovery mechanism 81 for maintaining or recovering the liquid ejection head. The maintenance and recovery mechanism 81 includes a nozzle surface cleaning device 2 that cleans the nozzle surface of the liquid ejection head.

[0171] The inkjet recording module 1 has a carriage 33. The carriage 33 is held slidably in the main scanning direction by a main guide rod 31 and a sub-metal guide 32, which are guide members that are hung horizontally on the left and right side plates 21A and 21B of the main body of the printing device 1. The carriage 33 moves and scans in the direction indicated by arrow D1 (carriage main scanning direction) via a timing belt driven by a main scanning motor.

[0172] The carriage 33 has recording heads 34a, 34b, 34c, and 34d (referred to as "recording heads 34" when not distinguishing between them) which are liquid ejection heads for ejecting ink droplets of each color, such as yellow (Y), cyan (C), magenta (M), and black (K). The recording head 34 has a nozzle row made up of multiple nozzles arranged in a sub-scanning direction (direction indicated by arrow D2) perpendicular to the main scanning direction. The recording head 34 is mounted on the carriage 33 with the ink droplet ejection direction facing downward.

[0173] The carriage 33 is equipped with a supply pump unit and sub-tanks for supplying ink of each color to the recording head 34. The sub-tanks are replenished with ink of each color by the supply pump unit via supply tubes 35 of each color from ink cartridges 6 of each color that are detachably mounted in the cartridge loading section.

[0174] When the inkjet recording module 1 has a plurality of recording heads 34, the plurality of recording heads 34 may be referred to as a head unit or the like. In the case of an inkjet recording module 1 that ejects a pre-treatment liquid or a post-treatment liquid, the inkjet recording module 1 may have one or more recording heads 34. The same treatment liquid may be ejected by the plurality of recording heads 34.

[0175] 8, maintenance and recovery mechanisms 81a and 81b for maintaining and recovering the state of the nozzles of the recording head 34 are arranged in the non-printing areas on both sides of the carriage 33 in the scanning direction. The maintenance and recovery mechanism 81a is equipped with cap members (hereinafter referred to as "caps") 82a, 82b, 82c, and 82d (referred to as "caps 82" when not distinguishing between them) for capping the nozzle surfaces of the recording head 34. The maintenance and recovery mechanism 81b is equipped with a wiping unit 83 that constitutes the nozzle surface cleaning device 2.

[0176] The maintenance and recovery mechanism 81a also includes an idle discharge receiver that receives droplets when idle discharge is performed to discharge droplets that do not contribute to recording in order to expel thickened recording liquid, and a carriage lock that locks the carriage 33. Furthermore, the maintenance and recovery mechanism 81a is provided with a fixed waste liquid tank that is not replaced below it to store waste liquid generated by maintenance and recovery operations, and a replaceable replacement waste liquid tank on one side of the maintenance and recovery mechanism 81a.

[0177] As in this example, it is preferable to provide a nozzle surface cleaning device 2 for each inkjet recording module 1. In this case, even if different inks and treatment liquids are used for each inkjet recording module 1, and even if cleaning operations are performed using the nozzle surface cleaning device 2, the components constituting the ink and treatment liquid do not mix. For example, if the same nozzle surface cleaning device is used when liquids with different polarities, such as treatment liquid and ink, are used, mixing of the liquids may occur within the nozzle surface cleaning device or on the nozzle surface, causing reaction, aggregation, or precipitation of the liquid components, which may result in ejection defects. On the other hand, according to this example, stable ejection can be maintained even when multiple liquids that cannot be mixed, such as treatment liquid and aqueous pigment ink, or liquids that lack stability after mixing are used.

[0178] 9 is an example of a control block diagram of the liquid deposition device of this example. The control means 160 controls the substrate holding member 3, inkjet recording module 1, etc. using instructions from an operation panel 165, etc. The substrate holding member 3 is controlled by, for example, a substrate transport control unit. Furthermore, the transport of the substrate 39 may be controlled using a substrate height detection unit or a group of various sensors.

[0179] The control means 160 controls the recording heads 34 via, for example, the inkjet recording control unit (IJ recording control unit), head control unit, and head driver of the inkjet recording module 1. In the drawing, a head unit is illustrated as a plurality of recording heads 34. The control means 160 also controls the liquid feed pump and the electromagnetic valve group via the supply system control unit. The control means 160 also controls the suction pump, cap, the electromagnetic valve group, and cleaning device via the maintenance system control unit. The cleaning device includes the nozzle surface cleaning device 2, etc. The control means 160 also controls the main scanning motor via the main scanning control unit. By controlling the main scanning motor, the scanning direction of the carriage 33 can be controlled.

