Inkjet printing method and ink set

Abstract

The invention provides an ink jet printing method and an ink set which have good friction fastness and color rendering property. The method comprises: a reaction liquid adhesion step in which a reaction liquid containing water and a coagulant that coagulates components in an ink is adhered to a fabric by an ink jet method; a clear ink attachment step for attaching a clear ink composition containing anionic resin particles and water to the fabric by an ink jet method; and a colored ink adhesion step in which a colored ink composition containing a pigment, resin particles, and water is adhered to the region to which the clear ink composition is adhered by an inkjet method, the reaction liquid adhesion step and the clear ink adhesion step having the following step 1, the range of the minimum value of the total adhesion amount of the reaction liquid and the clear ink composition per unit area / unit time is 34 mg / (s.inc2) or more. Step 1: The reaction liquid and the clear ink composition are applied to the same region of the fabric by one scan by an inkjet head.

Description

Technical Field

[0001] The invention relates to an inkjet printing and dyeing method and an ink set. Background Art

[0002] Conventionally, in printing and dyeing using an inkjet composition containing a pigment as a colorant (pigment printing and dyeing), it is known to treat fabric with a reaction solution containing a coagulant for coagulating components in the ink in order to improve friction fastness and color development.

[0003] For example, Patent Document 1 describes an inkjet printing method for printing on a fiber product substrate, which includes, in the following order: a) a step of providing the above-mentioned substrate; b) a step of applying a pretreatment composition containing polyvalent cations and / or acid salts; c) a step of applying by jetting a transparent ink containing a polymer binder; d) a step of applying by jetting a white ink; and e) a step of applying by jetting a non-white colored ink.

[0004] Patent Document 1: Japanese Patent Application No. 2022-548985

[0005] However, when the reaction liquid is attached to the fabric by the inkjet method, it is not possible to achieve good friction fastness and color development properties.

[0006] In addition, there is a problem of image quality being disturbed by the fuzzing of the fabric. Summary of the invention

[0007] One embodiment of the inkjet printing method according to the first embodiment of the present invention comprises: a reaction liquid attaching step of attaching a reaction liquid containing a coagulant for coagulating components in ink and water to a fabric by an inkjet method; a transparent ink attaching step of attaching a transparent ink composition containing anionic resin particles and water to a fabric by an inkjet method; and a colored ink attaching step of attaching a colored ink composition containing a pigment, resin particles, and water to a region to which the transparent ink composition is attached by an inkjet method, wherein the reaction liquid attaching step and the transparent ink attaching step comprise the following step 1, wherein the minimum value of the total amount of the reaction liquid and the transparent ink composition attached per unit area and per unit time is within the range of 34 mg / (s·inch 2 )above.

[0008] Step 1: Applying the reaction solution and the transparent ink composition to the same area of ​​the fabric by scanning the inkjet head once

[0009] One aspect of the ink set according to the first present invention is an ink set used in the inkjet printing method of the above aspect, comprising the above reaction solution, the above clear ink composition, and the above colored ink composition.

[0010] Second, one aspect of the inkjet printing method according to the present invention comprises: a reaction liquid attaching step of attaching a reaction liquid containing a coagulant for coagulating components in ink and water to a fabric; a transparent ink attaching step of attaching a transparent ink composition containing anionic resin particles and water that react with the coagulant and coagulate to the fabric; and a colored ink attaching step of attaching a colored ink composition containing a pigment, resin particles, and water to a region of the fabric to which the transparent ink composition is attached by an inkjet method, and after the reaction liquid attaching step and the transparent ink attaching step, a pressure imparting step of imparting pressure to the region of the fabric to which the reaction liquid and the transparent ink composition are attached, the fabric is placed on a mounting table, and the reaction liquid attaching step, the transparent ink attaching step, the pressure imparting step, and the colored ink attaching step are performed in a manner that does not change the relative positional relationship between the fabric and the mounting table between the steps.

[0011] One aspect of the ink set according to the second present invention is an ink set for use in the above-mentioned inkjet printing method, comprising the above-mentioned reaction liquid, the above-mentioned clear ink composition, and the above-mentioned colored ink composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 It is a perspective view of a serial printer according to a first embodiment of the present invention.

