INK SET, FLUID APPLYING APPARATUS, FLUID APPLYING METHOD, AND PRINTED PRODUCT

Abstract

An ink set contains: a pre-treatment fluid containing an organic acid and an amine compound; an aqueous pigment ink containing water; a pigment; and an organic solvent, and a post-treatment fluid containing a cationic resin particle.

Claims

1. An ink set comprising: a pre-treatment fluid comprising: an organic acid; and an amine compound; an aqueous pigment ink comprising: water; a pigment; and an organic solvent, and a post-treatment fluid comprising a cationic resin particle.

2. The ink set according to claim 1, wherein the organic acid comprises at least one of lactic acid, citric acid, or acetic acid.

3. The ink set according to claim 1, wherein the post-treatment fluid has a viscosity of 8.0 to 11.0 cP at 25 degrees Celsius.

4. The ink set according to claim 1, wherein the post-treatment fluid contains a solid content ranging from 5.0 to 20.0 percent by mass.

5. A fluid applying apparatus comprising: the ink set of claim 1; a pre-treatment fluid applying device to apply the pre-treatment fluid to a substrate; an ink applying device to apply the aqueous pigment ink to the substrate; and a post-treatment fluid applying device to apply the post-treatment fluid to the substrate.

6. The apparatus according to claim 5, wherein the ink applying device discharges the aqueous pigment ink and the post-treatment fluid applying device discharges the post-treatment fluid.

7. The apparatus according to claim 6, further comprising: one or more nozzle surface cleaning device each comprising a wiping member, wherein the ink applying device includes a nozzle surface with nozzles that discharge the aqueous pigment ink, wherein the post-treatment fluid applying device includes a nozzle surface with nozzles that discharge the post-treatment fluid, wherein the one or more nozzle surface cleaning devices clean at least one of the nozzle surface of the ink applying device or the nozzle surface of the post-treatment fluid applying device, the wiping member wipes off fluid on at least one of the nozzle surface of the ink applying device or the nozzle surface of the post-treatment fluid applying device.

8. A fluid applying method using the ink set of claim 1, the method comprising: applying the pre-treatment fluid to a substrate; applying the aqueous pigment ink to the substrate; and applying the post-treatment fluid to the substrate.

9. The method according to claim 8, wherein the method includes no heat drying between the applying the aqueous pigment ink and the applying the post-treatment fluid.

10. The method according to claim 8, wherein the applying the post-treatment fluid includes adjusting an applied amount of the post-treatment fluid.

11. The method according to claim 8, further comprising: pressing a region where the pre-treatment fluid has been applied after the applying the pre-treatment fluid and before the applying the aqueous pigment ink.

12. A printed product produced with the ink set of claim 1, comprising: a substrate; a print layer on the substrate, the print layer comprising the organic acid, the amine compound, and the pigment; and a layer on the print layer, the layer containing the cationic resin particle on the print layer.

Description

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

[0013] A more complete appreciation of the disclosure and many of the attendant advantages and features thereof can be readily obtained and understood from the following detailed description with reference to the accompanying drawings, wherein:

[0014] FIG. 1 is a schematic diagram illustrating an example of the fluid applying device;

[0015] FIG. 2 is an example of the function block diagram;

[0016] FIG. 3 is an example of the flow;

[0017] FIG. 4 is a schematic diagram illustrating another example of the fluid applying device;

[0018] FIG. 5 is a schematic diagram illustrating another example of the fluid applying device;

[0019] FIG. 6 is a diagram illustrating a perspective view of an example of a main tank;

[0020] FIG. 7 is a schematic plan view illustrating another example of the fluid applying device;

[0021] FIG. 8 is a diagram illustrating a schematic plan view of an example of the inkjet recording module;

[0022] FIG. 9 is another example of the function block diagram;

[0023] FIGS. 10A and 10B are a schematic plan view and a schematic plan view, respectively, to explain an example of maintenance recovery action;

[0024] FIGS. 11A and 11B are a schematic plan view and schematic plan view, respectively, to explain an example of cleaning of the nozzle surface;

[0025] FIGS. 12A to 12D are schematic cross sectional views to explain another example of cleaning of the nozzle surface;

[0026] FIGS. 13A to 13D are schematic cross sectional views to explain another example of cleaning of the nozzle surface;

[0027] FIG. 14 is a cross sectional observation image of an example of the printed matter;

[0028] FIG. 15 is a cross sectional schematic diagram of an example of the printed product; and

[0029] FIG. 16 is a schematic diagram illustrating an example of a device for manufacturing an electrode.

[0030] The accompanying drawings are intended to depict example embodiments of the present invention and should not be interpreted to limit the scope thereof. The accompanying drawings are not to be considered as drawn to scale unless explicitly noted. Also, identical or similar reference numerals designate identical or similar components throughout the several views.

DESCRIPTION OF THE EMBODIMENTS

[0031] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present invention. As used herein, the singular forms a, an, and the are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms includes and/or including, when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.

[0032] Embodiments of the present invention are described in detail below with reference to accompanying drawings. In describing embodiments illustrated in the drawings, specific terminology is employed for the sake of clarity. However, the disclosure of this patent specification is not intended to be limited to the specific terminology so selected, and it is to be understood that each specific element includes all technical equivalents that have a similar function, operate in a similar manner, and achieve a similar result.

[0033] For the sake of simplicity, the same reference number will be given to identical constituent elements such as parts and materials having the same functions and redundant descriptions thereof omitted unless otherwise stated.

[0034] According to the present disclosure, an ink set is provided which enables achieving good image density and high rubbing fastness even for pigment inks.

[0035] The ink set, fluid applying apparatus, fluid applying method, and printed product will now be described with reference to accompanying drawings. It is to be noted that the following embodiments are not limiting the present disclosure and any deletion, addition, modification, change, etc. can be made within a scope in which man in the art can conceive including other embodiments, and any of which is included within the scope of the present disclosure as long as the effect and feature of the present disclosure are demonstrated.

Ink Set

[0036] The ink set of the present disclosure contains a pre-treatment fluid, an aqueous pigment ink, and a post-treatment fluid. The pre-treatment fluid contains an organic acid and an amine compound. The pigment ink contains water, a pigment, and an organic solvent. The post-treatment fluid contains a cationic resin particle.

[0037] According to the present disclosure, good image density and high rubbing fastness can be achieved even for pigment inks. While the reasons for the effects of the present disclosure are not limited thereto, they are considered to include, for example, the following: The printed product produced using the ink set of the present disclosure includes a layer (also referred to as a print layer) a layer containing aggregated aqueous pigment ink caused by mixing the aqueous pigment ink with a post-treatment fluid, and a layer (also referred to as a continuous layer) formed by the post-treatment fluid. It is considered that these layers have different charges and can exist independently of each other. In particular, by using a cationic resin in the post-treatment fluid, it is possible to form a continuous layer containing no pigment on top of the print layer, as illustrated in, for example, FIG. 14 described below. This structure is considered to not only improve image density through the reflectance of the coating film, but also protect the print layer through the resin in the continuous layer.

[0038] The print layer, which contains the aqueous pigment ink containing aggregated aqueous pigment ink caused by mixing the aqueous pigment ink with a post-treatment fluid, may be obtained by removing liquid components through processes such as drying.

Pre-Treatment Fluid

[0039] First, the pre-treatment fluid used in the present disclosure will be described. The pre-treatment fluid used in the present disclosure contains an organic acid and an amine compound, and may further contain other components such as water.

Organic Acid

[0040] There are no particular restrictions on the organic acids used in the pre-treatment fluid. It is preferable to include a carboxylic acid with six or fewer carbon atoms. Carboxylic acids with six or fewer carbon atoms exhibit high water solubility, preventing the separation of water and carboxylic acid during long-term storage, which enhances the stability of the pre-treatment fluid.

[0041] Specific examples of carboxylic acids with six or fewer carbon atoms include, but are not limited to, saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, and hexanoic acid, as well as hydroxy acids such as lactic acid, malic acid, and citric acid. The carbon chain may be linear or branched, and it may be saturated or unsaturated. Among them, lactic acid, citric acid, and acetic acid are particularly preferred for use, as they are inexpensive, highly safe, and can efficiently aggregate the pigment in the ink.

[0042] Additionally, the content of the organic acid in the pre-treatment fluid is preferably at least 1 percent by mass and more preferably at least 2 percent by mass relative to the entire of the pre-treatment fluid. A content of at least 1 percent by mass promotes pigment aggregation, thereby reducing image bleeding. Furthermore, the content is preferably at most 50 percent by mass, and more preferably 15 percent by mass, relative to the entire of the pre-treatment fluid. If the organic acid content is at most 50 percent by mass, the effect of the pigment remaining on the fabric surface does not become excessive, making it easier to maintain friction fastness. The content is particularly preferably 10 to 15 percent by mass with respect to the entire of the pre-treatment fluid, and in such cases, image bleeding can be suitably minimized, and images with excellent friction fastness can be obtained. The content of the organic acid in the pre-treatment fluid may be 1.5 to 2.0 percent by mass with respect to the entire of the pre-treatment fluid. In this case, pigment aggregation can be induced, and image bleeding can be suppressed.

Amine Compound

[0043] The amine compound contained in the pre-treatment fluid used in the present disclosure is not particularly limited and can be selected as appropriate.

[0044] The organic amine compound includes primary, secondary, tertiary, and quaternary amines and salts thereof.

[0045] Specific examples include, but are not limited to, tetraalkylammonium, alkylamines, benzalkonium, alkylpyridinium, imidazolium, polyamines, and their derivatives or salts. Specific examples include, but are not limited to, amylamine, butylamine, propanolamine, propylamine, ethanolamine, N-ethylethanolamine, 2-ethylhexylamine, ethylmethylamine, benzylamine, ethylenediamine, octylamine, oleylamine, cyclooctylamine, cyclobutylamine, cyclopropylamine, cyclohexylamine, diisopropanolamine, diethanolamine, diethylamine, di(2-ethylhexyl)amine, diethylenetriamine, diphenylamine, dibutylamine, dipropylamine, dihexylamine, dipentylamine, 3-(dimethylamino)propylamine, dimethylethylamine, dimethylethylenediamine, dimethyloctylamine, 1,3-dimethylbutylamine, dimethyl-1,3-propanediamine, dimethylhexylamine, aminobutanol, aminopropanol, aminopropanediol, 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, trichylamine, bis(2-aminoethyl)-1,3-propanediamine, bis(3-aminopropyl)ethylenediamine, bis(3-aminopropyl)-1,3-propanediamine, bis(3-aminopropyl)methylamine, bis(2-ethylhexyl)amine, bis(trimethylsilyl)amine, butylisopropylamine, propanediamine, propyl diamine, hexylamine, pentylamine, 2-methylcyclohexylamine, methylpropylamine, methylbenzylamine, monoethanolamine, laurylamine, nonylamine, trimethylamine, triethylamine, dimethylpropylamine, propylenediamine, hexamethylenediamine, tetraethylenepentamine, diethylaminoethanol, tetramethylammonium chloride, tetraethylammonium bromide, dihydroxyethyl stearylamine, 2-heptadec-1-enyl-hydroxyethylimidazoline, lauryldimethylbenzylammonium chloride, cetylpyridinium chloride, stearamidomethylpyridinium chloride, diallyldimethylammonium chloride polymers, diallylamine polymers, and monoallylamine polymers.

[0046] The amount of the amine compound added in the present disclosure is preferably adjusted such that the molar ratio of amine functional groups to the acidic functional groups contained in the organic acid is from 0.05 to 1. Adjusting the amount within this range allows the pre-treatment fluid to maintain an appropriate level of aggregation force when the pre-treatment fluid is mixed with the ink, resulting in increased optical density of the printed product obtained using the ink set. In addition, adjusting the amount within this range allows the pH to be maintained in a neutral to weakly alkaline state, thereby reducing the risk of corrosion to the members from which the pre-treatment fluid is discharged or applied.

[0047] As a result, it is possible to stably perform liquid application processes such as printing over an extended period.

Additive

[0048] The pre-treatment fluid may furthermore optionally contain an organic solvent, surfactant, defoaming agent, preservative and antifungal agent, and corrosion inhibitor.

Organic Solvent

[0049] There is no specific limitation to the organic solvent for use in the present disclosure. For example, a water-soluble organic solvent can be used. It includes, but is not limited to, polyhydric alcohols, ethers such as polyhydric alcohol alkylethers and polyhydric alcohol arylethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds.

[0050] Specific examples of the water-soluble organic solvents include, but are not limited to, polyols such as 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-butane diol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butane triol, 1,2,3-butanetriol, 2,2,4-trimethyl-1,3-pentanediol, and petriol; polyol alkylethers such as ethylene glycol monoethylether, ethylene glycol monobutyl ether, diethylene glycol monomethylether, diethylene glycol monoethylether, diethylene glycol monobutyl ether, tetraethylene glycol monomethylether, and propylene glycol monoethylether; polyol arylethers such as ethylene glycol monophenylether and ethylene glycol monobenzylether; nitrogen-containing heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, -caprolactam, and -butyrolactone; amides such as formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethyl propionamide, and 3-buthoxy-N,N-dimethyl propionamide; amines such as monoethanolamine, diethanolamine, and triethylamine; sulfur-containing compounds such as dimethyl sulfoxide, sulfolane, and thiodiethanol; propylene carbonate, and ethylene carbonate.

[0051] It is preferable to use an organic solvent with a boiling point of at most 250 degrees Celsius, which serves as a humectant that dries quickly.