[0180] An example of printing in this example will be described. The substrate holding member 3 holds the substrate 39 in an initial position and moves to the recording start position of the inkjet recording module 1a, where it stops. The printing device drives the recording head 34 in accordance with an image signal while moving the carriage 33 of the inkjet recording module 1a in the main scanning direction D1. The inkjet recording module 1a ejects pretreatment liquid onto the substrate 39, which is intermittently transported in the direction D2 by the substrate holding member 3. Upon receiving a recording end signal or a signal indicating that the rear end of the substrate 39 has reached the recording area, the printing device ends the recording operation in the inkjet recording module 1a and sends the substrate 39 to the inkjet recording module 1b.

[0181] Inkjet recording module 1b ejects ink droplets onto recording medium 39, which is fixed and stationary on substrate holding member 3, to record one line, and then records the next line after substrate 39 has been transported a predetermined distance. Upon receiving a recording end signal or a signal indicating that the rear end of substrate 39 has reached the recording area, the printing device terminates the recording operation in inkjet recording module 1b and sends substrate 39 to inkjet recording module 1c.

[0182] The inkjet recording module 1c ejects post-treatment liquid onto the substrate 39, which is intermittently transported in the direction D2 by the substrate holding member 3. The printing device ends the recording operation in the inkjet recording module 1c when it receives a recording end signal or a signal indicating that the rear end of the substrate 39 has reached the recording area. When the recording operation ends, the substrate holding member 3 returns to its initial position, making the substrate available for recovery.

[0183] After the recording operation is completed, an operation is performed to maintain or restore the state of the nozzles of the recording head 34 (hereinafter referred to as "maintenance and recovery") as necessary. The maintenance and recovery operation includes, for example, nozzle suction, idle discharge, and nozzle surface cleaning. The maintenance and recovery operation includes, for example, moving the carriage 33 to a position facing the maintenance and recovery mechanism 81, which is the home position. Nozzle suction involves moving the carriage 33 to the home position, then capping with a cap 82, and then suctioning from the nozzles. Idle discharge involves moving the carriage 33 to the home position, then discharging droplets that do not contribute to image formation. Nozzle surface cleaning involves cleaning the nozzle surface using a nozzle surface cleaning device. By performing maintenance and recovery operations in this manner, image formation can be achieved through stable droplet discharge.

[0184] Next, an example of the nozzle surface cleaning device 2 will be described. The nozzle surface cleaning device 2 of this example has a first wiping member, a wiping member transporting means, a wiping member pressing member, a second wiping member, and a holder member.

[0185] The first wiping member is a long, rollable wiping member that wipes droplets off the nozzle surface. The wiping member transport means transports the first wiping member in the longitudinal direction. The wiping member pressing member brings the first wiping member into contact with the nozzle surface. The second wiping member is a blade-shaped wiping member that wipes droplets off the nozzle surface. The holder member supports the second wiping member so that it is fixed or rotatable.

[0186] Furthermore, the second wiping member rotates to come into contact with the first wiping member on the upstream side of the wiping member pressing member in the transport direction of the first wiping member. The droplets on the nozzle surface that are wiped by the nozzle surface cleaning device 2 are, for example, unnecessary liquid that is forcibly discharged from the nozzles during image formation or by the maintenance and recovery mechanism 81, or droplets that have adhered to the nozzles.

[0187] Next, the nozzle surface cleaning device 2 of this example will be described with reference to FIGS. Figures 10(A) and (B) are top views showing an example of the wiping unit 83 that constitutes the nozzle surface cleaning device 2. The position of the wiping subframe 85 differs between Figures 10(A) and 10(B). Figure 11 is a schematic cross-sectional view of an example of the nozzle surface cleaning device 2, showing an example of cleaning using a web. Figure 11 is a schematic cross-sectional view of another example of the nozzle surface cleaning device 2, showing an example of cleaning using a wiper blade. Figure 12 is a schematic cross-sectional view of another example of the nozzle surface cleaning device 2, showing an example of cleaning using a web and a wiper blade.

[0188] The wiping unit 83 has, for example, a wiping main frame 84 and a wiping sub-frame 85. The wiping main frame 84 is supported by the liquid ejection device main body. The wiping sub-frame 85 can reciprocate between the position shown in FIG. 10(A) and the position shown in FIG. 10(B). In the figure, arrow De indicates the wiping direction relative to the recording head 34, and arrow Dc indicates the transport direction of the first wiping member 90.

[0189] On the wiping subframe 85, a first wiping member 90, a wiping member transport means, a wiping member pressing member 91, a second wiping member 86, and a holder member 87 are arranged. The first wiping member 90 is a long, rollable wiping member that wipes droplets off the nozzle surface. Hereinafter, the first wiping member 90 may be referred to as a web.