[0013] Figure 2 It is a schematic diagram showing an example of the arrangement of nozzle rows of the inkjet head according to the first embodiment of the present invention.

[0014] Figure 3 It is a schematic side view of a line printer according to the first embodiment of the present invention.

[0015] Figure 4 This is a table showing composition examples of the reaction solution, the clear ink composition, and the color ink composition according to the first embodiment of the present invention.

[0016] Figure 5 This is a table showing recording conditions of the inkjet printing method according to each of the examples and comparative examples according to the first embodiment of the present invention.

[0017] Figure 6 This is a table showing recording conditions of the inkjet printing method according to each of the examples and comparative examples according to the first embodiment of the present invention.

[0018] Figure 7 This is a table showing recording conditions of the inkjet printing method according to each of the examples and comparative examples according to the first embodiment of the present invention.

[0019] Figure 8 This is a table showing evaluation results of the inkjet printing method according to each of the examples and comparative examples according to the first embodiment of the present invention.

[0020] Fig. 9 It is a perspective view of an inkjet printing device according to a second embodiment of the present invention.

[0021] Fig.10 It is a schematic side view of an inkjet printing device according to a second embodiment of the present invention.

[0022] Fig.11 It is a figure which shows the state of the object to be printed and the object to be printed placed on the placing table according to the second embodiment of the present invention.

[0023] Fig.12 It is a schematic diagram showing an example of the arrangement of nozzle rows of an inkjet head according to the second embodiment of the present invention.

[0024] Fig.13 It is a schematic side view of a line printer according to a second embodiment of the present invention.

[0025] Fig.14 This is a table showing composition examples of the reaction solution, the clear ink composition, and the color ink composition according to the second embodiment of the present invention.

[0026] Fig.15 This is a table showing recording conditions of the inkjet printing method according to each of Examples and Comparative Examples according to the second embodiment of the present invention.

[0027] Description of Reference Numerals

[0028] 20: serial printer; 220: conveying unit; 230: recording unit; 231: inkjet head; 234: carriage; 235: carriage moving mechanism; 1: line printer; 100: supply unit; 200: conveying mechanism; 201: first paper feed roller; 202: second paper feed roller; 300: line head; 310: first line head; 320: second line head; 330: third line head; 340: fourth line head; 500: control unit; Y: feeding direction; F: recording medium; SD: scanning direction; TD: conveying direction. DETAILED DESCRIPTION

[0029] Hereinafter, the first embodiment of the present invention will be described. The embodiment described below is a way of illustrating an example of the present invention. The present invention is not limited by the following embodiment, and also includes various deformation modes implemented within the scope of not changing the gist of the present invention. In addition, not all structures described below are necessary structures of the present invention.

[0030] In the present specification, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as a lower limit and an upper limit.

[0031] In this specification, the "inkjet method" refers to a droplet ejection method based on the inkjet method.

[0032] In the present specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid, and "(meth)acrylate" means acrylate or methacrylate.

[0033] 1. Inkjet printing and dyeing method

[0034] The inkjet printing method according to one embodiment of the present invention comprises: a reaction liquid attaching step of attaching a reaction liquid containing a coagulant for coagulating components in ink and water to a fabric by an inkjet method; a transparent ink attaching step of attaching a transparent ink composition containing anionic resin particles and water to a fabric by an inkjet method; and a colored ink attaching step of attaching a colored ink composition containing a pigment, resin particles, and water to a region to which the transparent ink composition is attached by an inkjet method, wherein the reaction liquid attaching step and the transparent ink attaching step comprise the following step 1: applying the reaction liquid and the transparent ink composition to the same region of the fabric by a single scan of an inkjet head, wherein in the step 1, the minimum value of the total amount of the reaction liquid and the transparent ink composition attached per unit area and per unit time is in the range of 34 mg / (s·inch 2 )above.

[0035] In the past, in order to improve the color development of the color material in inkjet printing, a reaction liquid that condenses the components of the ink is attached to the cloth. This treatment usually uses a device or equipment different from the inkjet recording device or is often a manual operation, so large equipment and complicated processes are required. Therefore, the following method is studied: not only the ink but also the reaction liquid is ejected by the inkjet method, so that the reaction liquid and the ink are continuously attached in the same device. If this method is used, it is not necessary to use other devices and equipment, and the process can be simplified.