[0052] The content of the organic solvent in the organic solvent has no particular limit and can be selected to a particular application. To ensure stable discharge or application of the pre-treatment fluid, and at the same time maintain good drying properties of the final printed product, the content is preferably from 10 to 60 percent by mass, more preferably from 20 to 60 percent by mass, and even more preferably from 20 to 26 percent by mass.

Surfactant

[0053] Examples of the surfactant include, but are not limited to, silicone-based surfactants, fluorochemical surfactants, amphoteric surfactants, nonionic surfactants, and anionic surfactants.

[0054] The silicone-based surfactant has no specific limit and can be suitably selected to suit to a particular application.

[0055] Of these, the surfactants not decomposable in a high pH environment are preferable.

[0056] Examples include, but are not limited to, side chain modified polydimethyl siloxane, both terminal-modified polydimethyl siloxane, one-terminal-modified polydimethyl siloxane, and side-chain-both-terminal-modified polydimethyl siloxane. Silicone-based surfactants having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modification group are particularly preferable because such an aqueous surfactant demonstrates good properties.

[0057] The silicone-based surfactant includes a polyether-modified silicone-based surfactant, one of which is a compound in which a polyalkylene oxide structure is introduced into the side chain of the Si site of dimethyl silooxane.

[0058] Specific examples of the fluorochemical surfactant include, but are not limited to, perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, ester compounds of perfluoroalkyl phosphoric acid, adducts of perfluoroalkyl ethylene oxide, and polyoxyalkylene ether polymer compounds having a perfluoroalkyl ether group in its side chain. These are particularly preferable because the fluorochemical surfactant does not readily produce foams.

[0059] Specific examples of the perfluoroalkyl sulfonic acid compounds include, but are not limited to, perfluoroalkyl sulfonic acid and salts of perfluoroalkyl sulfonic acid. Specific examples of the perfluoroalkyl carbonic acid compounds include, but are not limited to, perfluoroalkyl carbonic acid and salts of perfluoroalkyl carbonic acid.

[0060] Specific examples of the polyoxyalkylene ether polymer compounds having a perfluoroalkyl ether group in its side chain include, but are not limited to, sulfuric acid ester salts of polyoxyalkylene ether polymer having a perfluoroalkyl ether group in its side chain, and salts of polyoxyalkylene ether polymers having a perfluoroalkyl ether group in its side chain. Counter ions of salts in these fluorochemical surfactants are, for example, Li, Na, K, NH.sub.4, NH.sub.3CH.sub.2CH.sub.2OH, NH.sub.2(CH.sub.2CH.sub.2OH).sub.2, and NH(CH.sub.2CH.sub.2OH).sub.3.

[0061] Specific examples of the amphoteric surfactants include, but are not limited to, lauryl aminopropionic acid salts, lauryl dimethyl betaine, stearyl dimethyl betaine, and lauryl dihydroxyethyl betaine.

[0062] Specific examples of the nonionic surfactants include, but are not limited to, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkyl amines, polyoxyethylene alkyl amides, polyoxyethylene propylene block polymers, sorbitan aliphatic acid esters, polyoxyethylene sorbitan aliphatic acid esters, and adducts of acetylene alcohol with ethylene oxides.

[0063] Specific examples of the anionic surfactants include, but are not limited to, polyoxyethylene alkyl ether acetates, dodecyl benzene sulfonates, laurates, and polyoxyethylene alkyl ether sulfates.

[0064] These can be used alone or in combination.

[0065] The proportion of the surfactant in the pre-treatment fluid is not particularly limited and it can be suitably selected to suit a particular application. It is preferably from 0.001 to 5 percent by mass and more preferably from 0.05 to 5 percent by mass to achieve good wettability and discharging stability and enhance the image quality.

[0066] The defoaming agent has no particular limit. Examples include, but are not limited to silicon-based defoaming agents, polyether-based defoaming agents, and aliphatic acid ester-based defoaming agents. These can be used alone or in combination. Of these, silicone-based defoaming agents are preferable to enhance the ability of braking foams.

Preservatives and Fungicides

[0067] The preservatives and fungicides (preservative and antifungal agents) are not particularly limited. One specific example is 1,2-benzisothiazoline-3-one.

Corrosion Inhibitor

[0068] The corrosion inhibitor has no particular limit. Specific examples include, but are not limited to, acid sulfites and sodium thiosulfates.

Ink

[0069] Next, the aqueous pigment ink for use in the present disclosure is described. The aqueous pigment ink used in the present disclosure contains at least water, a pigment, and an organic solvent. Additionally, the aqueous pigment ink may simply be referred to as ink in the following description.

Pigment

[0070] The pigment includes an inorganic pigment or organic pigment. These can be used alone or in combination. Mixed crystal can also be used as the coloring material.

[0071] Examples of the pigments include, but are not limited to, black pigments, yellow pigments, magenta pigments, cyan pigments, white pigments, green pigments, orange pigments, and gloss or metallic pigments of gold, silver, and others.

[0072] Carbon black available from known methods such as contact methods, furnace methods, and thermal methods can be used as the inorganic pigment in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow.

[0073] Specific examples of the organic pigments include, but are not limited to, 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 type chelates and acid dye type chelates), nitro pigments, nitroso pigments, and aniline black. Of these pigments, pigments with high affinity with solvents are preferable. Hollow resin particles and hollow inorganic particles can also be used.

[0074] Specific examples of the pigments for black include, but are not limited to, carbon black (C.I. Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, metals such as copper, iron (C.I. Pigment Black 11), and titanium oxide, and organic pigments such as aniline black (C.I. Pigment Black 1).

[0075] Specific examples of the pigments for color include, but are not limited to, C.I. 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, and 213; C.I. Pigment Orange 5, 13, 16, 17, 36, 43, and 51, C.I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48:2 {Permanent Red 2B(Ca)}, 48:3, 48:4,49:1, 52:2, 53:1, 57:1 (Brilliant Carmine 6B), 60:1, 63:1, 63:2, 64:1, 81, 83, 88, 101 (rouge), 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, and 264; C.I. Pigment Violet 1 (Rhodamine Lake), 3, 5:1, 16, 19, 23, and 38; C.I. Pigment Blue 1, 2, 15 (Phthalocyanine Blue), 15:1, 15:2, 15:3, 15:4, (Phthalocyanine Blue), 16, 17:1, 56, 60, and 63, C.I. Pigment Green 1, 4, 7, 8, 10, 17, 18, and 36.

[0076] The proportion of the pigment in the ink is preferably from 0.1 to 15 percent by mass and more preferably from 1 to 10 percent by mass to enhance the image density, fixability, and discharging stability.

[0077] To obtain the ink, the pigment is dispersed by, for example, preparing a self-dispersible pigment by introducing a hydrophilic functional group into the pigment, coating the surface of the pigment with resin, or using a dispersant.

[0078] To introduce a hydrophilic group into a pigment to make a pigment self-dispersible, it is possible to add a functional group such as a sulfone group and a carboxyl group to a pigment (e.g., carbon) to make the pigment dispersible in water.

[0079] One method of coating the surface of a pigment with resin and dispersing it is to encapsulate the pigment in microcapsules, allowing it to be dispersed in water. This microencapsulated pigment is also referred to as a resin-coated pigment. The resin-coated pigment particles in ink are not necessarily entirely coated with resin.

[0080] Pigment particles not partially or wholly covered with resin may be dispersed in ink unless such particles have an adverse impact.

[0081] One such method of using a dispersant for dispersing a pigment is to use a known dispersant of a small or large molecular weight, typically a surfactant.

[0082] As the dispersant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, or others can be selected depending on a pigment. Also, a nonionic surfactant, RT-100, available from TAKEMOTO OIL & FAT CO., LTD. and a formalin condensate of naphthalene sodium sulfonate are suitable as the dispersant. Those can be used alone or in combination.

Pigment Dispersion

[0083] It is possible to obtain an ink by mixing a coloring material with a material such as water and an organic solvent. It is also possible to mix a pigment with water, a dispersant, and other substances to prepare a pigment dispersion and thereafter mix the pigment dispersion with materials such as water and an organic solvent to manufacture ink.

[0084] The particle size of this pigment dispersion is adjusted by dispersing with water, a pigment, a pigment dispersant, and other optional components. It is good to use a dispersing device for dispersion.

[0085] The particle diameter of the pigment in the pigment dispersion has no particular limit. For example, when the maximum frequency is preferably from 20 to 500 nm and more preferably from 20 to 150 nm in the maximum number conversion, dispersion stability of the pigment is enhanced and discharging stability and the image quality such as image density are also improved. The particle diameter of a pigment can be analyzed using a particle size analyzer (Nanotrac Wave-UT151, available from MicrotracBEL Corp).

[0086] The proportion of the pigment in the pigment dispersion is not particularly limited and can be suitably selected to suit a particular application. It is preferably from 0.1 to 50 percent by mass and more preferably from 0.1 to 30 percent by mass to achieve good discharging stability and high image density.

[0087] It is preferable that the pigment dispersion be filtered with an instrument such as filter

Organic Solvent

[0088] The ink of the present disclosure contains an organic solvent, and the organic solvent contained in the ink may have the same composition as the organic solvent contained in the pre-treatment fluid. For example, the type and amount of the organic solvent contained in the ink may be the same as the type and amount of the organic solvent contained in the pre-treatment fluid.

Resin

[0089] The ink of the present disclosure preferably contains a resin to ensure high friction fastness.

[0090] The resin in the present disclosure may be added to the ink in any form; however, it is preferably included in a state where resin particles are dispersed in the ink composition.

[0091] The resin particles generally bind together as water, the main solvent in aqueous ink, or a water-soluble organic solvent in the ink evaporates or penetrates, thereby promoting the fixing of the pigment onto a recording medium.

[0092] The type of the resin contained in the ink has no particular limit and can be suitably selected to suit to a particular application. It includes, but are not limited to, urethane resins, polyester resins, acrylic-based resins, vinyl acetate-based resins, styrene-based resins, butadiene-based resins, styrene-butadiene-based resins, vinylchloride-based resins, acrylic styrene-based resins, and acrylic silicone-based resins.

[0093] Resin particles formed of these resins may be used. It is possible to obtain an ink by mixing a resin emulsion in which such resin particles are dispersed in water as a dispersion medium with materials such as a coloring material and an organic solvent. The resin particle can be synthesized or procured. These resins can be used alone or two or more types of the resin particles.

[0094] The volume average particle diameter of the resin particle is not particularly limited and can be suitably selected to suit to a particular application. The volume average particle diameter is preferably from 10 to 1,000 nm, more preferably from 10 to 200 nm, and particularly preferably from 10 to 100 nm to achieve good fixability and image robustness. The volume average particle diameter can be measured by using a device such as a particle size analyzer (Nanotrac Wave-UT151, available from MicrotracBEL Corp.).

[0095] The proportion of the resin is not particularly limited and can be suitably selected to suit to a particular application. It is preferably from 1 to 30 percent by mass and more preferably from 5 to 20 percent by mass to the entire ink to ensure fixability and storage stability of the ink.

Additive

[0096] The ink of the present disclosure, like the pre-treatment fluid, may additionally contain a surfactant, defoaming agent, preservative and antifungal agent, and corrosion inhibitor. The types and amounts of these additives that can be used are the same as those described for the pre-treatment fluid described above.

[0097] Therefore, a detailed description is omitted here.

Property of Ink

[0098] Properties of the ink are not particularly limited and they can be suitably selected to suit to a particular application. The ink preferably has properties, such as viscosity, surface tension, and pH, in the following ranges.

[0099] The ink preferably has a viscosity of from 5 to 30 mPa.Math.s and more preferably from 5 to 25 mPa.Math.s at 25 degrees Celsius to enhance the print density and text quality and achieve good dischargeability. Viscosity can be measured with equipment such as a rotatory viscometer, RE-80L, available from TOKI SANGYO CO., LTD. The measuring conditions are as follows: [0100] Standard cone rotor (1 34R24) [0101] Sample liquid amount: 1.2 mL [0102] Rate of rotations: 50 rotations per minute (rpm) [0103] 25 degrees Celsius [0104] Measuring time: three minutes.

[0105] The surface tension of the ink is preferably at most 35 mN/m and more preferably at most 32 mN/m at 25 degrees Celsius because the ink suitably levels on a recording medium and the ink dries in a short time.

[0106] pH of the ink is preferably from 7 to 12 and more preferably from 8 to 11 to prevent corrosion of the metal material in contact with liquid.

Post-Treatment Fluid

[0107] The post-treatment fluid is described next. In the present disclosure, a post-treatment fluid is used after the ink is applied, for the purpose of enhancing color development and improving friction fastness. The post-treatment fluid used in the present disclosure contains cationic resin particles, and may further contain water and other materials.

Cationic Resin Particle

[0108] The cationic resin particles can quickly aggregate when applied onto the previously applied ink, and remain on the surface to form a coating layer. This layer formation contributes to improve color development and friction fastness.

[0109] The cationic resin particles contained in the post-treatment fluid are preferably added as a resin emulsion in which the resin particles are dispersed in water as the dispersion medium, and are preferably of the self-emulsifying type.

[0110] The cationic component of the cationic resin is not particularly limited, but it is preferably a quaternary ammonium salt.

[0111] The cationic resin particles are preferably acrylic resin or urethane resin. The resin particle can be synthesized or procured. These resins can be used alone or two or more types of the resin particles.

[0112] The method of synthesizing cationic resin particles is not particularly limited, and known synthesis methods can be used. For example, the following methods may be used.