[0190] The wiping member transport means transports the first wiping member 90 in the longitudinal direction. The wiping member transport means is composed of, from the upstream side in the transport direction of the web 90, a feed roll 94, an upstream roller 95, a roller 91a pressed by the pressing member 91, a downstream roller 96, and a take-up roll 97.

[0191] The wiping member pressing member 91 brings the first wiping member 90 into contact with the nozzle face. The wiping member pressing member 91 is a member that presses the web 90 against the nozzle face of the recording head 34 via a roller 91a, and is preferably elastic, such as a compression spring or an elastic material such as rubber. The position of the wiping member pressing member 91 in the pressing direction is not limited, and the height in the pressing direction can be changed using a cam, for example, and the pressing pressure of the web can be changed from non-contact to contact and when in contact.

[0192] The second wiping member 86 is a blade-shaped wiping member that wipes droplets off the nozzle surface. Hereinafter, the second wiping member 86 may be referred to as a wiper blade.

[0193] The holder member 87 fixedly or rotatably supports the second wiping member 86. Hereinafter, the holder member 87 may be referred to as a wiper holder. The wiper holder 87 is supported by the wiping subframe 85 and can fix or rotate the wiper blade 86. The wiper blade 86 rotates to come into contact with the web 90 on the upstream side of the pressing member 91 in the web transport direction. The position of the wiper holder 87 is not limited to the position shown in FIGS. 12 and 13, as long as the wiper blade 86 can be brought into contact with the web 90 on the upstream side of the pressing member 91.

[0194] A rotary encoder 92 is coaxially mounted on the downstream roller 96. A transmission sensor 93 capable of monitoring the transport of the web 90 is also provided to manage the transport amount of the web 90.

[0195] The nozzle surface cleaning device 2 of this example is capable of three types of cleaning operations. (1) Web wiping (e.g., Figure 11) In a single cleaning operation, the web wiping wipes droplets off the nozzle surface using a first wiping member (web) 90. The web wiping has a high ability to remove ink that has adhered to the nozzle surface, and its cleaning ability can be enhanced by soaking the web in cleaning liquid. The web is made of fibers, for example, and comes into point contact with the nozzle, which gives it high cleaning ability, but also increases the frictional force against the nozzle, making it more likely to deteriorate the water-repellent film on the nozzle surface after repeated wiping.

[0196] (2) Blade wiping (see Figure 12 for example) Blade wiping involves wiping droplets off the nozzle surface with the second wiping member (wiper blade) 86 and removing droplets adhering to the second wiping member (wiper blade) 86 with the first wiping member (web) 90 in a single cleaning operation. Blade wiping is highly capable of removing liquid from the nozzle surface and excels in forming a meniscus on the nozzle after cleaning. Furthermore, because it comes into contact with the nozzle through line contact and surface contact, the frictional force against the nozzle is low, and the water-repellent film on the nozzle surface is less likely to deteriorate with the number of wiping operations.

[0197] (3) Web and blade wiping (e.g., Figure 13) Web and blade wiping involves wiping droplets off the nozzle surface with a first wiping member (web) 90, wiping droplets off the nozzle surface with a second wiping member (wiper blade) 86, and removing droplets adhering to the second wiping member (wiper blade) 86 with the first wiping member (web) 90, in that order, in one cleaning operation. This wiping method is highly effective at removing ink that has adhered to the nozzle surface and at forming a meniscus on the nozzle after cleaning. It also reduces the number of times the web is wiped, which helps prevent deterioration of the water-repellent film on the nozzle surface.

[0198] Below, a supplementary explanation will be given regarding FIGS. 11 to 13.

[0199] (1) Web Wiping 11(A) schematically shows the state before the nozzle surface is wiped by the web 90, and (B) schematically shows the state after the nozzle surface has been wiped by the web 90. Cleaning of the nozzle surface is performed by a wiping subframe 85 moving relatively to the recording head 34 after the recording head 34 has been moved to the maintenance and recovery mechanism 81 and a suction operation is performed by a cap 82 connected to a suction pump. Alternatively, cleaning is performed by a supply pump supplying ink to the recording head 34 after the recording head 34 has been moved to the maintenance and recovery mechanism 81 and pressurizing it to discharge the ink from the head, and then the wiping subframe 85 moving relatively to the recording head 34. FIG. 11(A) schematically shows droplets (ink) 50 to be wiped that are present on the nozzle surface of the recording head 34 before cleaning and after the suction operation by the cap 82.