[0036] However, when the above-mentioned method is adopted, as the total amount of the attached reaction liquid and ink increases, it becomes more difficult to achieve both friction fastness and color development. This is presumably because when the total amount of the attached reaction liquid and ink increases, the water content increases, so the condensation effect based on the reaction liquid when the ink lands tends to become insufficient, and the ink continues to penetrate into the cloth, thereby reducing the color development.

[0037] It is also speculated that due to the increase in water content, i) the drying property is reduced and the bonding of the ink layer is likely to become insufficient, and ii) as the moisture content of the fabric texture increases, the permeability of the ink texture is reduced, thereby generating a gap between the ink layer and the surface layer of the texture, and the bonding is likely to become insufficient. Therefore, the adhesion between the ink layer and the fabric is reduced, resulting in a reduction in frictional firmness.

[0038] In particular, when printing on colored fabrics, a white ink layer is sometimes provided as a base in order to improve color rendering. However, the amount of white ink adhered in this printing is relatively large, and therefore the total amount of the adhered reaction liquid and ink tends to increase, making it particularly difficult to strike a balance between friction fastness and color rendering.

[0039] In contrast, according to the inkjet printing method of this embodiment, the coagulant in the reaction solution coagulates the transparent ink composition on the fabric, thereby forming a transparent ink layer (resin layer, foundation) near the surface of the fabric. Here, the fabric absorbs the landed droplets, so if the amount of droplet attachment per unit time is different, even if the amount of attachment is the same, the attachment method is different. That is, when the amount of droplet attachment per unit time is small relative to the absorption speed of the droplets in the fabric, it is difficult for ink to remain near the surface of the fabric.

[0040] Therefore, by making the total amount of adhesion per unit time / per unit area in the reaction liquid and the transparent ink composition greater than a predetermined value, that is, making the total amount of instantaneous adhesion greater than a predetermined value, the ink coagulates before penetrating the fabric, and a resin layer can be well formed near the surface of the fabric.

[0041] If such a well-formed resin layer is used, even if a colored ink is further attached thereto and the total amount of the reaction liquid and the ink attached increases, the penetration of the colored ink into the fabric can be suppressed, thereby obtaining good color development. In addition, the resin layer functions as a bonding layer between the fabric and the colored ink layer, thereby obtaining good friction fastness.

[0042] In the inkjet printing method according to the present embodiment, it is preferred that the total amount of the reaction liquid, the transparent ink composition, and the colored ink composition deposited on the fabric in the region where the reaction liquid, the transparent ink composition, and the colored ink composition are deposited is 100 mg / inch. 2 In this case, the total amount of the attached reaction liquid and ink is relatively large, so it is difficult to balance friction fastness and color development. However, the inkjet printing method involved in this embodiment can obtain good friction fastness and color development. The upper limit of the total amount of such adhesion is not particularly limited, but is preferably 500 mg / inch 2 Below, more preferably 300 mg / inch 2Below, more preferably 200 mg / inch 2 Below, particularly preferably 150 mg / inch 2 the following.

[0043] Hereinafter, each step of the inkjet printing method according to the present embodiment will be described.

[0044] 1.1 Reaction solution adhesion process

[0045] The inkjet printing method according to the present embodiment includes a reaction liquid adhering step of making a reaction liquid containing a coagulant for coagulating components in ink and water adhere to a fabric by an inkjet method.

[0046] 1.1.1 Process 1

[0047] In the inkjet printing method according to the present embodiment, the reaction liquid attachment step and the transparent ink attachment step described later include step 1: applying the reaction liquid and the transparent ink composition to the same area of ​​the fabric by scanning the inkjet head once. In step 1, the minimum value of the total attachment amount of the reaction liquid and the transparent ink composition per unit area and unit time is in the range of 34 mg / (s·inch 2 )above.

[0048] According to the coating in step 1, the reaction liquid and the clear ink composition can be continuously applied to the fabric in the same device.