Cationic Urethane Resin Particles

[0113] One example of the production of cationic urethane resin particles will be described. Cationic urethane resin particles can be produced from a polyol, a polyisocyanate, and a tertiary amine-containing polyol. For example, a polyol, a polyisocyanate, and a separately prepared tertiary amine-containing polyol are reacted in a solvent or under solvent-free conditions to produce a urethane prepolymer having isocyanate groups at its ends. Subsequently, the urethane prepolymer is chain-extended using a polyamine to prepare a liquid dispersion of urethane resin particles. Then the tertiary amine groups in the liquid dispersion of urethane resin particle are neutralized with an acid or quaternized with a quaternizing agent. Through this process, cationic resin particles of the urethane resin type can be produced.

[0114] As another example of the production method, a polyol, a polyisocyanate, and a tertiary amine-containing polyol are reacted in a solvent or under solvent-free conditions to prepare a polyurethane. The tertiary amine groups in the resulting polyurethane may then be neutralized with an acid or quaternized with a quaternizing agent.

[0115] The tertiary amine-containing polyol can be prepared by the following method.

[0116] First, a compound (described later) having two epoxy groups per molecule is combined with a secondary amine in a ratio of one equivalent of NH groups to one equivalent of epoxy groups. These components are then subjected to a ring-opening addition reaction at approximately 20 degrees Celsius or under heating, to produce the tertiary amine-containing polyol.

[0117] The compounds having two epoxy groups per molecule include, but are not limited to, ethylene glycol diglycidyl ether, 1,2-propanediol diglycidyl ether, 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 3-methyl-1,5-pentanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polybutadiene glycol diglycidyl ether, 1,4-cyclohexanediol diglycidyl ether, 2,2-bis(4-hydroxycyclohexyl)propane (hydrogenated bisphenol A) diglycidyl ether, and isomer mixtures of hydrogenated dihydroxydiphenylmethane (hydrogenated bisphenol F) diglycidyl ether.

[0118] Specific examples of acids for neutralizing the tertiary amino group in the polyurethane resin particle liquid dispersion or the tertiary amino group in the polyurethane include, but are not limited to, one or more of 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, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, and tetrahydrophthalic acid; organic sulfonic acids such as sulfonic acid, p-toluenesulfonic acid, and methanesulfonic acid; and inorganic acids such as phosphoric acid, boric acid, hypophosphorous acid, hydrochloric acid, sulfuric acid, and nitric acid.

[0119] Specific examples of quaternizing agents for quaternizing the tertiary amino group in the polyurethane resin particle dispersion or the tertiary amino group in the polyurethane include, but are not limited to, one or more of dialkyl sulfates such as dimethyl sulfate and diethyl sulfate; alkyl or aryl sulfonate methyl compounds such as methyl methanesulfonate and methyl p-toluenesulfonate; epoxides 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.

Cationic Acrylic Resin Particle

[0120] One example of the methods of producing cationic acrylic resin particles is described below.

[0121] Cationic acrylic resin particles may be produced, for example, by emulsion polymerization of vinyl monomers such as (meth)acrylic monomers, styrene, or -methylstyrene using a cationic emulsifier; by emulsion polymerization of vinyl monomers using a polymer containing cationic groups as a protective colloid; or by inverse emulsion polymerization of cationic water-soluble monomers.

[0122] The term (meth)acrylic refers to either acrylic or its corresponding methacrylic compound.

[0123] Cationic acrylic resin particles may also be produced from the aforementioned materials by employing a cationic surfactant as an emulsification stabilizer. Specific examples of the cationic surfactants include, but are not limited to, laurylamine salts, stearyltrimethylenediamine salts, octadecylamine salts, laurylpyridinium chloride, stearylammonium chloride, dioleylammonium chloride, and octylbenzyldimethylammonium chloride.

[0124] Cationic acrylic resin particles may also be produced by performing emulsion polymerization using the above materials together with a nonionic surfactant, followed by post-addition of a cationic substance such as a cationic surfactant, polyoxyethylene alkylamine, or polyethyleneimine.

[0125] Cationic acrylic resin particles may also be produced by radical copolymerization of N-substituted aminoalkyl (meth)acrylates such as (meth)acrylic acid dimethylaminoethyl ester or (meth)acrylic acid diethylaminoethyl ester, or N-substituted aminoalkyl (meth)acrylamides such as (meth)acrylamide dimethylaminopropyl, with other (meth)acrylic monomers, styrene, or -methylstyrene, followed by quaternization with an alkylating agent.

[0126] In general, cationic acrylic resin particles are produced from the aforementioned materials by solution polymerization using a solvent or by emulsion polymerization using an emulsifier.

[0127] Specific examples of the alkylating agents used in the aforementioned solution or emulsion polymerization include, but are not limited to, octyl chloride, octyl bromide, dodecyl chloride, dodecyl bromide, tetradecyl chloride, tetradecyl bromide, hexadecyl chloride, and hexadecyl bromide.

[0128] Commercially available cationic resin particles may also be used as described above.

[0129] Specific examples of commercially available products include SUPERFLEX 620 and 650 (by Dai-ichi Kogyo Seiyaku), Hydran CP-7520 and CP-7610 (by DIC Corporation), Permarin UC-20 (by Sanyo Chemical Industries), Vinibran 2687 (by Nippon Shokubai), and Mobinyl M-9410 (by Japan Coating Resin).

[0130] The average particle diameter of the cationic resin particles is preferably 10 to 300 nm, more preferably 20 to 200 nm. This range suppresses penetration into the print layer, enhances the smoothness of the final coating layer, and particularly improves color development and abrasion resistance.

Solid Content

[0131] The solid content of the post-treatment fluid is preferably 1.0 to 20.0 percent by mass to the total mass of the post-treatment fluid, and more preferably 5.0 to 20.0 percent by mass. Within this range, sufficient color development can be obtained, the friction fastness can be improved, and a reduction in discharge reliability can be minimized. The amount of solids in the post-treatment fluid can be calculated by dropping 1 g of the post-treatment fluid into an aluminum cup, drying it at 120 degrees Celsius for 5 hours to volatilize the volatile components, and calculating the difference in weight before and after drying. Drying only needs to remove the volatile components, and from the standpoint of improving measurement accuracy, vacuum drying is preferred.

[0132] When vacuum drying, a vacuum level of 0.1 MPa is preferred.

Property of Post-Treatment Fluid

[0133] The properties of the post-treatment fluid are not particularly limited and can be suitably selected to suit to a particular application. To more effectively achieve the advantages of the present disclosure, it is beneficial to sufficiently reduce the penetration of the post-treatment fluid into the print layer. From this perspective, the viscosity of the post-treatment fluid at 25 degrees Celsius is preferably at least 8.0 cP, and from the standpoint of achieving stable discharge performance, it is preferably at most 25.0 cP and more preferably at most 15.0 cP. From the perspective of improving discharge properties, the viscosity of the post-treatment fluid at 25 degrees Celsius is preferably 8.0 to 11.0 cP. Note that 1 cP=1 mPa-s.

[0134] Other physical properties, such as surface tension, are not particularly limited and may be adjusted as appropriate.

Fluid Applying Apparatus and Fluid applying Method

[0135] The fluid applying apparatus of the present disclosure includes a pre-treatment fluid applying device for applying the pre-treatment fluid to a substrate, an ink applying device for applying the aqueous pigment ink to the substrate, and a post-treatment fluid applying device for applying the post-treatment fluid to the substrate.

[0136] The fluid applying method of the present disclosure includes applying the pre-treatment fluid to a substrate, applying the aqueous pigment ink to the substrate after the application of the pre-treatment fluid, and applying the post-treatment fluid to the substrate after the aqueous pigment ink application.

[0137] The apparatus of the present disclosure is capable of applying the pre-treatment fluid, ink, and post-treatment fluid to the substrate, as well as other optional various treatment fluids. The method of the present disclosure is executed for printing with this apparatus. According to the apparatus and the method of the present disclosure, excellent image density and high friction fastness can be obtained.

[0138] The apparatus of the present disclosure may be, for example, a printing apparatus, image forming apparatus, recording apparatus, printing device, or printer. The method of the present disclosure may be, for example, a printing method, image forming method, recording method, printing method, or print method. The method of the present disclosure can be suitably performed using the apparatus of the present disclosure.

[0139] The method of the present disclosure applies the pre-treatment fluid, the aqueous pigment ink, and the post-treatment fluid in this order onto a substrate. The pre-treatment fluid applying step may be referred to as the first step, the ink applying step as the second step, and the post-treatment fluid applying step as the third step. The aqueous pigment ink may simply be referred to as ink.

[0140] The substrate refers to a material onto which the pre-treatment fluid, ink, post-treatment fluid, and other optional various treatment fluids can be temporarily deposited. The substrate may be appropriately selected, with fabric being preferred.

[0141] Examples of the fabric used in the present disclosure include woven fabrics, knitted fabrics, and non-woven fabrics. Fibers used to form the fabric include, but are not limited to, natural fibers such as cotton, rayon, hemp, silk, and wool, semi-synthetic fibers such as acetate and triacetate, and synthetic fibers such as polyester, polyamide, and acrylic.

[0142] The terms of image forming, recording, and printing in the present disclosure represent the same meaning.

[0143] Also, recording media, printing media, media, printed product (matter), and substrates have the same meaning in the present disclosure unless otherwise specified.

[0144] In addition, the apparatus and the method of the present disclosure are not limited to those for producing meaningful visible images such as text and figures with ink. Apparatuses and devices for creating patterns like geometric design and 3D images are included.

Pre-Treatment Fluid Applying Step and Pre-Treatment Fluid Applying Device

[0145] In the pre-treatment fluid applying step, the pre-treatment fluid is applied to a substrate.

[0146] The pre-treatment fluid applying device applies the pre-treatment fluid to a substrate.

[0147] The pre-treatment fluid applying step is suitably executed by the pre-treatment fluid applying device.

[0148] The method of applying the pre-treatment is not particularly limited and can be suitably selected to suit to a particular application. The pre-treatment fluid can be applied by one of known methods.

[0149] Specific examples of applying the pre-treatment fluid include, but are not limited to, dipping, spraying, inkjetting, 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, micro gravure coating, reverse roll coating, four roll coating. five roll coating, dip coating, curtain coating, slide coating, and die coating.

[0150] In the dipping method, the pre-treatment fluid is applied to immerse the substrate in the fluid. In the spraying method, the pre-treatment fluid is sprayed onto a substrate using equipment such as a spray device. In the inkjet method, the pre-treatment fluid is discharged onto a substrate by inkjetting. In the roll coating method, the pre-treatment fluid is applied to a substrate using equipment such as a roll coater.

[0151] Among these, the dipping method, roll coating method, and spraying method are preferred in view of their simple equipment configuration and the ability to quickly apply the pre-treatment fluid. The inkjet method is also preferred because it allows the pre-treatment fluid to be applied only to are regions where ink will be applied, enables uniform application in small amounts, and reduces cost. In the inkjet method, either a serial type or a line type may be used.

[0152] The amount of pre-treatment fluid applied per unit area of the substrate (also referred to as coating amount) is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of achieving both sufficient color development and drying performance of the ink on the substrate, the amount is preferably 5 to 500 g/m.sup.2, and more preferably 5 to 300 g/m.sup.2. An amount of at least 5 g/m.sup.2 is preferred because it provides ink aggregation functionality, reduces ink penetration into a substrate, and enables the formation of high-quality images without bleeding. An amount of at most 500 g/m.sup.2 is preferred because it prevents the amount of applied volatile components from becoming excessive, thereby improving drying performance and, for example, preventing the pressing time required for drying printed matter from becoming too long.

Ink Applying Step and Ink Applying Device

[0153] In the ink applying step, the ink is applied to a substrate and may be applied to a region where the pre-treatment fluid has been applied.

[0154] The ink applying device applies ink to a substrate and may apply ink to a region where the pre-treatment fluid has been applied.

[0155] The ink applying step is preferably carried out by the ink applying device.

[0156] The method of applying the ink can be appropriately selected; however, a method of discharging by an inkjet system is preferable. When ink is discharged by inkjetting, the equipment configuration is simple, ink is applied quickly, and the ink can also be applied selectively to the desired locations, resulting in cost reduction.

[0157] It is preferable that the aqueous pigment ink (ink) and the post-treatment fluid be discharged to a substrate by inkjetting. That is, the ink applying device preferably discharges an aqueous pigment ink, and the post-treatment fluid applying device preferably discharges the post-treatment fluid. Also, in the ink applying process, the aqueous pigment ink is discharged by inkjetting, and, in the post-treatment fluid applying process, the post-treatment fluid is discharged by inkjeting. In this case, not only can a high-quality image be formed, but the post-treatment fluid can also be selectively applied to the areas where ink is applied, allowing for uniform application of a small amount and resulting in cost reduction.

[0158] The type of ink to be applied is not particularly limited and may be appropriately selected. A single type of ink may be used, or two or more types may be used.

[0159] The application amount of ink per unit area of the substrate is not particularly limited and may be appropriately selected according to a particular application. From the viewpoint of achieving both sufficient color development and drying performance of the ink on fabric, the amount is preferably 5 to 50 g/m.sup.2, and more preferably 5 to 30 g/m.sup.2. An amount of at least 5 g/m.sup.2 is preferable because it provides color development sufficient for practical use. An amount of at most 50 g/m.sup.2 is preferable because the amount of volatile components applied does not become excessive, thereby improving drying properties and, for example, preventing the pressing time required for drying the printed matter from becoming too long.

Processing Fluid Applying Step and Processing Fluid Applying Device

[0160] In the post-treatment fluid applying step, the post-treatment fluid is applied and the post-treatment fluid may be applied to the region where ink has been applied.

[0161] The post-treatment fluid applying device applies a post-treatment fluid and may apply the post-treatment fluid to the post-treatment fluid applying device applies the region where ink has been applied.

[0162] The post-treatment fluid applying step is preferably carried out by the post-treatment fluid applying device.