[0200] The droplets 50 on the nozzle surface are wiped away and absorbed by the web 90 as the wiping subframe 85 moves in the direction of the arrow in Fig. 11(A) and the web 90, which is pressed by the pressing member 91 via the roller 91a, comes into contact with the nozzle surface. The direction of the arrow in Fig. 11(A) corresponds to the De direction in Fig. 10.

[0201] Figure 11(C) shows a schematic diagram of the state where the droplets 50 have been wiped away by the web 90 as a result of the operation shown in Figure 11(A). The droplets 50 remaining on the nozzle surface are removed by the web 90 wiping the nozzle surface. A known configuration can be applied as the means (mechanism) for driving and transporting the web 90 to perform these operations.

[0202] (2) Blade wiping Figures 12(A) and (B) schematically show the state before wiping by the wiper blade 86. Figure 12(C) schematically shows the state after the nozzle surface has been wiped by the wiper blade 86. Figure 12(D) schematically shows the state in which the wiper blade 86 is being cleaned (adhered droplets are removed) by the web 90.

[0203] Cleaning of the nozzle surface is performed by performing a suction operation on the recording head 34, which has been moved to the maintenance and recovery mechanism 81, using the cap 82 connected to the suction pump, and then moving the wiping sub-frame 85 relative to the recording head 34. Alternatively, cleaning is performed by supplying ink from a supply pump to the recording head 34, which has been moved to the maintenance and recovery mechanism 81, and applying pressure to discharge ink from the recording head, and then moving the wiping sub-frame 85 relative to the recording head 34.

[0204] Figure 12(A) schematically shows droplets (ink) 50 to be wiped away that are present on the nozzle face of the recording head 34 after the suction operation by the cap 82 and before cleaning. The droplets 50 on the nozzle face are wiped away and removed when the wiping subframe 85 moves in the direction of the arrow in Figure 12(A) and the wiper blade 86 comes into contact with the nozzle face. The direction of the arrow in Figure 12(A) corresponds to the direction De in Figure 10.

[0205] As shown in FIG. 12(C), the droplets 50 removed from the nozzle surface adhere to the wiper blade 86.

[0206] 12(D) shows the cleaning operation of the wiper blade 86. The droplets 50 removed from the nozzle surface and attached to the wiper blade 86 are absorbed by the web 90 when the wiper blade 86 comes into contact with the web 90 as the wiper holder 87 rotates, and are then removed from the wiper blade 86.

[0207] The operation of the wiper holder 87 is, for example, fixed when wiping the nozzle surface, and after wiping the nozzle surface, rotates downstream in the transport direction until the wiper blade 86 abuts against the web 90. A known configuration can be applied as a means (mechanism) for driving the wiper holder 87 to perform these operations.

[0208] (3) Web and blade wiping Fig. 13(A) schematically shows the state before the nozzle surface is wiped by the web 90. Fig. 13(B) schematically shows the state after the nozzle surface has been wiped by the web 90 and before wiping by the wiper blade 86. Fig. 13(C) schematically shows the state after the nozzle surface has been wiped by the wiper blade 86. Fig. 13(D) schematically shows the state in which the wiper blade 86 is being cleaned by the web 90 (removing adhering droplets).

[0209] Cleaning of the nozzle surface is performed by performing a suction operation on the recording head 34, which has been moved to the maintenance and recovery mechanism 81, using the cap 82 connected to the suction pump, and then moving the wiping sub-frame 85 relative to the recording head 34. Alternatively, cleaning is performed by supplying ink from a supply pump to the recording head 34, which has been moved to the maintenance and recovery mechanism 81, and applying pressure to discharge ink from the recording head, and then moving the wiping sub-frame 85 relative to the recording head 34.

[0210] 13A schematically shows droplets (ink) 50 to be wiped away that are present on the nozzle face of the recording head 34 after the suction operation by the cap 82 and before cleaning. The wiping subframe 85 moves in the direction of the arrow in the figure, and the web 90, pressed by the wiping member pressing member 91 via the roller 91a, comes into contact with the nozzle face. As a result, the droplets 50 on the nozzle face are wiped away and absorbed by the web 90.

[0211] 13(B) schematically shows droplets 50a wiped by web 90 in the operation of Fig. 13(A), and droplets (ink) 50b remaining on the nozzle face without being wiped by web 90. The droplets 50b remaining on the nozzle face are wiped and removed by the wiper blade 86 coming into contact with the nozzle face.

[0212] As shown in FIG. 13(C), the droplets 50 removed from the nozzle surface adhere to the wiper blade 86.