[0049] <Scan>

[0050] Here, "scanning" in step 1 means moving the inkjet head relative to the recording area on the cloth. In this case, the inkjet head may be moved relative to the cloth, or the cloth may be moved relative to the inkjet head. In addition, the relative positional relationship between the inkjet head and the cloth may be changed by moving both the inkjet head and the cloth.

[0051] Therefore, the "scanning" in step 1, for example, Figure 1 In the serial inkjet recording apparatus 20 shown in the figure, the carriage 234 including the inkjet head 231 performs recording while moving in the scanning direction SD intersecting with the conveyance direction TD of the recording medium F.

[0052] In the case of a serial recording method, from the viewpoint of improving recording resolution, the cloth may be conveyed between scans. The cloth is conveyed by moving the relative positions of the inkjet head and the cloth in a direction intersecting the scanning direction. In addition, during the conveyance of the cloth, the ink is not ejected from the inkjet head and attached to the recording medium.

[0053] That is, in the inkjet printing method according to the present embodiment, the step 1 is performed multiple times, and the reaction liquid adhesion step and the transparent ink adhesion step have a step 2: the cloth is transported in a direction intersecting the scanning direction, and the step 2 is performed between the multiple steps 1. Thus, the reaction liquid and the transparent ink composition can be applied multiple times to the same area of ​​the cloth.

[0054] More specifically, for example, in Figure 1 In the case where a single conveying length of the recording medium F in the conveying direction TD is one-fourth the length of the nozzle array in the conveying direction TD of the inkjet head arranged in a direction intersecting the scanning direction SD, process 1 is performed 4 times on the same part (the same scanning area) with respect to a rectangular scanning area that is the length of the single conveying direction TD in the conveying direction TD and extends in the scanning direction SD.

[0055] The process 1 that is performed multiple times is 2 or more times, 3 or more times, or 4 or more times. The upper limit of process 1 is not particularly limited, but it may be less than 20 times, less than 15 times, or less than 10 times. In addition, it is preferred that when process 1 is performed n times (n is an integer greater than 2), process 2 is performed n-1 times. It is preferred that process 1 and process 2 are performed alternately and repeatedly.

[0056] On the other hand, the "scanning" in process 1 Figure 3 In the line-type inkjet recording apparatus 1 shown in the figure, recording is performed while the recording medium F is relatively moved in a direction intersecting the width direction relative to a line head 300 having a length corresponding to the width of the recording medium F. In line-type recording, the inkjet head (line head) does not move during recording but is fixed, and recording is performed by one scan.

[0057] "The length equivalent to the width of the recording medium" is not limited to the case where the width of the recording medium and the length (width) of the line head are completely consistent, but can also be a length greater than the length equivalent to the width of the recording medium, or can be a length equivalent to the width of the recording medium to which ink should be ejected (image should be recorded) (recorded width).

[0058] <Amount of adhesion per unit area and unit time>

[0059] In step 1, the minimum value of the total amount of the reaction solution and the clear ink composition deposited per unit area and unit time is in the range of 34 mg / (s·inch 2 ) or more, but preferably 40 mg / (s·inch 2 ) or more, more preferably 45 mg / (s·inch 2 ) or more, more preferably 50 mg / (s·inch 2) or more, particularly preferably 55 mg / (s·inch 2 ) or more, more preferably 60 mg / (s·inch 2 )above.

[0060] By making the minimum value range 34 mg / (s·inch 2 ) or more, thereby increasing the total instantaneous adhesion amount, causing the ink to coagulate before penetrating the fabric, thereby enabling a good resin layer to be formed near the surface of the fabric.

[0061] The maximum value of the total amount of the reaction solution and the clear ink composition deposited per unit area and unit time is not particularly limited, but is preferably 250 mg / (s·inch 2 ) or less, more preferably 225 mg / (s·inch 2 ) or less, more preferably 200 mg / (s·inch 2 ) or less, and more preferably 150 mg / (s·inch 2 ) or less, particularly preferably 100 mg / (s·inch 2 ) or less, more preferably 80 mg / (s·inch 2 )the following.

[0062] When the maximum value is within the above range, the texture of the fabric tends to be better.