[0163] The method of applying the post-treatment fluid is not particularly limited and may be appropriately selected according to a particular application. The same methods as those used for the pre-treatment fluid may be employed. Accordingly, detailed explanation is omitted, but immersion, roll coating, and spraying methods are preferred, and the inkjet method is more preferred.

[0164] The amount of the post-treatment fluid applied per unit area of the substrate is not particularly limited and may be appropriately selected according to a particular application. From the viewpoint of achieving both sufficient color development and drying properties of the ink on a substrate, it is preferably from 5 to 50 g/m.sup.2, and more preferably from 5 to 30 g/m.sup.2. An amount of at least 5 g/m.sup.2 is preferable because it tends to form a continuous transparent resin film without penetrating into the printed layer. An amount of at most 50 g/m.sup.2 is preferred because it is less likely to impair the texture of the printed matter.

[0165] In the printing method of the present disclosure, the ink applying step and the post-treatment fluid applying step are carried out separately, so the ratio between the amount of ink applied and the amount of post-treatment fluid applied can be freely adjusted. Adjusting the ratio between the amount of ink and the post-treatment fluid allows control over their effects, enabling a balanced trade-off between fastness and image quality (e.g., density and chroma). Moreover, the ratio of ink applied and post-treatment fluid applied can be adjusted, which leads to effective utilization of the post-treatment fluid as a treatment fluid regardless of the mixing stability between components contained in the ink and those in the post-treatment fluid.

[0166] For this reason, it is preferable that the post-treatment fluid applying step include a step of adjusting an amount of the post-treatment fluid applied. Adjusting the amount of the post-treatment fluid applied and applying the post-treatment fluid in the amount adjusted leads to the control over the ratio between the amount of ink applied and the amount of post-treatment fluid applied, thus achieving the above-described effects such as adjusting the balance between fastness and image quality (such as density and chroma).

[0167] In the step of adjusting the amount, for example, a control device 160 selects the amount applied, and a post-treatment fluid applying control unit 163 controls the post-treatment fluid applying device 130 so that the selected amount is applied. The adjustment of the amount of the post-treatment fluid applied is not particularly limited and may be performed for each job or for each individual substrate. The amount applied may also be determined by the control unit based on input information from a user.

[0168] The ratio between the amount of the ink and the amount of the post-treatment may be appropriately selected. Although not particularly limited, for example, if improved fixability is desired, the amount of post-treatment fluid may be increased. It is possible to increase the amount of post-treatment fluid, enhancing ink fixation and the friction fastness. Conversely, to preserve the color image quality provided by the aqueous pigment ink, the amount of post-treatment fluid may be reduced.

Heat Drying Step and Heat Drying Device

[0169] The fluid applying method of the present disclosure may include a heat drying step, and preferably executes this step after the post-treatment fluid applying step. If the heat drying step is performed after applying the post-treatment fluid, friction fastness can be improved.

[0170] The fluid applying device of the present disclosure may include a heat drying device, and preferably performs heat drying using this heat drying device after applying the post-treatment fluid. When heat drying is performed after applying the post-treatment fluid, friction fastness can be improved.

[0171] The heat drying step dries one or more fluids selected from the pre-treatment fluid, ink, and post-treatment fluid applied to a substrate, and is carried out by the heat drying device.

[0172] There are no particular limitations on the method of heat drying, and an appropriate method may be selected depending on the intended purpose.

[0173] Examples include, but are not limited to, hot air drying, radiant heating, conductive heating, high-frequency drying, microwave drying, heat pressing, and fixation rollers. These can be used alone or in combination. Either contact or non-contact types may be used. From the perspective of improving fastness and shortening heating time, hot air drying and heat pressing are preferred. In the case of hot air drying or heat pressing, the volatile components in the ink can be efficiently evaporated after the pre-treatment fluid, ink, and post-treatment fluid have been applied to a substrate, thereby improving the fastness of the printed matter (printed product).

[0174] The term heat drying process and heat drying device is used herein because this step and device encompass both heating and drying without distinction. When the substrate is heated and dried at a temperature exceeding natural drying conditions, it is considered to fall under heat drying. Although the temperature exceeding natural drying conditions may vary depending on factors such as the operating environment of the apparatus, it is, for example, 35 degrees Celsius or higher.

[0175] There are no particular limitations on the temperature for heat drying, but it is preferably 100 to 200 degrees Celsius, and more preferably 100 to 180 degrees Celsius. Since thermal shrinkage, yellowing, and color transfer may occur depending on the substrate, the heat drying temperature is preferably selected as appropriate.

[0176] There are no particular limitations on the heat drying time either, and it may be, for example, one minute or longer.

[0177] It is preferable that the fluid applying method of the present disclosure do not include a heat drying process between the pre-treatment fluid applying step and the post-treatment fluid applying step. That is, no heat drying is performed after applying the pre-treatment fluid and before applying the ink, and no heat drying is performed after applying the ink and before applying the post-treatment fluid.

[0178] In other words, although a heat drying step may be included between the first step and the second step or between the second step and the third step, it is preferable not to include a heat drying step between these steps in view of promoting the reactivity between the pre-treatment fluid and the ink, or between the ink and the post-treatment fluid.

[0179] Not including a heat drying step between the pre-treatment fluid applying step and the post-treatment fluid applying step, image density can be improved, and friction fastness can be enhanced. The reactivity between the pre-treatment fluid and the ink increases, resulting in higher image density and images free from bleeding. Moreover, by not including a heat drying step after the ink applying step, the occurrence of voids between the print layer and the post-treatment fluid layer can be prevented, thereby facilitating improved fastness.

[0180] The method of the present disclosure may omit the heat drying process, and the fluid applying device of the present disclosure may be free of any heat drying device. If the apparatus of the present disclosure does not include a heat drying device and the method of the present disclosure does not include a heat drying step, the device can be advantageously downsized.

Pressure Applying Step and Pressure Applying Device

[0181] In the method of the present disclosure, it is preferable to perform a pressurizing steps on the area to which the pre-treatment fluid has been applied, after the pre-treatment fluid applying step and before the ink applying step.

[0182] It is preferable that the apparatus of the present disclosure include a pressurizing device between the pre-treatment fluid applying device and the ink applying device 120. The pressurizing device pressurizes the area to which the pre-treatment fluid has been applied, after the pre-treatment fluid has been applied to the substrate and before the ink is applied.

[0183] Performing the pressurizing process using the pressurizing device allows for even spreading of the pre-treatment fluid, thereby preventing blotchiness. Furthermore, when the substrate is a fabric, the pressurizing device can smooth the surface by flattening the fiber fuzz. This allows for uniformity in ink landing positions and penetration, thereby improving the image quality.

Storage Device

[0184] The fluid applying device of the present disclosure may include a storage device for storing each fluid. The storage device may be, for example, a pre-treatment fluid container, an ink container, or a post-treatment fluid container. One specific example is an ink cartridge.

Example of Fluid Applying Apparatus and Fluid Applying Method

[0185] One example of the fluid applying apparatus of the present disclosure and the fluid applying method of the present disclosure will now be described with reference to the drawings.

[0186] FIG. 1 is a schematic diagram illustrating an example of the apparatus of the present disclosure. FIG. 2 is a schematic diagram illustrating an example of the control device of the apparatus illustrated in FIG. 1. FIG. 3 is a flowchart illustrating an example of the operation of the apparatus illustrated in FIG. 1. The apparatus and method are described using a printing device and a printing method as examples.

[0187] In the printing method of the present disclosure, the pre-treatment fluid applying step, the ink applying step, and the post-treatment fluid applying step may be performed using the same printing device or separate, independent equipment (e.g., printing devices).

[0188] A printing device 100 includes a pre-treatment fluid applying device 110, an ink applying device 120, a post-treatment fluid applying device 130, and a control device 160. It may furthermore optionally include a heat drying device 140, a conveying device 150, a storage unit (memory) 170, and other members.

[0189] The pre-treatment fluid applying device 110 applies the pre-treatment fluid to a substrate M. The method of applying the pre-treatment fluid is not particularly limited and may use the methods described above. In the pre-treatment fluid applying device 110 in this example, a roll coating method is used.

[0190] The ink applying device 120 applies an aqueous pigment ink to the substrate M. The method of applying the ink is not particularly limited and may use the methods described above. In the ink applying device 120 in this example, inkjetting is used.

[0191] The post-treatment fluid applying device 130 applies the aqueous pigment ink to the substrate M. The method of applying the post-treatment fluid is not particularly limited and may use the methods described above. In the post-treatment fluid applying device 130 in this example, inkjetting is used.

[0192] The control device 160 is, for example, a central processing unit (CPU) or a read only memory (ROM), providing instructions to the storage unit 170 and respective control units. The control device 160 also includes a random access memory (RAM), host interface (I/F), input/output (I/O) unit, non-volatile random access memory (NVRM), and application specific integrated circuit (ASIC).

[0193] The storage unit 170 is, for example, a hard disk drive (HDD) and retains data such as images to be printed.

[0194] The control device 160 includes, for example, a pre-treatment fluid applying control unit 161, an ink applying control unit 162, and a post-treatment fluid applying control unit 163. The pre-treatment fluid applying control unit 161 controls the driving of the pre-treatment fluid applying device 110. The ink applying control unit 162 controls the driving of the ink applying device 120. The post-treatment fluid applying control unit 163 controls the driving of the post-treatment fluid applying device 130.

[0195] The printing device 100 may also include a unit for applying ink other than aqueous pigment ink.

[0196] In such a case, the ink applying control unit 162 also controls the driving of the unit that applies ink other than aqueous pigment ink. The ink other than aqueous pigment ink is not particularly limited, and one example is clear ink.

[0197] The printing device 100 may include the heat drying device 140 that heats and dries the print surface (front surface) and the reverse surface of the substrate M to which the pre-treatment fluid, ink, and post-treatment fluid have been applied. The heat drying device 140 may be omitted. Optionally, the substrate M can be heated and dried after other liquids containing the post-treatment fluid are applied and before and after applying each fluid.

[0198] The conveying device 150 conveys the substrate M. There is no specific limitation to the conveying device 150 as long as it can convey the substrate M. A conveyance belt or a platen can be used as the conveying device 150. The conveying device 150 can be omitted.

[0199] The printing device 100 may furthermore include a fixing unit for heat-fixing an image formed on the substrate M. The fixing unit is not particularly limited. The fixing unit can be a fixing roller or a heat press.

[0200] The apparatus of the present disclosure can also be used as a desktop printer. When used as a desktop printer, for example, it is preferable that the pre-treatment fluid, ink, and post-treatment fluid be discharged by an inkjet printing method. As one mode of the pre-treatment fluid applying device and post-treatment fluid applying device, an inkjet printing method may be used, similar to that used for typical color inks such as black (K), cyan (C), magenta (M), and yellow (Y). When using such a mode employing inkjet printing, for example, a fluid containing unit containing the pre-treatment fluid, ink, and post-treatment fluid, along with a fluid discharge head, is added.

[0201] One example of fluid application will now be described with reference to FIG. 3. One example of image formation-fluid application-is described. An image forming apparatus is described as an example of the fluid applying device.

[0202] On receiving an instruction of starting image forming, the image forming apparatus initiates an image forming operation.

[0203] In Step S1, the image forming apparatus conveys the substrate M by the conveying device 150 and the pre-treatment fluid applying device 110 applies the pre-treatment fluid to the substrate M.

[0204] At this time, the pre-treatment fluid applying device 110 may apply the pre-treatment fluid only to the areas where an image is to be formed, or to the entire surface of the substrate. When the pre-treatment fluid is applied only to the image-forming areas, the application range may be determined in accordance with instructions from the pre-treatment fluid applying control unit 161, and the pre-treatment fluid applying device 110 applies the pre-treatment fluid within that range. When the pre-treatment fluid is applied to the entire surface of the substrate, the pre-treatment fluid applying device 110 applies the pre-treatment fluid to the entire surface in accordance with instructions from the pre-treatment fluid applying control unit 161.

[0205] In step S2, ink is applied to the substrate M, which has been conveyed by the conveying device 150 and to which the pre-treatment fluid has been applied, by the ink applying device 120. At this time, the ink applying device 120 may apply ink only to the areas where the pre-treatment fluid has been applied, or to the entire surface of the substrate. However, in the present disclosure, it is preferable that the ink applying device 120 apply the ink to the areas where the pre-treatment fluid has been applied.

[0206] When the ink is applied only to the areas where the pre-treatment fluid has been applied, the application range may be determined in accordance with instructions from the ink applying control unit 162, and the ink applying device 120 applies ink within that range. When the ink is applied to the entire surface of the substrate, the ink applying device 120 applies the ink to the entire surface in accordance with instructions from the ink applying control unit 162.

[0207] In step S3, the post-treatment fluid is applied to the substrate M, which has been conveyed by the conveying device 150 and to which the pre-treatment fluid and the ink have been applied, by the post-treatment fluid applying device 130. At this time, the post-treatment fluid applying device 130 may apply the post-treatment fluid only to the areas where the pre-treatment fluid and the ink have been applied, or to the entire surface of the substrate. However, in the present disclosure, it is preferable that the post-treatment fluid applying device 130 apply the post-treatment fluid to the areas where the pre-treatment fluid and ink have been applied.

[0208] When the post-treatment fluid is applied only to the image-forming areas, the discharge range may be determined in accordance with instructions from the post-treatment fluid applying control unit 163, and the post-treatment fluid applying device 130 applies the post-treatment fluid within that discharge range. When the post-treatment fluid is applied to the entire surface of the substrate, the post-treatment fluid applying device 130 applies the post-treatment fluid to the entire surface in accordance with instructions from the post-treatment fluid applying control unit 163.