[0213] 13(D) shows the cleaning operation of the wiper blade 86. The liquid droplets 50b removed from the nozzle surface and adhering to the wiper blade 86 are absorbed by the web 90 and removed from the wiper blade 86 when the wiper holder 87 rotates and the wiper blade 86 abuts against the web 90. The operation of the wiper holder 87 is, for example, such that the wiper holder 87 is fixed when wiping the nozzle surface, and after wiping the nozzle surface, the wiper blade 86 rotates downstream in the transport direction until it abuts against the web 90. A known configuration can be applied as the means (mechanism) for driving the wiper holder 87 to perform these operations.

[0214] (Printed material) Next, the printed matter of the present invention will be described. The printed matter of the present invention is a printed matter obtained using the ink set of the present invention, and is characterized by having a substrate, and a printed layer containing the organic acid, the amine compound, and a pigment, and a layer containing a cationic resin, on the substrate.

[0215] The printed matter of the present invention has good image density and high rub fastness. The printed matter of the present invention is produced by the liquid application method of the present invention. Furthermore, the printed matter of the present invention is produced by the liquid application apparatus of the present invention. The printed matter may also be called a printed matter, a recorded matter, etc.

[0216] Fig. 14 is a cross-sectional observation image of an example of the printed matter of the present invention. Fig. 15 is a cross-sectional schematic diagram for schematically explaining the layer structure of an example of the printed matter of the present invention. The base material 39 is a fiber base material (cotton). The printed layer 191 is a layer containing an organic acid, an amine compound, and a pigment, and corresponds to a layer formed from a pretreatment liquid and an aqueous pigment ink. In Fig. 15, a pigment 195 is schematically shown to be contained in the printed layer 191. The continuous layer 192 is a layer formed by post-treatment and is a continuous layer without pigment. The continuous layer 192 corresponds to a layer formed with a post-treatment liquid and containing a cationic resin. It is named continuous layer 192 because, for example, it does not contain a pigment and is a continuous layer formed only by the binding of the cationic resin contained in the post-treatment liquid. It is possible to form a continuous layer without pigment on top of a printed layer, which is thought to improve image density due to the reflective strength of the coating film and also to protect the printed layer with the resin of the continuous layer. The embedding resin 193 is an epoxy resin that has been hardened in advance in order to prepare a cross-sectional thin section of the printed matter for observation. [Example]

[0217] The present invention will be explained in more detail below by showing examples, but the present invention is not limited to these examples.

[0218] (Preparation of Black Pigment Dispersion A) <Preparation of Polymer Solution A> A 1-L flask equipped with a mechanical stirrer, a thermometer, a nitrogen gas inlet tube, a reflux condenser, and a dropping funnel was thoroughly purged with nitrogen gas, and then 11.2 g of styrene, 2.8 g of acrylic acid, 12.0 g of lauryl methacrylate, 4.0 g of polyethylene glycol methacrylate, 4.0 g of styrene macromer, and 0.4 g 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, 108.0 g of lauryl methacrylate, 36.0 g of polyethylene glycol methacrylate, 60.0 g of hydroxyethyl methacrylate, 36.0 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 dropwise 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, 0.8 g of azobismethylvaleronitrile was added, and the mixture was further aged for 1 hour. After completion of the reaction, 364 g of methyl ethyl ketone was added to the flask, yielding 800 g of polymer solution A with a concentration of 50% by mass.

[0219] <Preparation of Pigment-Containing Polymer Microparticle Dispersion> 28 g of polymer solution A, 42 g of carbon black pigment (trade name: Monarch 800, manufactured by Cabot Corporation), 13.6 g of 1 mol / L potassium hydroxide aqueous solution, 20 g of methyl ethyl ketone, and 13.6 g of ion-exchanged water were thoroughly stirred and then kneaded using a roll mill. The resulting paste was added to 200 g of pure water and thoroughly stirred. After that, the methyl ethyl ketone and water were distilled off using an evaporator. The dispersion was then pressure-filtered through a polyvinylidene fluoride membrane filter with an average pore size of 5.0 μm to remove coarse particles, yielding resin-coated black pigment dispersion A with a pigment concentration of 15% by mass and a solids concentration of 20% by mass.

[0220] (Preparation of Black Pigment Dispersion B) 100 g of carbon black: Seast SP (SRF-LS) manufactured by Tokai Carbon Co., Ltd. was added to 3000 mL of 2.5 N (normal) sodium hypochlorite solution, and the mixture was stirred at a temperature of 60°C and a speed of 300 rpm for 10 hours to carry out an oxidation treatment, resulting in a pigment with carboxylic acid groups attached to the surface of the carbon black. This reaction solution was filtered, and the separated carbon black was neutralized with a sodium hydroxide solution and subjected to ultrafiltration. Next, the pigment dispersion and ion-exchanged water were subjected to ultrafiltration using a dialysis membrane, and then ultrasonic dispersion was carried out to concentrate the pigment solid content to 20%, thereby obtaining a self-dispersing black pigment dispersion B.