[0063] The total amount of the reaction solution and the clear ink composition deposited per unit area and unit time can be appropriately adjusted by changing the printing area in one scan, the ink application amount, the carriage moving speed, the head driving frequency, and the like.

[0064] The printing area in one scan is preferably 3 to 30 inches, for example. 2 , more preferably 5 to 20 inches 2 , more preferably 7 to 15 inches 2 .

[0065] The amount of the reaction solution and the clear ink composition applied in one scan is, for example, preferably 100 to 1000 mg, more preferably 200 to 800 mg, and even more preferably 400 to 600 mg.

[0066] The carriage moving speed in the serial method is, for example, preferably 6 to 40 inch / s, more preferably 6 to 30 inch / s, further preferably 6 to 20 inch / s, particularly preferably 8 to 17 inch / s, and even more particularly preferably 10 to 15 inch / s.

[0067] The ratio (A / B) of the amount of the reaction solution attached per unit area / unit time to the amount of the transparent ink composition attached per unit area / unit time in step 1 is preferably 0.5 to 2.0, more preferably 0.6 to 1.7, further preferably 0.7 to 1.5, particularly preferably 0.8 to 1.3, and even more preferably 0.9 to 1.1. When the ratio (A / B) is within the above range, there is a tendency to form a resin layer better near the surface of the fabric, and better color development and friction fastness may be obtained.

[0068] 1.1.2 Cloth

[0069] As the form of the fabric used in the inkjet printing method involved in this embodiment, for example, cloth, clothing, other clothing, etc. Cloth includes woven fabrics, knitted fabrics, non-woven fabrics, etc. Clothing and other clothing include not only sewn T-shirts, handkerchiefs, scarves, towels, handbags, cloth bags, curtains, sheets, bedspreads, wallpapers and other items, but also cloth before and after cutting as parts before sewing. As their forms, they include: long strips rolled into rolls, items cut into a specified size, items in product shapes, etc.

[0070] As materials constituting the fabric, for example, natural fibers such as cotton, linen, wool, and silk, synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, and polyurethane, and biodegradable fibers such as polylactic acid may be cited, and blended fibers thereof may also be used. Among these materials, cotton, polyester, or a blend of cotton and polyester is preferred because it is easily available.

[0071] In addition, the fabric is preferably L * The value is below 75. * The value may be 60 or less, or 50 or less. When printing and dyeing such a fabric, in order to obtain excellent color development, a relatively large amount of a colored ink composition (especially white ink) is sometimes attached. Therefore, it can be said that it is particularly difficult to balance friction fastness and color development. In contrast, according to the inkjet printing method involved in this embodiment, even when using such a fabric, excellent friction fastness and color development can be obtained.

[0072] In addition, L * Indicates L * a * b * The brightness of the color space. L * The value can be measured using a known colorimeter, for example, Spectrolino (Gretag).

[0073] In addition, as L *The fabric having a value of 75 or less may be, for example, a colored fabric that has been pre-dyed with a dye or the like. Examples of dyes that pre-dyed the fabric include water-soluble dyes such as acid dyes and basic dyes, disperse dyes used in combination with a dispersant (surfactant), reactive dyes, and the like. As a method for dyeing the fabric, a known method may be used depending on the material and form of the fabric.

[0074] From the viewpoint of easy availability and being able to enjoy the effects of the present invention more, the fabric is preferably L * 75 or less, cotton, polyester, or a blend of cotton and polyester.

[0075] 1.1.3 Reaction solution

[0076] The reaction liquid used in the reaction liquid adhesion step contains a coagulant for coagulating components in the ink and water.

[0077] Hereinafter, each component contained in the reaction solution will be described.

[0078] <Coagulant>

[0079] The reaction liquid contains a coagulant for coagulating the components in the ink. The coagulant has the following function: by acting on the dispersibility of the components such as the anionic resin particles contained in the transparent ink composition and the pigment and resin particles contained in the colored ink composition, at least one of these components is coagulated. The degree of coagulation of the dispersion by the coagulant varies depending on the type of the coagulant and the object, and can be adjusted. By such a coagulation action, for example, the color development and fixability of the image can be improved.