[0209] In step S3, the amount of the post-treatment fluid applied may be adjusted. In this amount adjustment step, the ratio between the applied amount of the ink and the applied amount of the post-treatment fluid can be adjusted.

[0210] The image forming apparatus may optionally include a sensor for recognizing the position and place of the substrate. By providing sensors for detecting the position or location of the substrate, the pre-treatment fluid applying device 110, ink applying device 120, and post-treatment fluid applying device 130 can more efficiently apply the pre-treatment fluid, ink, and post-treatment fluid to the substrate in steps S1, S2, and S3, respectively.

[0211] After Step S3, a drying step may be performed in which the substrate to which the pre-treatment fluid, ink, and post-treatment fluid have been applied is conveyed by the conveying device 150 to the heat drying device 140 and dried. The heat drying device 140 and the heat drying step are not indispensable but optional in the fluid applying device and fluid applying method of the present disclosure.

[0212] If the heating and drying process is not performed, the user may manually perform the heat drying using separate heat drying equipment. When the heat drying step is performed, the heating drying time and temperature may be constant or may be adjusted according to the amounts of the pre-treatment fluid, ink, and post-treatment fluid applied. It is more preferable to adjust them according to the amounts of the pre-treatment fluid, ink, and post-treatment fluid applied.

[0213] The image forming apparatus may include a sensor for recognizing the amounts of the pre-treatment fluid, ink, and post-treatment fluid applied to the substrate. With this sensor, the heating and drying time and temperature can be set or adjusted according to the amounts of the pre-treatment fluid, ink, and post-treatment fluid applied to the recording medium applied. Accordingly, the heat drying device 140 can heat and dry the substrate more efficiently.

[0214] The sensor may recognize the amount of the pre-treatment fluid, ink, and post-treatment fluid applied to the substrate based on the amount of the fluid actually attached to the substrate. Alternatively, it can recognize the amount discharged from each applying device (unit) to the substrate by measuring.

[0215] After the substrate is subjected to heating and drying as necessary, the image formation by the image forming apparatus is completed. Additionally, the step may include removing the substrate from the image forming apparatus or conveying the substrate.

Another Example of Apparatus and Method

[0216] Next, another example of the apparatus for applying the ink set and the method of applying the ink set of the present disclosure will now be described.

[0217] FIG. 4 is a schematic diagram for explaining another example of the apparatus for applying the ink set of the present disclosure. The apparatus and method are described using a printing device and printing method as an example. The printing device 100 of this example includes a pressurizing unit 180 between the pre-treatment fluid applying device 110 and the ink applying device 120. The pressurizing unit 180 applies pressure to the region where the pre-treatment fluid has been applied after the pre-treatment fluid is applied to the substrate and before the ink is applied.

[0218] In this printing method, a pressurizing step is executed to apply pressure to the region where the pre-treatment fluid has been applied after the pre-treatment fluid application step and before the ink application step.

[0219] The pressurizing unit 180 may have a cylindrical or columnar shape such as a pressurizing roller, or may have a flat-plate shape in which the pressurizing area is a flat surface.

[0220] Performing the pressurizing process using the pressurizing unit 180 allows for even spreading of the pre-treatment fluid, thereby preventing blotchiness. In addition, when the substrate is a fabric, the pressurizing step using the pressurizing unit 180 can flatten and smooth the fibrous nap on the fabric surface. This allows for uniformity in ink landing positions and penetration, thereby improving the image quality.

[0221] Other examples of the apparatus and the method of the present disclosure will be described below.

[0222] The ink set of the present disclosure can be suitably used for various recording devices employing an inkjet printing method, such as printing devices, printers, facsimile machines, photocopiers, multifunction peripherals (serving as a printer, a facsimile machine, and a photocopier), and solid freeform fabrication devices (3D printers, additive manufacturing devices).

[0223] The apparatus may furthermore optionally include a device relating to feeding, conveying, and ejecting a printing medium and other devices referred to as a pre-treatment device and a post-treatment device in addition to the head portion for discharging an ink.

[0224] In addition, the apparatus includes both a serial type device with a movable fluid discharge head and a line type device with a fixed fluid discharge head, unless otherwise specified.

[0225] Furthermore, in addition to the desktop type, the apparatus includes a device capable of printing images on a wide recording medium having, for example, A0 size and a continuous printer capable of using continuous paper rolled in a roll-like form as a substrate.

[0226] The apparatus of this example is described using an example with reference to FIG. 5 and FIG. 6. FIG. 5 is a diagram illustrating a perspective view of the same apparatus. FIG. 6 is a diagram illustrating a perspective view of a tank. A printing device 400 of this example is a serial image forming device. The printing device 400 includes a mechanical unit 420 inside an exterior 401. Each ink accommodating unit (ink container) 411 of each tank 410 (410k, 410c, 410m, and 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is made of a packaging member such as aluminum laminate film. The ink accommodating unit 411 is housed in, for example, a plastic container housing unit 414 and L represents liquid contained in the ink accommodating unit 411. The tank 410 is used as an ink cartridge of each color.

[0227] A cartridge holder 404 is disposed on the rear side of the opening appearing when a cover 401c is opened. The tank 410 is detachably attached to the cartridge holder 404. This configuration enables each ink discharging outlet 413 of the tank 410 to communicate with a discharge head 434 for each color via a supplying tube 436 for each color so that the ink can be discharged from the discharge head 434 to a printing medium.

[0228] In this example, the apparatus may be provided not only with the discharge head 434 for discharging the ink, but also with a pre-treatment fluid discharge head for discharging the pre-treatment fluid and a post-treatment fluid discharge head for discharging the post-treatment fluid. The apparatus of this example may also be provided with a pre-treatment fluid container for storing the pre-treatment fluid, and the pre-treatment fluid is supplied from the pre-treatment fluid container to the pre-treatment fluid discharge head. Further, the apparatus of this example may be provided with a post-treatment fluid container for storing the post-treatment fluid, and the post-treatment fluid is supplied from the post-treatment fluid container to the post-treatment fluid discharge head. In this manner, the pre-treatment fluid, ink, and post-treatment fluid can also be applied to a substrate in this example of the apparatus.

Electrode Manufacturing Device

[0229] The apparatus (fluid applying device) according to the present disclosure also includes a manufacturing device for electrodes and electrochemical elements. The following is a description of an electrode manufacturing device.

[0230] FIG. 16 is a schematic diagram illustrating an example of the electrode manufacturing device according to embodiments of the present disclosure. The electrode manufacturing device manufactures electrodes including a layer containing an electrode material by discharging fluid compositions such as pre-treatment fluid, aqueous pigment ink, and post-treatment fluid using a head module that includes a fluid discharge head.

Device for Forming Layer Containing Electrode Material, Step for Forming Layer Containing Electrode Material

[0231] The discharge device provided in the electrode manufacturing device illustrated in FIG. 16 is a head module according to the embodiment of the present disclosure mentioned above. Discharging the fluid composition from the discharge head of the head module allows it to be applied to a target object, forming a fluid composition layer. There is no particular limitation on the target object (hereinafter also referred to as the discharge target) as long as it is a target on which a layer containing an electrode material is to be formed, and it may be appropriately selected according to a particular application. Examples of the target object include, but are not limited to, an electrode substrate (current collector), an active material layer, and a layer containing a solid electrode material. The target object may also be an electrode mixture layer containing an active material formed on an electrode substrate (current collector). The discharge device and discharge step may form a layer containing an electrode material by directly discharging a fluid composition onto the discharge target, provided that they are capable of forming a layer containing an electrode material on the discharge target. Alternatively, the discharge device and discharge process may form a layer containing an electrode material by indirectly discharging a fluid composition.

Other Optional Configuration and Other Optional Step

[0232] There are no particular limitations on other configurations included in the device for producing an electrode mixture layer, and such configurations may be appropriately selected according to a particular application. There are no particular limitations on other steps included in the method of producing an electrode mixture layer, and such steps may be appropriately selected according to a particular application. Examples of configurations and steps that may be included in the device and method of producing an electrode mixture layer include a heating device and a heating step.

Heating Device and Heating Step

[0233] The heating device included in the device for producing an electrode mixture layer heats the fluid composition discharged by the discharge device. The heating steps included in the method of producing an electrode mixture layer heats the fluid composition discharged in the discharge step. Heating the fluid composition results in drying the fluid composition layer.

Configuration for Forming Layer Containing Electrode Material by Direct Discharge of Fluid Composition

[0234] As an example of an electrode manufacturing device, an electrode manufacturing device that forms an electrode mixture layer containing an active material on an electrode substrate (current collector) will be described. As illustrated in FIG. 16, the electrode manufacturing device includes a discharge process device 210, which performs a discharge step that applies a fluid composition onto a print substrate 704 having a discharge target to form a fluid composition layer, and a heating process device 230, which performs a heating step that heats the fluid composition layer to obtain an electrode mixture layer.

[0235] The electrode manufacturing device includes a conveying unit 705 that conveys the print substrate 704. The conveying unit 705 conveys the print substrate 704 through the discharge process device 210 and a heating process device 230, in that order, at a predetermined speed. There are no particular limitations on the method of manufacturing the print substrate 704 having a discharge target such as an active material layer, and any known method may be appropriately selected. The discharge process device 210 includes a fluid discharge head 281a that performs an applying step for applying a fluid composition onto the print substrate 704, a storage container 281b that accommodates the fluid composition 707, and a supply tube 281c that supplies the fluid composition 707 stored in the storage container 281b to the fluid discharge head 281a.

[0236] In the discharge process device 210, the fluid composition 707 is discharged from the fluid discharge head 281a and applied onto the print substrate 704, thereby forming a thin film of the fluid composition layer. The storage container 281b may be configured to be integrated with or detachable from the electrode composite layer manufacturing device. Additionally, the storage container 281b may be designed to add materials to a container that is either integrated with or detachable from the electrode composite layer manufacturing device.

[0237] The storage container 281b and the supply tube 281c can be arbitrarily selected as long as the fluid composition 707 can be stably stored and supplied.

[0238] In the heating process device 230, a solvent removal step is performed to remove the solvent remaining in the fluid composition layer by heating. Specifically, the solvent remaining in the fluid composition layer is heated and dried by the heating device 703 of the heating process device 230, thereby being removed from the fluid composition layer. As a result, the electrode mixture layer is formed. The solvent removal step in the heating process device 230 may also be carried out under reduced pressure.

[0239] There is no particular limitation on the heating device 703, and it can be appropriately selected according to a particular application.

[0240] For example, the heating device 703 may include a substrate heater, IR heater, or hot air heater.

[0241] The heating device 703 may also be a combination of at least two of the substrate heater, IR heater, and hot air heater. Further, the heating temperature and the heating time can be appropriately selected according to the boiling point of the solvent contained in the fluid composition 707 and the thickness of formed film.

[0242] The electrode manufacturing device according to an embodiment of the present disclosure makes it possible to discharge the fluid composition precisely onto the targeted area of the discharge object. The electrode composite layer can be suitably used, for example, as part of the configuration of an electrochemical device. There is no particular limitation on the configuration other than the electrode composite layer in the electrochemical device, and known configuration can be appropriately selected. For example, the configuration other than the electrode composite layer include, but is not limited to, a positive electrode, a negative electrode, and a separator.

Example of Nozzle Surface Cleaning

[0243] Next, another example of the apparatus (fluid applying device) and method (fluid applying method) of the present disclosure will now be described. This example of the fluid applying device includes one or more nozzle surface cleaning devices, and this example of the fluid applying method includes a nozzle surface cleaning step.

[0244] In this example, the ink applying device has a nozzle surface provided with nozzles that discharge the aqueous pigment ink, and the post-treatment fluid applying device has a nozzle surface provided with nozzles that discharge the post-treatment fluid.

[0245] The fluid applying device includes a nozzle surface cleaning device that cleans at least one of the nozzle surfaces of the ink applying device and the post-treatment fluid applying device, and the nozzle surface cleaning device has a wiping member that wipes liquid from the nozzle surface.

[0246] The fluid applying device with the nozzle surface cleaning device can keep the nozzle surface clean, making it easier to maintain good discharge performance. Inclusion of a nozzle surface cleaning step in the printing method facilitates maintenance of a clean nozzle surface and stable discharge performance.

[0247] FIG. 7 is a schematic diagram illustrating the fluid applying device of this example. The fluid applying device will be described using a printing device as an example. The printing device 100 of this example is an example of a serial-type inkjet recording device. The printing device 100 of this example includes inkjet recording modules 1a, 1b, 1c, and a substrate support member 3.

[0248] The inkjet recording modules 1a, 1b, and 1c each have a recording head that discharges fluid. In this example, the inkjet printing module 1a discharges the pre-treatment fluid, the inkjet printing module 1b discharges the ink, and the inkjet printing module 1c discharges the post-treatment fluid. When referring to the inkjet recording modules 1a, 1b, and 1c collectively without distinction, they may be called inkjet printing module1.

[0249] The substrate support member 3 holds a substrate 39 and moves to scan in the direction indicated by an arrow D2. The substrate support member 3 moves to scan beneath the recording heads of the inkjet recording modules 1a, 1b, and 1c. The inkjet recording modules discharge fluid onto the substrate 39 held by the substrate support member 3 to perform printing.

[0250] FIG. 8 is a schematic diagram illustrating an example of the inkjet printing module1.

[0251] The inkjet printing module1 is a liquid discharge device including a recording head 34 that includes a fluid discharge head that discharges droplets from nozzles, and a maintenance and recovery mechanism 81 for maintaining or recovering the fluid discharge head. The maintenance and recovery mechanism 81 includes a nozzle surface cleaning device 2 that cleans the nozzle surface of the fluid discharge head.