[0221] (Preparation of ink, pre-treatment liquid and post-treatment liquid) The materials were mixed and stirred according to the formulations and blending amounts (mass %) shown in Tables 1 to 3 below, and filtered through a 1.2 μm cellulose acetate filter (Minisart, manufactured by Sartorius), to obtain the liquids of Ink Preparation Examples 1 to 4, Pre-treatment Liquid Preparation Examples 1 to 8, and Post-treatment Liquid Preparation Examples 1 to 10. The amounts of resin emulsions and pigments added are shown as solid contents.

[0222] The details of the materials used and listed in Tables 1 to 3 are shown below. Surfynol 440 (acetylene glycol surfactant manufactured by Nissin Chemical Co., Ltd.) Silface SAG-014 (a silicone surfactant manufactured by Nissin Chemical Co., Ltd.) Takelac W-6110 (Mitsui Chemicals urethane resin emulsion) Permarin UA-368 (urethane resin emulsion manufactured by Sanyo Chemical Industries, Ltd.) Nikasol FX-2033 (acrylic resin emulsion manufactured by Nippon Carbide Industries Co., Ltd.) Adeka Bontitor HUX-561S (Adeka urethane resin emulsion) Emulgen LS-106 (Kao Corporation hydrocarbon surfactant) Hydran CP7520 (DIC urethane resin emulsion, cationic) Superflex 650 (urethane resin emulsion, cationic, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Movinyl M-9410 (Japan Coating Resin acrylic resin emulsion, cationic) PUE-800 (non-ionic urethane resin emulsion manufactured by Murayama Scientific Research Institute) Proxel LV (preservative manufactured by Arcsada) Other reagents used were purchased from Kanto Chemical Co., Ltd. The viscosity of the post-treatment liquid after preparation is shown in Table 3. The viscosity is the value at 25°C.

[0223] [Table 1]

[0224] [Table 2]

[0225] [Table 3]

[0226] (Examples 1 to 14, Comparative Examples 1 to 6) For each example and comparative example, the following evaluations were carried out for the combination of pre-treatment, ink, and post-treatment shown in Table 4. Heat drying "○" in the table indicates that a heat drying step was performed, and heat drying was carried out in a hot air oven at 160°C for 5 minutes. The evaluations shown in Table 4 were specifically carried out using the methods described below, and all substrates used were cotton broadcloth 40 with sill manufactured by Irozome Co., Ltd. The substrates used were fabrics.

[0227] <Image density evaluation> The pre-treatment liquid, ink, and post-treatment liquid of each of the Examples and Comparative Examples were filled into separate RICOH Ri100s manufactured by Ricoh Co., Ltd., and the deposition amount of the pre-treatment liquid, ink, and post-treatment liquid was 20 g / m 2 Thereafter, a solid print was performed on the substrate at 600 × 600 dpi, and in some examples, a drying step was performed between applications, and finally, the print was dried for 10 minutes in a hot air oven set at 160°C to produce a printed matter. The pre-treatment liquid, ink, and post-treatment liquid were ejected onto the substrate by an inkjet method, as shown in FIG. The image density of the solid image produced by the above method was measured and evaluated using an X-rite Exact manufactured by X-rite Co., Ltd. The evaluation criteria are as follows: Grades up to B are within the acceptable range.

[0228] [Evaluation criteria] AA: Solid density is 1.5 or more A: Solid area density is 1.4 or more B: Solid area density is 1.3 or more and less than 1.4 C: Solid area density is less than 1.3

[0229] <System stability evaluation> The pre-treatment liquid, ink, and post-treatment liquid of each of the Examples and Comparative Examples were filled into separate RICOH Ri100s manufactured by Ricoh Co., Ltd., and the deposition amount of the pre-treatment liquid, ink, and post-treatment liquid was 20 g / m 2 The device was then placed in a thermostatic chamber at 50°C and left there for one month. After removing it from the chamber and allowing the entire device to return to room temperature, the amount of adhesion was measured again. The evaluation criteria are as follows: Grades up to B are within the acceptable range.

[0230] [Evaluation criteria] A: The change in adhesion amount is less than 5% B: The change in adhesion amount is 5% or more but less than 10% C: The change in adhesion amount is 10% or more.

[0231] <Dry rubbing fastness evaluation> A solid image was prepared in the same manner as in the image density evaluation, and a rub fastness test (dry rub) was conducted using a Gakushin-type rub fastness tester in accordance with Japanese Industrial Standards (JIS) L0849, and the color OD transferred to cotton fabric was measured. The evaluation criteria are as follows: B is acceptable.