[0080] The reaction solution preferably contains, as a coagulant, at least one selected from, for example, an organic acid, a polyvalent metal salt, and a cationic polymer. If such a coagulant is used, friction fastness and color development may be further improved.

[0081] As the organic acid, for example, preferably there can be mentioned: poly(meth)acrylic acid, formic acid, acetic acid, propionic acid, glycolic acid, oxalic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, citric acid, tartaric acid, lactic acid, pyruvic acid, pyrrolidonecarboxylic acid, pyronecarboxylic acid, pyrrolecarboxylic acid, furancarboxylic acid, picolinic acid, coumaric acid, thiophenecarboxylic acid, nicotinic acid or derivatives of compounds thereof or salts thereof.

[0082] The organic acid may be used alone or in combination of two or more. In addition, a substance that is both a salt of an organic acid and a metal salt is included in the metal salt described below.

[0083] The polyvalent metal salt is a compound composed of a metal ion having a valence of two or more and an anion. Examples of the metal ion having a valence of two or more include ions of calcium, magnesium, copper, nickel, zinc, barium, aluminum, titanium, strontium, chromium, cobalt, and iron. From the viewpoint of excellent coagulation of the components of the ink, at least one of a calcium ion and a magnesium ion is also preferred among the metal ions constituting the polyvalent metal salt.

[0084] Anions constituting the polyvalent metal salt are inorganic ions or organic ions. Examples of such inorganic ions include chloride ions, bromide ions, iodide ions, formate ions, nitrate ions, sulfate ions, hydroxide ions, etc. Examples of organic ions include organic acid ions, such as carboxylic acid ions.

[0085] As the specific example of the above-mentioned polyvalent metal salt, calcium carbonate, calcium formate, calcium nitrate, calcium chloride, calcium sulfate, magnesium sulfate, calcium hydroxide, magnesium chloride, magnesium carbonate, barium sulfate, barium chloride, zinc carbonate, zinc sulfide, aluminum silicate, calcium silicate, magnesium silicate, copper nitrate, calcium acetate, magnesium acetate, aluminum acetate, calcium propionate, magnesium propionate, aluminum propionate, calcium lactate, magnesium lactate, aluminum lactate, etc. such as heavy calcium carbonate and light calcium carbonate can be cited. These polyvalent metal salts can also be used alone or in combination of two or more. From the viewpoint of being able to obtain sufficient solubility in water, among these, preferably at least any one of magnesium sulfate, calcium formate, calcium nitrate, aluminum lactate, and calcium propionate. In addition, these metal salts can also be metal salts having hydration water in the raw material form such as magnesium sulfate heptahydrate and magnesium sulfate tetrahydrate.

[0086] Cationic polymers refer to polymer compounds having a cationic group. Examples of cationic polymers include cationic polyurethane resins, cationic olefin resins, cationic amine resins, and cationic amide resins.

[0087] The cationic amine resin may be any resin having an amino group, and examples thereof include allylamine resins, polyamine resins, and quaternary ammonium salt polymers.

[0088] As allylamine resin, there can be mentioned resins having a structure derived from allyl groups in the main skeleton of the resin. As polyamine resin, there can be mentioned resins having amino groups in the main skeleton of the resin. As quaternary ammonium salt polymer, there can be mentioned resins having quaternary ammonium salts in the structure. Among cationic polymers, cationic amine resins are not only excellent in reactivity, but also easy to obtain, and therefore are preferred.

[0089] The coagulants may be used alone or in combination of two or more.

[0090] From the viewpoint of better color development and friction fastness, the lower limit of the content of the coagulant is preferably 0.5 mass % or more, more preferably 1 mass % or more, further preferably 2 mass % or more, particularly preferably 3 mass % or more, and even more preferably 4 mass % or more, relative to the total mass of the reaction solution.

[0091] The upper limit of the content of the coagulant is not particularly limited, but is, for example, preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, particularly preferably 8% by mass or less, and even more preferably 7% by mass or less, relative to the total mass of the reaction solution.

[0092] <Water>

[0093] The reaction solution contains water. Examples of water include pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water, and water with reduced ionic impurities such as ultrapure water. In addition, if water is sterilized by ultraviolet irradiation or addition of hydrogen peroxide, the generation of bacteria and fungi can be suppressed when the reaction solution is stored for a long time.