[0252] The inkjet printing module1 has a carriage 33. The carriage 33 is slidably supported in the main scanning direction by a main guide rod 31 and a sub sheet metal guide 32, which are guide members spanning the left and right side plates 21A and 21B of the printing device 100. The carriage 33 moves and scans in the direction indicated by arrow D1 (the carriage main scanning direction) via a timing belt driven by the main scanning motor.

[0253] The carriage 33 has recording heads 34a, 34b, 34c, and 34d (collectively recording head 34 when not distinguished) including fluid discharge heads that discharge inks of various colors such as yellow (Y), cyan (C), magenta (M), and black (K). The recording head 34 arranges nozzle rows, each having multiple nozzles, in the sub-scanning direction orthogonal to the main scanning direction (direction indicated by an arrow D2). The recording head 34 is mounted on the carriage 33 with the ink droplet discharge direction facing downward.

[0254] The carriage 33 is equipped with a supply pump unit and sub-tanks for supplying inks of each color corresponding to the recording heads 34. Inks of each color are replenished and supplied from ink cartridges 6 detachably mounted on a cartridge mounting section into the sub-tanks via supply tubes 35 by the supply pump unit.

[0255] When the inkjet printing module1 has multiple recording heads 34 (34a to 34d), the multiple recording heads 34 may be referred to as a head unit or the like. In the case of an inkjet printing module1 that discharges the pre-treatment fluid or post-treatment fluid, the recording head 34 it has may be either a single one or multiple. The same treatment fluid may be discharged from the multiple recording heads 34.

[0256] As illustrated in FIG. 8, maintenance and recovery mechanisms 81a and 81b are arranged in the non-printing areas on both sides of the scanning direction of the carriage 33 to maintain and recover the condition of the nozzles of the recording head 34. The maintenance and recovery mechanism 81a includes respective cap members (hereinafter referred to as caps) 82a, 82b, 82c, and 82d (collectively referred to as cap 82 when distinction is unnecessary) for capping the nozzle surfaces of the recording head 34. The maintenance and recovery mechanism 81b includes a wiping unit 83 that constitutes the nozzle surface cleaning device 2.

[0257] The maintenance and recovery mechanism 81a also includes a dummy droplet receiver for receiving droplets discharged during dummy discharge, which discharges droplets that do not contribute to recording in order to discharge thickened recording fluid, as well as a carriage lock for locking the carriage 33. Furthermore, on the lower side of the maintenance and recovery mechanism 81a, a fixed waste liquid tank that is not replaced is provided to collect waste liquid generated by maintenance and recovery operations, and on the lateral side of the maintenance and recovery mechanism 81a, a replaceable exchangeable waste liquid tank is provided.

[0258] As in this example, it is preferable that each inkjet printing module1 is equipped with its own nozzle surface cleaning device 2. In this case, even if different inks or treatment fluids are used for each inkjet printing module1, and cleaning operations are performed by the nozzle surface cleaning device 2, the components constituting the inks or treatment fluids do not mix. For example, when using liquids with different polarities such as treatment fluid and ink, if the same nozzle surface cleaning device is used, mixing of fluids may occur within the cleaning device or on the nozzle surface, causing reactions, aggregation, or precipitation of the fluid components, which may lead to discharge failures. On the other hand, according to this example, even when multiple liquids that cannot be mixed, such as the treatment fluid and aqueous pigment ink, or fluids that become unstable after mixing, are used, stable discharge can be maintained.

[0259] FIG. 9 is an example of a control block diagram of the fluid applying device of this example. The control device 160 controls the substrate support member 3, the inkjet printing module1, and others, using instructions from an operation panel 165, which includes a display, input panel, and speaker. The substrate support member 3 is controlled, for example, by the substrate conveying control unit. The conveyance of the substrate 39 may also be controlled using a substrate height detector or various sensor groups.

[0260] The control device 160 controls the recording head 34 via the inkjet printing control unit (IJ printing control unit), head control unit, and head driver of the inkjet printing module 1. In FIG. 9, a head unit is illustrated as multiple recording heads 34. The control device 160 also controls the fluid supply pump and solenoid valves via the supply system control unit. Additionally, the control device 160 controls the suction pump, cap, electromagnetic valves, and cleaning devices via the maintenance control unit. The cleaning devices include the nozzle surface cleaning device 2 and others. Moreover, the control device 160 controls the main scanning motor via the main scanning control unit. Controlling the main scanning motor allows control over the scanning direction of the carriage 33.

[0261] An example of printing in this example will be described.

[0262] The substrate support member 3 holds the substrate 39 at the initial position, moves to the print start position of the inkjet printing module1a, and stops. The printing device 100 moves the carriage 33 of the inkjet printing module lain the main scanning direction D1 while driving the recording head 34 according to the image signal. The inkjet printing module 1a discharges the pre-treatment fluid onto the substrate 39 intermittently conveyed in the D2 direction by the substrate support member 3. Upon receiving a print complete signal or a signal indicating that the trailing edge of the substrate 39 has reached the printing area, the printing apparatus ends the print operation of the inkjet printing module 1a and sends the substrate 39 to the inkjet printing module 1b.

[0263] The inkjet printing module1b discharges ink droplets onto the substrate 39 fixed and stopped by the substrate support member 3 to print one line, and after the substrate 39 is conveyed by a predetermined amount, prints the next line. Upon receiving a printing complete signal or a signal indicating that the trailing edge of the substrate 39 has reached the print area, the printing device 100 ends the recording operation of the inkjet printing module1b and sends the substrate 39 to the inkjet printing module1c.

[0264] The inkjet printing module1c discharges a post-treatment fluid onto the substrate 39 intermittently conveyed in the D2 direction by the substrate support member 3. Upon receiving a printing end signal or a signal indicating that the trailing edge of the substrate 39 has reached the print area, the printing operation of the inkjet printing module1c ends. When the printing operation ends, the substrate support member 3 returns to the initial position, making the substrate 39 ready for collection.

[0265] After the recording operation ends, a maintenance and recovery operation (hereinafter referred to as maintenance and recovery) is performed as necessary to maintain or restore the state of the recording head 34 nozzles. The maintenance and recovery operation includes, for example, nozzle suction, dummy discharge, and nozzle surface cleaning. The maintenance and recovery operation involves moving the carriage 33 to the home position facing the maintenance and recovery mechanism 81. Nozzle suction is performed by moving the carriage 33 to the home position, capping with the cap 82, and applying suction to the nozzles. Dummy discharging is performed by moving the carriage 33 to the home position and discharging droplets that do not contribute to image formation. Nozzle surface cleaning is performed by the nozzle surface cleaning device.

[0266] Such maintenance and recovery operations ensure image formation by stable droplet discharging.

[0267] Next, one example of the nozzle surface cleaning device 2 will be described.

[0268] The nozzle surface cleaning device 2 in this embodiment includes a first wiping member, a wiping member conveying device, a wiping member pressing member, a second wiping member, and a holder member.

[0269] The first wiping member is a rollable, elongated wiping member that wipes droplets on the nozzle surface.

[0270] The wiping member conveying device conveys the first wiping member in the longitudinal direction. The wiping member pressing member presses the first wiping member against the nozzle surface. The second wiping member is a blade-shaped wiping member that wipes droplets on the nozzle surface. The holder member supports the second wiping member either fixedly or pivotably.

[0271] Further, the second wiping member contacts the first wiping member by pivoting on the upstream in the conveying direction of the first wiping member relative to the wiping member pressing member. The droplets wiped by the nozzle surface cleaning device 2 are, for example, attached during image formation or unnecessary fluid forcibly discharged from the nozzles by the maintenance and recovery mechanism 81, or attached mist.

[0272] Next, the nozzle surface cleaning device 2 of this embodiment will be described with reference to FIGS. 10 to 13.

[0273] FIGS. 10A and 10B are plan views illustrating an example of the wiping unit 83 constituting the nozzle surface cleaning device 2. FIGS. 10A and 10B differ in the position of the wiping subframe 85. FIGS. 11A and 11B are schematic cross-sectional views of an example of the nozzle surface cleaning device 2, illustrating cleaning using a web. FIG. 12 is a schematic cross-sectional view of another example of the nozzle surface cleaning device 2, illustrating cleaning using both a web and a wiper blade.

[0274] The wiping unit 83 includes, for example, a wiping main frame 84 and a wiping subframe 85. The wiping main frame 84 is supported by the fluid discharging device. The wiping subframe 85 is capable of reciprocating movement between the position illustrated in FIG. 10A and the position shown in FIG. 10B. In FIGS. 10A and 10B, an arrow De indicates the wiping direction relative to the recording head 34, and an arrow Dc indicates the conveying direction of a first wiping member 90.

[0275] The wiping subframe 85 is equipped with the first wiping member 90, a wiping member conveying device, a wiping member pressing member 91, a second wiping member 86, and a holder member 87.

[0276] The first wiping member 90 is a rollable, elongated wiping member that wipes droplets on the nozzle surface. Hereinafter, the first wiping member 90 is sometimes referred to as the web.

[0277] The wiping member conveying device conveys the first wiping member 90 in the longitudinal direction. The wiping member conveying device includes a feed roller 94, an upstream roller 95, a roller 91a pressed by a wiping member pressing member 91, a downstream roller 96, and a winding roller 97 from the upstream in the conveying direction of the web 90.

[0278] The wiping member pressing member 91 presses the first wiping member 90 against the nozzle surface.

[0279] The wiping member pressing member 91 presses the web 90 against the nozzle surface of the recording head 34 via the roller 91a and preferably has elasticity, such as a compression spring or an elastic material like rubber. The position of the wiping member pressing member 91 in the pressing direction is not fixed; for example, the pressing height can be adjusted by a cam, allowing the web to be switched from non-contact to contact and the pressing pressure during contact to be varied.

[0280] The second wiping member 86 is a blade-shaped wiping member that wipes droplets on the nozzle surface. Hereinafter, the second wiping member 86 may be referred to as the wiper blade.

[0281] The holder member 87 supports the second wiping member 86 so that it can be fixed or pivoted. Hereinafter, the holder member 87 may be referred to as the wiper holder.

[0282] The wiper holder 87 is supported by the wiping subframe 85 and can fix or pivot the wiper blade 86.

[0283] The wiper blade 86 contacts the web 90 by pivoting on the upstream of the wiping member pressing member 91 in the web's conveying direction.

[0284] The mounting position of the wiper holder 87 is not limited to the positions illustrated in FIGS. 12 and 13 as long as it allows the wiper blade 86 to contact the web 90 upstream of the wiping member pressing member 91.

[0285] A rotary encoder 92 is mounted coaxially on the roller 96 downstream. In addition, a transmissive sensor 93 capable of monitoring the web 90 conveyance is provided to manage the amount of web 90 conveyed.

[0286] The nozzle surface cleaning device 2 of this example is capable of three types of cleaning operations.

(1) Web Wiping (for Example, FIG. 11)

[0287] In web wiping, the first wiping member (web) 90 wipes droplets on the nozzle surface during one cleaning operation. Web wiping is highly effective to remove ink attached to the nozzle surface, and its cleaning performance can be enhanced by impregnating the web with a cleaning liquid.

[0288] The web is, for example, made of fibers and contacts the nozzle at point contact, resulting in high cleaning ability; however, this also causes strong frictional force against the nozzle, which may degrade the water-repellent film on the nozzle surface when wiping is repeated multiple times.

(2) Blade Wiping (for Example, FIG. 12)

[0289] In blade wiping, during one cleaning operation, the second wiping member (wiper blade) 86 wipes droplets on the nozzle surface, and the first wiping member (web) 90 removes droplets adhering to the second wiping member (wiper blade) 86. Blade wiping has a high ability to remove liquid from the nozzle surface and excels at forming a meniscus on the nozzle after cleaning. Since it contacts the nozzle by line contact and surface contact, the frictional force on the nozzle is low, making it less likely to degrade the water-repellent film on the nozzle surface despite repeated wiping.

(3) Web and Blade Wiping (for Example, FIG. 13)

[0290] In web and blade wiping, during one cleaning operation, the first wiping member (web) 90 wipes droplets on the nozzle surface, the second wiping member (wiper blade) 86 wipes droplets on the nozzle surface, and the first wiping member (web) 90 removes droplets adhering to the second wiping member (wiper blade) 86, in this order.

[0291] This wiping method has a high ability to remove ink fixated on the nozzle surface and excels at forming a meniscus on the nozzle after cleaning. Also, since the number of web wiping operations can be reduced, it is less likely to degrade the water-repellent film on the nozzle surface.

[0292] Additional descriptions will be made regarding FIGS. 11 to 13.

(1) Web Wiping

[0293] FIG. 11A schematically illustrates the state before wiping the nozzle surface with the web 90, and FIG. 11B schematically illustrates the state after wiping the nozzle surface with the web 90. Cleaning of the nozzle surface is performed by relatively moving the wiping subframe 85 with respect to the recording head 34 that has moved to the maintenance and recovery mechanism 81, after a suction operation by the cap 82 connected to a suction pump is performed on the recording head 34. Alternatively, cleaning is performed by relatively moving the wiping subframe 85 with respect to the recording head 34 that has moved to the maintenance and recovery mechanism 81, after the ink is supplied and pressurized from a supply pump to forcibly discharge the ink from the recording head 34. In FIG. 11A, a droplet (ink) 50 targeted for wiping, which remains on the nozzle surface of the recording head 34 before cleaning after the suction operation by the cap 82, is schematically illustrated.

[0294] The droplet 50 on the nozzle surface is wiped by moving the wiping subframe 85 in the direction indicated by the arrow in FIG. 11A, pressing the web 90 by the wiping member pressing member 91 against the nozzle surface via the roller 91a, and absorbed into the web 90. The arrow direction in FIG. 11A corresponds to the De direction in FIG. 10.