[0232] [Evaluation criteria] AA: Transfer OD of cotton fabric after test is less than 0.10 A: The transfer OD of the cotton fabric after the test is 0.10 or more and less than 0.15 B: The transfer OD of the cotton fabric after the test is 0.15 or more and less than 0.20 C: Transfer OD of cotton fabric after test is 0.20 or more

[0233] <Wet rubbing fastness evaluation> A solid image was prepared in the same manner as in the image density evaluation, and a rub fastness test (wet rub) was conducted using a Gakushin-type rub fastness tester in accordance with Japanese Industrial Standards (JIS) L0849, and the color OD transferred to cotton fabric was measured. The evaluation criteria are as follows: B is acceptable.

[0234] [Evaluation criteria] AA: Transfer OD of cotton fabric after test is less than 0.10 A: The transfer OD of the cotton fabric after the test is 0.10 or more and less than 0.15 B: The transfer OD of the cotton fabric after the test is 0.15 or more and less than 0.20 C: Transfer OD of cotton fabric after test is 0.20 or more

[0235] (Examples 15 and 16) In the evaluation of Example 1, the deposition amount of the pre-treatment liquid, post-treatment liquid, and ink was 20 g / m 2 The amount of post-treatment liquid applied was adjusted to 30 g / m. 2 , 5g / m 2 The results were used as Examples 15 and 16, respectively.

[0236] [Table 4]

[0237] Example 17 The pre-treatment liquid, ink, and post-treatment liquid of Example 1 were filled into a RICOH Ri100 manufactured by Ricoh Co., Ltd., and used as evaluation device 1. Similarly, the pre-treatment liquid, ink, and post-treatment liquid of Example 1 were filled into a modified RICOH Ri100 machine to create evaluation device 2. The modified RICOH Ri100 machine that served as evaluation device 2 was equipped with a nozzle surface cleaning device. The nozzle surface cleaning device had a wiping member that wiped away liquid from the nozzle surface of the RICOH Ri100. Evaluation device 1 and evaluation device 2 filled with each liquid were placed in a constant temperature bath at 50°C and left for three months. The amount of adhesion when a test image was printed before and after leaving the device was measured, and the number of maintenance operations required until the change in adhesion amount before and after leaving the device was less than 5% was determined. As a result, evaluation device 1 required five maintenance operations before the change in adhesion amount before and after leaving the device was less than 5%. On the other hand, evaluation device 2 required only two maintenance operations before the change in adhesion amount before and after leaving the device was less than 5%. Note that for evaluation device 2, nozzle surface cleaning shown in Figure 11 was performed as a maintenance operation. In this way, a liquid deposition device equipped with a nozzle surface cleaning device can clean the nozzle surface, making it easier to maintain good ejection performance.

[0238] For example, aspects of the present invention are as follows. <1> An ink set including a pretreatment liquid, an aqueous pigment ink, and a posttreatment liquid, the pretreatment liquid contains an organic acid and an amine compound, The post-treatment liquid contains cationic resin particles. An ink set characterized by: <2> The organic acid contained in the pretreatment solution is at least one selected from lactic acid, citric acid, and acetic acid. Characterized by <1> The ink set according to claim 1. <3> The viscosity of the post-treatment liquid at 25°C is 8.0 cP or more and 11.0 cP or less. Characterized by <1> or <2> The ink set according to claim 1. <4> The content of solids in the post-treatment liquid is 5.0% by mass or more and 20.0% by mass or less based on the total mass of the post-treatment liquid. Characterized by <1> from <3> 1. The ink set according to claim 1 , <5> <1> from <4> an ink set according to any one of a pretreatment liquid applying means for applying the pretreatment liquid to a substrate; an ink applying means for applying the aqueous pigment ink to a substrate; a post-treatment liquid applying means for applying the post-treatment liquid to the substrate. A liquid application device characterized by: <6> the ink applying means ejects the aqueous pigment ink; The post-treatment liquid applying means ejects the post-treatment liquid. Characterized by <5> The liquid applying device according to claim 1. <7> the ink applying means has a nozzle surface provided with nozzles for ejecting the aqueous pigment ink; the post-treatment liquid applying unit has a nozzle surface provided with nozzles for ejecting the post-treatment liquid, the liquid deposition device includes a nozzle surface cleaning device that cleans at least one of a nozzle surface of the ink deposition unit and a nozzle surface of the posttreatment liquid deposition unit, The nozzle surface cleaning device has a wiping member that wipes the liquid off the nozzle surface. Characterized by <6> The liquid applying device according to claim 1. <8> <1> from <4> A liquid application method using the ink set according to any one of the preceding claims, a pretreatment liquid applying step of applying the pretreatment liquid to a substrate; an ink applying step of applying the aqueous pigment ink to a substrate after the pretreatment liquid applying step; a post-treatment liquid applying step of applying the post-treatment liquid to the substrate after the ink applying step. A liquid application method comprising: <9> The step of applying the pre-treatment liquid and the step of applying the post-treatment liquid do not include a heat drying step. Characterized by <8> The liquid applying method according to claim 1. <10> The post-treatment liquid application step includes an application amount adjustment step of adjusting the application amount of the post-treatment liquid. Characterized by <8> or <9> The liquid applying method according to claim 1. <11> After the pretreatment liquid application step, but before the ink application step, a pressurizing step is performed in which the area to which the pretreatment liquid has been applied is pressurized. Characterized by <8> from <10> 10. The liquid applying method according to claim 9, wherein <12> <1> from <4> A printed matter obtained by using the ink set according to any one of a substrate; and a printed layer containing the organic acid, the amine compound, and a pigment, and a layer containing a cationic resin, on the substrate. A printed matter characterized by: [Explanation of symbols]