[0094] The content of water is preferably 40% by mass or more, more preferably 45% by mass or more, more preferably 50% by mass or more, and particularly preferably 60% by mass or more relative to the total mass of the reaction solution. The upper limit of the content of water is not particularly limited, but for example, it is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less relative to the total mass of the reaction solution.

[0095] <Organic solvents>

[0096] The reaction liquid may contain an organic solvent. Examples of the organic solvent include esters, alkylene glycol ethers, cyclic esters, amides, alcohols, and polyols.

[0097] Examples of the esters include glycol monoacetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and methoxybutyl acetate; and glycol diesters such as ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, ethylene glycol diacetate propionate, ethylene glycol butyric acid acetate, diethylene glycol butyric acid acetate, diethylene glycol propionate acetate, diethylene glycol butyric acid acetate, propylene glycol propionate acetate, propylene glycol butyric acid acetate, dipropylene glycol butyric acid acetate, and dipropylene glycol propionate acetate.

[0098] The alkylene glycol ethers may be monoethers or diethers of alkylene glycols, and are preferably alkyl ethers. Specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, and tripropylene glycol monobutyl ether. Alkylene glycol monoalkyl ethers; and alkylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol methyl butyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and tripropylene glycol dimethyl ether.

[0099] Examples of the cyclic esters include cyclic esters (lactones) such as β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, β-butyrolactone, β-valerolactone, γ-valerolactone, β-caprolactone, γ-caprolactone, δ-caprolactone, β-heptanolactone, γ-heptanolactone, δ-heptanolactone, ε-heptanolactone, γ-octanolactone, δ-octanolactone, ε-octanolactone, δ-nonanolactone, ε-nonanolactone, and ε-decanolactone, and compounds wherein the hydrogen of the methylene group adjacent to the carbonyl group thereof is substituted with an alkyl group having 1 to 4 carbon atoms.

[0100] Examples of the amides include cyclic amides, non-cyclic amides, etc. Examples of the non-cyclic amides include alkoxyalkylamides, etc.

[0101] Examples of the cyclic amides include lactams, and examples of the lactams include pyrrolidones such as 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone.

[0102] Examples of the alkoxyalkylamides include 3-methoxy-N,N-dimethylpropionamide, 3-methoxy-N,N-diethylpropionamide, 3-methoxy-N,N-methylethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-diethylpropionamide, 3-ethoxy-N,N-methylethylpropionamide, 3-n-butoxy-N,N-dimethylpropionamide, 3-n-butoxy-N,N-diethylpropionamide, 3-n-butoxy-N,N-methylethylpropionamide, 3-n-propoxy-N,N-dimethylpropionamide, 3-n-propoxy-N,N-diethylpropionamide, 3-n-propoxy-N,N-methylethylpropionamide, 3-isopropoxy-N,N-dimethylpropionamide, 3-isopropoxy-N,N-diethylpropionamide, 3-isopropoxy-N,N-methylethylpropionamide, 3-tert-butoxy-N,N-dimethylpropionamide, 3-tert-butoxy-N,N-diethylpropionamide, 3-tert-butoxy-N,N-methylethylpropionamide, N,N-dimethylisobutyramide, etc.

[0103] Examples of alcohols include compounds in which one hydrogen atom of an alkane is replaced by a hydroxyl group. The alkane is preferably a structure having 10 or less carbon atoms, more preferably a structure having 6 or less carbon atoms, and more preferably a structure having 3 or less carbon atoms. The alkane has 1 or more carbon atoms, preferably 2 or more carbon atoms. The alkane may be a straight chain type or a branched chain type. Examples of alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert-butanol, isobutanol, n-pentanol, 2-pentanol, 3-pentanol, tert-pentanol, 2-phenoxyethanol, benzyl alcohol, phenoxypropanol, and the like.

[0104] Polyols have a structure having two or more hydroxyl groups in a molecule. Polyols can be divided into, for example, alkanediols and polyols.