[0295] FIG. 11B schematically illustrates the state in which droplets have been wiped by the web 90 through the operation in FIG. 11A. A droplet 50 remaining on the nozzle surface is removed by the web 90 wiping the nozzle surface. Known configurations can be applied as devices (mechanisms) for driving and conveying the web 90 to perform these operations.

(2) Blade Wiping

[0296] FIGS. 12A and 12B schematically illustrate the state before wiping with the wiper blade 86. FIG. 12C schematically illustrates the state after the nozzle surface has been wiped with the wiper blade 86. FIG. 12D schematically illustrates the state in which the web 90 is cleaning the wiper blade 86 (removing attached droplets).

[0297] Cleaning of the nozzle surface is performed by relatively moving the wiping subframe 85 with respect to the recording head 34 that has moved to the maintenance and recovery mechanism 81, after a suction operation by the cap 82 connected to a suction pump is performed on the recording head 34. Alternatively, cleaning is performed by relatively moving the wiping subframe 85 with respect to the recording head 34 that has moved to the maintenance and recovery mechanism 81, after the ink is supplied and pressurized from a supply pump to forcibly discharge the ink from the recording head 34.

[0298] FIG. 12A schematically illustrates the droplet (ink) 50 targeted for wiping that remains on the nozzle surface of the recording head 34 before cleaning, after the suction operation by the cap 82. The droplet 50 on the nozzle surface is wiped and removed by moving the wiping subframe 85 in the direction indicated by the arrow in FIG. 12A, causing the wiper blade 86 to come into contact with the nozzle surface. The arrow direction in FIG. 12A corresponds to the De direction in FIG. 10.

[0299] As illustrated in FIG. 12C, the droplet 50 removed from the nozzle surface adheres to the wiper blade 86.

[0300] FIG. 12D illustrates the cleaning operation of the wiper blade 86. The droplet 50, which has been removed from the nozzle surface and adhered to the wiper blade 86, is absorbed into the web 90 and thereby removed from the wiper blade 86 when the wiper blade 86 comes into contact with the web 90 through rotation of the wiper holder 87.

[0301] The operation of the wiper holder 87 is such that, for example, it is fixed during wiping of the nozzle surface, and after wiping, it rotates downstream in the conveying direction until the wiper blade 86 comes into contact with the web 90. Known configurations can be applied as devices (mechanisms) for driving wiper holder 87 to perform these operations.

(3) Web and Blade Wiping

[0302] FIG. 13A schematically illustrates the state before nozzle surface wiping with the web 90. FIG. 13B schematically illustrates the state after nozzle surface wiping with the web 90 and before wiping with the wiper blade 86. FIG. 13C schematically illustrates the state after nozzle surface wiping with the wiper blade 86. FIG. 13D schematically illustrates the state in which the web 90 is cleaning the wiper blade 86 (removing attached droplets).

[0303] Cleaning of the nozzle surface is performed by relatively moving the wiping subframe 85 with respect to the recording head 34 that has moved to the maintenance and recovery mechanism 81, after a suction operation by the cap 82 connected to a suction pump is performed on the recording head 34. Alternatively, cleaning is performed by relatively moving the wiping subframe 85 with respect to the recording head 34, after ink is supplied and pressurized from a supply pump to forcibly discharge ink from the recording head 34 moved to the maintenance and recovery mechanism 81

[0304] FIG. 13A schematically illustrates the droplet (ink) 50 targeted for wiping that remains on the nozzle surface of the recording head 34 before cleaning, after the suction operation by the cap 82. The wiping subframe 85 moves in the direction indicated by the arrow in FIG. 13A, and the web 90, which is pressed against the nozzle surface by the wiping member pressing member 91 via the roller 91a, comes into contact with the nozzle surface. As a result, the droplet 50 on the nozzle surface are wiped off and absorbed into the web 90.

[0305] FIG. 13B schematically illustrates a droplet 50a that has been wiped by the web 90 through the operation in FIG. 13A, and a droplet 50b that remains on the nozzle surface without being wiped off. The remaining droplet 50b on the nozzle surface is wiped off and removed by bringing the wiper blade 86 into contact with the nozzle surface.

[0306] As illustrated in FIG. 13C, the droplet 50 removed from the nozzle surface adheres to the wiper blade 86.

[0307] FIG. 13D illustrates the cleaning operation of the wiper blade 86. The droplet 50b, which has been removed from the nozzle surface and adhered to the wiper blade 86, is absorbed into the web 90 and thereby removed from the wiper blade 86 when the wiper blade 86 comes into contact with the web 90 through rotation of the wiper holder 87. The operation of the wiper holder 87 is such that, for example, it is fixed during wiping of the nozzle surface, and after wiping, it rotates downstream in the conveying direction until the wiper blade 86 comes into contact with the web 90. Known configurations can be applied as devices (mechanisms) for driving wiper holder 87 to perform these operations.

Printed Product

[0308] Next, the printed product (printed matter) of the present disclosure is described.

[0309] The printed matter of the present disclosure is obtained using the ink set of the present disclosure, and includes a substrate, a print layer provided on the substrate and containing the organic acid, the amine compound, and a pigment, and a layer containing a cationic resin.

[0310] The printed matter of the present disclosure exhibits good image density and high friction fastness. The printed matter of the present disclosure is produced by the fluid applying method of the present disclosure. Additionally, the printed matter of the present disclosure is produced by the fluid applying device of the present disclosure.

[0311] The printed matter may also be referred to as a printed article or a recorded article.

[0312] FIG. 14 is a cross-sectional observation image of an example of the printed matter of the present disclosure. FIG. 15 is a schematic cross-sectional view illustrating the layer structure of an example of the printed matter of the present disclosure.

[0313] The substrate 39 is a fiber substrate (cotton).

[0314] The print layer 191 contains an organic acid, an amine compound, and a pigment, and corresponds to a layer formed by the pre-treatment fluid and the aqueous pigment ink.

[0315] In FIG. 15, the pigment 195 is schematically shown as being contained in the print layer 191.

[0316] The continuous layer 192 is a layer formed by post-treatment and does not contain pigment. The continuous layer 192 corresponds to the layer containing a cationic resin formed by a post-treatment fluid. The term continuous layer 192 refers, for example, to a layer formed solely by the fixation of a cationic resin contained in the post-treatment fluid, without inclusion of any pigment. It is considered that a continuous layer without pigment can be formed over the print layer on a fiber substrate, which not only improves image density through the reflective intensity of the coating film, but also provides protection for the print layer via the resin in the continuous layer.

[0317] An embedded resin 193 is an epoxy resin used in the embedding process performed prior to observation, in which a cross-sectional thin section of the printed article is prepared by embedding it in epoxy resin.

[0318] Having generally described preferred embodiments of this disclosure, further understanding can be obtained by reference to certain specific examples which are provided herein for the purpose of illustration only and are not intended to be limiting. In the descriptions in the following examples, the numbers represent weight ratios in parts, unless otherwise specified.

EXAMPLES

[0319] Next, embodiments of the present disclosure are described in detail with reference to Examples but are not limited thereto.

Preparation of Black Pigment Dispersion A

Preparation of Polymer Solution A

[0320] After a through replacement with nitrogen gas in a one litter flask equipped with a mechanical stirrer, a thermometer, a nitrogen gas introducing tube, a reflux tube, and a dripping funnel, 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 mercapto ethanol were admixed in the flask followed by heating to 65 degrees Celsius.

[0321] Next, a liquid mixture 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 mercapto ethanol, 2.4 g of azobismethyl valeronitrile, and 18 g of methylethyl ketone was added dropwise to the flask in 2.5 hours. Subsequently, a liquid mixture of 0.8 g of azobismethyl valeronitrile and 18 g of methylethyl ketone was added dropwise to the flask in 0.5 hours. The resulting mixture was aged at 65 degrees Celsius for one hour. Thereafter, 0.8 g of azobismethyl valeronitrile was added followed by aging for another hour. After the reaction was complete, 364 g of methylethyl ketone was added to the flask to obtain 800 g of polymer solution A having a concentration of 50 percent by mass.

Preparation of Liquid Dispersion of Polymer P Fine Particle Containing Pigment

[0322] Twenty eight g of the polymer solution A, 42 g of carbon black pigment (Monarch 800, available from Cabot Corporation), 13.6 g of 1 mol/L potassium hydroxide aqueous solution, 20 g of methylethyl ketone, and 13.6 g of deionized water were sufficiently stirred and then mixed and kneaded using a roll mill. The thus-obtained paste was charged in 200 g of pure water followed by sufficient stirring. Thereafter, methylethyl ketone and water were distilled away using an evaporator. To remove coarse particles, the thus-obtained liquid dispersion was filtered with a polyvinylidene fluoride membrane filter having an average hole diameter of 5.0 m under pressure. As a result, a liquid dispersion of resin-coated black pigment A was obtained which included a pigment portion in an amount of 15 percent by mass with a solid portion concentration of 20 percent by mass.

Preparation of Black Pigment Dispersion B

[0323] A total of 100 g of carbon black (SEAST SP, SRF-LS, available from TOKAI CARBON CO., LTD.) was added to 3,000 mL of sodium hypochlorite at 2.5 normal, followed by stirring at 300 rpm at 60 degrees Celsius to allow reaction for 10 hours for oxidization. As a result, a pigment in which a carboxylic acid group was placed on the surface of carbon black was obtained.

[0324] The reaction liquid was filtered and the thus-filtered carbon black was neutralized with sodium hydroxide solution followed by ultra-filtering.

[0325] Thereafter, the resulting pigment dispersion and deionized water were subjected to ultra filtration by dialysis membrane followed by ultrasonic dispersion so that self dispersive black pigment dispersion B having a pigment solid content concentrated to 20 percent was obtained.

Preparation of Ink, Post-processing Fluid, and Post-processing Fluid

[0326] Inks of Preparation Examples 1 to 4, pre-treatment fluids of Preparation Examples 1 to 8, and post-treatment fluid of Preparation Examples 1 to 10 were obtained by mixing and stirring the materials according to the prescriptions and proportions (percent by mass) shown in Tables 1 to 3 below, followed by filtration using a 1.2 m cellulose acetate filter (Minisart, available from Sartorius AG). For the resin emulsions and pigments, the added amounts are shown as solid content.

[0327] The details of the materials shown in Tables 1 to 3 are as follows. [0328] Surfinol 440 (acetylene glycol surfactant, available from Nissin Chemical co., ltd.) [0329] SILFACE SAG-014 (silicone surfactant, available from Nissin Chemical co., ltd.) [0330] TAKELAC W-6110: Urethane resin emulsion, available from Mitsui Chemicals, Inc. [0331] PERMARIN UA-368 (Urethane resin emulsion, available from SANYO CHEMICAL INDUSTRIES) [0332] Nikazol FX-2023 (acrylic resin emulsion, available from NIPPON CARBIDE INDUSTRIES CO., INC.) [0333] ADEKA BONTIGHTER HUX-561S (urethane resin emulsion, available from ADEKA CORPORATION) [0334] EMULGEN LS-106 (fluorochemical surfactant, available from Kao Corporation) [0335] HYDRAN CP7520 (cationic urethane resin emulsion, available from DIC Corporation) [0336] SUPERFLEX 650 (cationic urethane resin emulsion, available from DKS Co. Ltd.) [0337] Mowinyl M-9410 (cationic acrylic resin, available from Japan Coating Resin co.,ltd.) [0338] PUE-800 (nonionic urethane resin emulsion, available from Murayama Chemical Laboratory Co., Ltd.) [0339] PROXEL LV (preservative, available from Arxada JAPAN) [0340] The other reagents were procured for use from Kanto Chemical CO.,INC. [0341] Regarding the post-treatment fluid, its thickness after preparation was shown in Table 3. The thickness represents the value at 25 degrees Celsius.