[0239] 1 Inkjet printing module 2 Nozzle surface cleaning device 3. Substrate holding member 33 Carriage 34 Recording head 39 Base material 50 droplets 81 Maintenance and Recovery Mechanism 86 wiper blade 90 Web 400 Printing equipment 401 Printing device exterior 401c Device body cover 404 Cartridge Holder 410 Main Tank 410k, 410c, 410m, 410y Main tanks for black (K), cyan (C), magenta (M), and yellow (Y) 411 Ink storage unit 413 Ink outlet 414 Storage container case 420 Mechanism Department 434 Discharge Head 436 Supply Tube [Prior art documents] [Patent documents]

[0240] [Patent Document 1] Japanese Patent Application Publication No. 2017-132946 [Patent Document 2] Japanese Patent Publication No. 2023-088510 [Patent Document 3] WO2020 / 090212 publication

Claims

1. An ink set including a pretreatment liquid, an aqueous pigment ink, and a posttreatment liquid, the pretreatment liquid contains an organic acid and an amine compound, The post-treatment liquid contains cationic resin particles. An ink set characterized by:

2. The organic acid contained in the pretreatment solution is at least one selected from lactic acid, citric acid, and acetic acid. The ink set according to claim 1 .

3. The viscosity of the post-treatment liquid at 25°C is 8.0 cP or more and 11.0 cP or less. The ink set according to claim 1 .

4. The content of solids in the post-treatment liquid is 5.0% by mass or more and 20.0% by mass or less based on the total mass of the post-treatment liquid. The ink set according to claim 1 .

5. The ink set according to any one of claims 1 to 4, a pretreatment liquid applying means for applying the pretreatment liquid to a substrate; an ink applying means for applying the aqueous pigment ink to a substrate; a post-treatment liquid applying means for applying the post-treatment liquid to the substrate. A liquid application device characterized by:

6. the ink applying means ejects the aqueous pigment ink; The post-treatment liquid applying means ejects the post-treatment liquid. The liquid application device according to claim 5 .

7. the ink applying means has a nozzle surface provided with nozzles for ejecting the aqueous pigment ink; the post-treatment liquid applying unit has a nozzle surface provided with nozzles for ejecting the post-treatment liquid, the liquid deposition device includes a nozzle surface cleaning device that cleans at least one of a nozzle surface of the ink deposition unit and a nozzle surface of the posttreatment liquid deposition unit, The nozzle surface cleaning device has a wiping member that wipes the liquid off the nozzle surface. The liquid application device according to claim 6 .

8. A liquid application method using the ink set according to any one of claims 1 to 4, a pretreatment liquid applying step of applying the pretreatment liquid to a substrate; an ink applying step of applying the aqueous pigment ink to a substrate after the pretreatment liquid applying step; a post-treatment liquid applying step of applying the post-treatment liquid to the substrate after the ink applying step. A liquid application method comprising:

9. The step of applying the pre-treatment liquid and the step of applying the post-treatment liquid do not include a heat drying step.

9. The liquid application method according to claim 8.

10. The post-treatment liquid application step includes an application amount adjustment step of adjusting the application amount of the post-treatment liquid.

9. The liquid application method according to claim 8.

11. After the pretreatment liquid application step, but before the ink application step, a pressurizing step is performed in which the area to which the pretreatment liquid has been applied is pressurized.

9. The liquid application method according to claim 8.

12. A printed matter obtained by using the ink set according to any one of claims 1 to 4, a substrate; and a printed layer containing the organic acid, the amine compound, and a pigment, and a layer containing a cationic resin, on the substrate. A printed matter characterized by:

Images