TABLE-US-00001 TABLE 1 Ink Prepa- Prepa- Prepa- Prepa- ration ration ration ration Exam- Exam- Exam- Exam- ple 1: ple 2: ple 3: ple 4: Triethylene glycol 20.0 15.0 10.0 5.0 Glycerin 10.0 5.0 10.0 5.0 2-pyrroridone 10.0 10.0 20.0 Triethylene glycol 2.0 2.0 2.0 2.0 monobutyl ether OLFINE E1010 0.5 0.5 BYK-348 0.5 0.5 TAKELAC.sup.trademark W- 13.0 6110, solid content PERMARIN UA-368 13.0 (solid content) Nikazol FX-2033 13.0 (solid content) ADEKA BONTIGHTER 13.0 HUX-561S (solid content) Black pigment dispersion 5.0 5.0 A (solid content) Black pigment dispersion 5.0 5.0 B (solid content) Proxel XLII 0.1 0.1 0.1 0.1 Highly pure water Balance Balance Balance Balance Total amount 100 100 100 100

TABLE-US-00002 TABLE 2 Pre-treatment fluid Prepa- Prepa- Prepa- Prepa- ration ration ration ration Exam- Exam- Exam- Exam- ple 1: ple 2: ple 3: ple 4: Triethylene glycol 20.0 10.0 20.0 2-pyrroridone 10.0 20.0 1,2-hexanediol 5.0 3.0 5.0 BYK-348 0.3 0.3 0.3 0.3 Lactic acid 15.0 Citric acid 10.0 Acetic acid 10.0 Formic acid 15.0 Maleic acid Magnesium nitrate Calcium lactate Triethanol amine 2.0 2.0 2-amino-2-methyl-1,3-propane 1.5 diol Diethylamine 1.5 Proxel XLII 0.1 0.1 0.1 0.1 Highly pure water Balance Balance Balance Balance Total amount 100 100 100 100 Pre-treatment fluid Prepa- Prepa- Prepa- Prepa- ration ration ration ration Exam- Exam- Exam- Exam- ple 5: ple 6: ple 7: ple 8: Triethylene glycol 20.0 20.0 20.0 20.0 2-pyrroridone 1,2-hexanediol 5.0 BYK-348 0.3 0.3 0.3 0.3 Lactic acid 15.0 Citric acid Acetic acid Formic acid Maleic acid 15.0 Magnesium nitrate 15.0 Calcium lactate 15.0 Triethanol amine 2.0 2.0 2.0 2-amino-2-methyl-1,3-propane diol Diethylamine Proxel XLII 0.1 0.1 0.1 0.1 Highly pure water Balance Balance Balance Balance Total amount 100 100 100 100

TABLE-US-00003 TABLE 3 Post-treatment fluid Prepa- Prepa- Prepa- Prepa- Prepa- ration ration ration ration ration Exam- Exam- Exam- Exam- Exam- ple 1: ple 2: ple 3: ple 4: ple 5: Triethylene glycol 40.0 20.0 35.0 2-pyrroridone 20.0 45.0 45.0 1,2-hexanediol 5.0 3.0 5.0 5.0 BYK-348 0.3 0.3 0.3 0.3 0.3 HYDRAN 10.0 10.0 10.0 CP7520 (solid content) SUPERFLEX 5.0 650 (solid content) Mowinyl M-9410 17.0 (solid content) TAKELAC.sup.trademark W-6110, solid content PUE-800 (solid content) Proxel XLII 0.1 0.1 0.1 0.1 0.1 Highly pure water Balance Balance Balance Balance Balance Total amount 100 100 100 100 100 solid content 10.0 5.0 17.0 10.0 10.0 Viscosity (cP) 8.2 9.5 10.9 7.7 11.3 Post-treatment fluid Prepa- Prepa- Prepa- Prepa- Prepa- ration ration ration ration ration Exam- Exam- Exam- Exam- Exam- ple 6: ple 7: ple 8: ple 9: ple 10: Triethylene glycol 48.0 10.0 40.0 40.0 60.0 2-pyrroridone 1,2-hexanediol 5.0 5.0 5.0 5.0 5.0 BYK-348 0.3 0.3 0.3 0.3 0.3 HYDRAN 4.8 20.1 CP7520 (solid content) SUPERFLEX 650 (solid content) Mowinyl M-9410 (solid content) TAKELAC.sup.trademark 10.0 W-6110, solid content PUE-800 (solid 10.0 content) Proxel XLII 0.1 0.1 0.1 0.1 0.1 Highly pure water Balance Balance Balance Balance Balance Total amount 100 100 100 100 100 solid content 4.8 20.1 10.0 10.0 0 Viscosity (cP) 8.6 10.4 8.4 9.7 8.1

Examples 1 to 14 and Comparative Examples 1 to 6

[0342] For each Example and Comparative Example, evaluation was conducted using the combinations of pre-treatment, ink, and post-treatment shown in Table 4. In the table, * in the column of heat drying means that a heat drying process was performed, which was carried out in a hot air oven at 160 degrees Celsius for 5 minutes. The evaluations listed in Table 4 were specifically conducted according to the methods described below. All substrates used were cotton broadcloth with a 40-sheen finish, available from SHIKISENSHA CO., LTD. The substrate used was a woven fabric.

Evaluation on Image Density

[0343] The pre-treatment fluid, ink, and post-treatment fluid for each Example and Comparative Example were each filled into a separate Ricoh Ri 100 printer, available from Ricoh Co., Ltd., and the applied amount of the pre-treatment fluid, ink, and post-treatment fluid was adjusted to 20 g/m.sup.2 each. Subsequently, a solid image was printed at 600600 dpi on the substrate, with drying steps inserted between the applications depending on Examples, followed by drying the substrate in a hot air oven at 160 degrees Celsius for 10 minutes to obtain printed product.

[0344] The pre-treatment fluid, ink, and post-treatment fluid were discharged onto the substrate by the inkjet method as illustrated in FIG. 7.

[0345] The image density of the solid prints prepared by executing the method specified above was measured using an X-Rite Exact spectrophotometer, available from X-Rite, Inc. and the results were evaluated. The evaluation criteria were as follows: Grades A and B are considered acceptable.

Evaluation Criteria

[0346] AA: Density of the solid portion is at least 1.5 [0347] A: Density of the solid portion is at least 1.4 [0348] B: Density of the solid portion is from 1.3 to less than 1.4 [0349] C: Density of the solid portion is less than 1.3

Evaluation on System Stability

[0350] The pre-treatment fluid, ink, and post-treatment fluid for each Example and Comparative Example were each filled into a separate Ricoh Ri 100 printer, available from Ricoh Co., Ltd., and the applied amount of the pre-treatment fluid, ink, and post-treatment fluid was adjusted to 20 g/m.sup.2 each. Thereafter, the devices were placed in a constant temperature chamber at 50 degrees Celsius and left for one month. After being removed from the chamber and allowed to return to room temperature, the applied amounts were measured again. The evaluation criteria were as follows: Grades A and B are considered acceptable.

Evaluation Criteria

[0351] A: Change in attached amount is less than 5 percent [0352] B: Change in attached amount is 5 to less than 10 percent [0353] C: Change in attached amount is at least 10 percent

Evaluation of Dry Friction Fastness

[0354] The solid images prepared by executing the same method above mentioned as that for Image Density Evaluation were subjected to a friction fastness test (dry rubbing) according to a JIS L0849 (test methods for color fastness to rubbing)-compliant Gakushin-type friction fastness tester. The optical density (OD) of the transferred ink on cotton fabric was measured. The evaluation criteria were as follows: Grades A and B are considered acceptable.

Evaluation Criteria

[0355] AA: Transfer OD of the cotton fabric after testing is less than 0.10 [0356] A: Transfer OD of the cotton fabric after testing is 0.10 to less than 0.15 [0357] B: Transfer OD of the cotton fabric after testing is 0.15 to less than 0.20 [0358] C: Transfer OD of the cotton fabric after testing is at least 0.20

Evaluation of Wet Friction Fastness

[0359] The solid images prepared by executing the same method above mentioned as that for Image Density Evaluation were subjected to a friction fastness test (wet rubbing) according to a JIS L0849 (test methods for color fastness to rubbing)-compliant Gakushin-type friction fastness tester. The optical density (OD) of the transferred ink on cotton fabric was measured.

[0360] The evaluation criteria were as follows: Grades A and B are considered acceptable.

Evaluation Criteria

[0361] AA: Transfer OD of the cotton fabric after testing is less than 0.10 [0362] A: Transfer OD of the cotton fabric after testing is 0.10 to less than 0.15 [0363] B: Transfer OD of the cotton fabric after testing is 0.15 to less than 0.20 [0364] C: Transfer OD of the cotton fabric after testing is at least 0.20

Examples 15 and 16

[0365] In the evaluation of Example 1, the applied amounts of the pre-treatment liquid, post-treatment liquid, and ink were each adjusted to 20 g/m.sup.2.

[0366] In Examples 15 and 16, the applied amount of the post-treatment liquid was adjusted to 30 g/m.sup.2 and 5 g/m.sup.2, respectively, while keeping the other conditions the same.

TABLE-US-00004 TABLE 4 Prescription Drying with heat Pre- Post- Between Between treatment treatment first and second and fluid Ink fluid second steps third steps Example 1 1 1 1 Example 2 2 1 2 Example 3 3 1 3 Example 4 1 2 2 Example 5 1 3 3 Example 6 2 4 2 Example 7 1 1 1 A Example 8 1 1 1 A Example 9 4 1 1 Example 10 5 1 1 Example 11 1 1 4 Example 12 1 1 5 Example 13 1 1 6 Example 14 1 1 7 Example 15 1 1 1 Example 16 1 1 1 Comparative 6 1 1 Example 1 Comparative 7 1 1 Example 2 Comparative 8 1 1 Example 3 Comparative 1 1 8 Example 4 Comparative 1 1 9 Example 5 Comparative 1 1 10 Example 6 Evaluation results Dry Wet Image System rubbing rubbing density stability fastness fastness Other Example 1 A A A A Example 2 A A A A Example 3 A A A A Example 4 A A A A Example 5 A A A A Example 6 A A A A Example 7 B A A B Example 8 B A B B Example 9 B A A A Example 10 B A B A Example 11 A B A B Example 12 A B A A Example 13 B A B B Example 14 A B A A Example 15 B A AA AA Change of applied amount Example 16 AA A A B Change of applied amount Comparative A A B C Example 1 Comparative A B B C Example 2 Comparative A C A A Example 3 Comparative B A A C Example 4 Comparative A A B C Example 5 Comparative C A C C Example 6

Example 17

[0367] The pre-treatment liquid, ink, and post-treatment liquid of Example 1 were filled into a RICOH Ri 100 printer, available from Ricoh, which was defined as Evaluation Device 1.

[0368] The pre-treatment liquid, ink, and post-treatment liquid of Example 1 were filled into a RICOH Ri 100 printer, available from Ricoh, which was defined as Evaluation Device 1.

[0369] Similarly, the pre-treatment liquid, ink, and post-treatment liquid of Example 1 were filled into a remodeled RICOH Ri 100 printer, available from Ricoh, which was defined as Evaluation Device 2.

[0370] Evaluation Device 2, the modified RICOH Ri 100, was equipped with a nozzle surface cleaning device. The nozzle surface cleaning device includes a wiping member that wipes off liquid from the nozzle surface in the RICOH Ri 100.

[0371] Evaluation Devices 1 and 2, each filled with the respective fluids, were placed in a constant temperature chamber at 50 degrees Celsius and left to rest for three months. The amount of attached material when a test image was printed before and after the resting period was measured, and the number of maintenance operations required until the change in attached amount before and after resting became less than 5 percent by mass was determined. As a result, Evaluation Device 1 required five maintenance operations to reduce the change in attached amount to less than 5 percent. In contrast, Evaluation Device 2 required only two maintenance operations to achieve the same level. In Evaluation Device 2, the maintenance operations included nozzle surface cleaning illustrated in FIG. 11.

[0372] The fluid applying device with the nozzle surface cleaning device can keep the nozzle surface clean, making it easier to maintain good discharge performance.

[0373] The aspects of the present disclosure are, for example, as follows:

Aspect 1

[0374] An ink set contains a pre-treatment fluid containing an organic acid and an amine compound, an aqueous pigment ink containing water, a pigment, and an organic solvent, and a post-treatment fluid containing a cationic resin particle.

Aspect 2

[0375] The ink set according to Aspect 1 mentioend above, wherein the organic acid contains at least one of lactic acid, citric acid, and acetic acid.

Aspect 3

[0376] The ink set according to Aspect 1 or 2 mentioned above, wherein the post-treatment fluid has a viscosity of 8.0 to 11.0 cP at 25 degrees Celsius.

Aspect 4

[0377] The ink set according to any one of Aspects 1 to 3 mentioned above, wherein the post-treatment fluid contains a solid content ranging from 5.0 to 20.0 percent by mass.

Aspect 5

[0378] A fluid applying apparatus includes the ink set of any one of Aspects 1 to 4 mentioned above, includes a pre-treatment fluid applying device to apply the pre-treatment fluid to a substrate, an ink applying device to apply the aqueous pigment ink to the substrate; and a post-treatment fluid applying device to apply the post-treatment fluid to the substrate.

Aspect 6

[0379] The apparatus according to Aspect 5 mentioned above, wherein the ink applying device discharges the aqueous pigment ink and the post-treatment fluid applying device discharges the post-treatment fluid.

Aspect 7

[0380] The apparatus according to Aspect 6 mentioned above, further includes one or more nozzle surface cleaning device each including a wiping member, wherein the ink applying device includes a nozzle surface with nozzles that discharge the aqueous pigment ink, [0381] wherein the post-treatment fluid applying device includes a nozzle surface with nozzles that discharge the post-treatment fluid, wherein the one or more nozzle surface cleaning devices clean at least one of the nozzle surface of the ink applying device and the nozzle surface of the post-treatment fluid applying device, the wiping member wipes off fluid on at least one of the nozzle surface of the ink applying device and the nozzle surface of the post-treatment fluid applying device.

Aspect 8

[0382] A fluid applying method using the ink set of any one of Aspects 1 to 4 mentioned above includes applying the pre-treatment fluid to a substrate, applying the aqueous pigment ink to the substrate, and applying the post-treatment fluid to the substrate.

Aspect 9

[0383] The method according to Aspect 8 mentioned above, includes no heat drying between the applying the aqueous pigment ink and the applying the post-treatment fluid.

Aspect 10

[0384] The method according to Aspect 8 or 9 mentioned above, wherein the applying the post-treatment fluid includes adjusting an applied amount of the post-treatment fluid.

Aspect 11

[0385] The method according to any one of Aspects 8 to 10, further includes pressing a region where the pre-treatment fluid has been applied after the applying the pre-treatment fluid and before the applying the aqueous pigment ink.

Aspect 12

[0386] A printed product produced with the ink set of any one of Aspects 1 to 4 mentioned above, includes a substrate, a print layer on the substrate, the print layer containing the organic acid, the amine compound, and the pigment, and a layer disposed on the print layer, containing the cationic resin particle on the print layer. The above-described embodiments are illustrative and do not limit the present invention. Thus, numerous additional modifications and variations are possible in light of the above teachings. For example, elements and/or features of different illustrative embodiments may be combined with each other and/or substituted for each other within the scope of the present invention. Any one of the above-described operations may be performed in various other ways, for example, in an order different from the one described above.