[0105] Examples of alkanediols include compounds in which an alkane is substituted with two hydroxyl groups. Examples of alkanediols include 1,2-alkanediol, which is a general term for compounds in which the 1- and 2-positions of an alkane are substituted with hydroxyl groups, and other alkanediols other than 1,2-alkanediol.

[0106] Examples of 1,2-alkanediols include ethylene glycol, 1,2-propylene glycol (propylene glycol), 1,2-butanediol (1,2BD), 1,2-pentanediol (1,2PD), 1,2-hexanediol (1,2HD), 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 3-methyl-1,2-butanediol, 3-methyl-1,2-pentanediol, 4-methyl-1,2-pentanediol, 3,4-dimethyl-1,2- Pentanediol, 3-ethyl-1,2-pentanediol, 4-ethyl-1,2-pentanediol, 3-methyl-1,2-hexanediol, 4-methyl-1,2-hexanediol, 5-methyl-1,2-hexanediol, 3,4-dimethyl-1,2-hexanediol, 3,5-dimethyl-1,2-hexanediol, 4,5-dimethyl-1,2-hexanediol, 3-ethyl-1,2-hexanediol, 4-ethyl-1,2-hexanediol, 3-ethyl-4-methyl-1,2-hexanediol, and the like.

[0107] Examples of other alkanediols include 1,3-propanediol, 1,3-butanediol (also known as 1,3-butanediol), 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2,4-pentanediol, 2-methyl-1,3-propanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,3-pentanediol, 3-methyl-1,5-pentanediol, 2-methylpentane-2,4-diol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, and 2-methyl-2-propyl-1,3-propanediol.

[0108] Examples of the polyols include condensates obtained by intermolecular condensation of two or more molecules of alkanediols at hydroxyl groups, and compounds having three or more hydroxyl groups.

[0109] Examples of the condensate obtained by intermolecular condensation of two or more molecules of alkanediols at a hydroxyl group include dialkylene glycols such as diethylene glycol and dipropylene glycol; and trialkylene glycols such as triethylene glycol and tripropylene glycol.

[0110] The compound having three or more hydroxyl groups is a compound having three or more hydroxyl groups with an alkane or polyether structure as a skeleton. Examples of the compound having three or more hydroxyl groups include glycerol, trimethylolethane, trimethylolpropane, 1,2,5-hexanetriol, 1,2,6-hexanetriol, pentaerythritol, and polyoxypropylenetriol.

[0111] The organic solvent may be used alone or in combination of two or more.

[0112] Among these, the organic solvent preferably contains alkanediols, more preferably contains 1,2-alkanediol, and particularly preferably contains propylene glycol. When the organic solvent contains these solvents, the color development property and friction fastness may be more excellent.

[0113] The content of the organic solvent is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, further preferably 15 to 35% by mass, and particularly preferably 20 to 30% by mass relative to the total amount of the reaction solution. When the content of the organic solvent is within the above range, the color development and friction fastness may be further improved.

[0114] <pH Adjuster>

[0115] The reaction solution may contain a pH adjuster for adjusting the pH. The pH adjuster is not particularly limited, but examples thereof include an acid, a base, and an appropriate combination of a weak acid and a weak base.

[0116] Examples of acids and bases used in such a combination include sulfuric acid, hydrochloric acid, nitric acid, etc. as inorganic acids; lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium dihydrogen phosphate, disodium hydrogen phosphate, potassium carbonate, sodium carbonate, sodium bicarbonate, ammonia, etc. as inorganic bases; triethanolamine, diethanolamine, monoethanolamine, tripropanolamine, triisopropanolamine, diisopropanolamine, trishydroxymethylaminomethane (THAM), etc. as organic bases; adipic acid, citric acid, succinic acid, lactic acid, N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid, etc. as organic acids. (BES), 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES), morpholinoethanesulfonic acid (MES), carbamoyl iminodiacetic acid (ADA), piperazine-1,4-bis(2-ethanesulfonic acid) (PIPES), N-(2-acetylamino)-2-aminoethanesulfonic acid (ACES), choline hydrochloride, N-tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid (TES), acetamido glycine, glycine, glycine amide, Good buffer such as bis(hydroxyethyl)glycine, phosphate buffer, citrate buffer, Tris buffer, etc. Among these, inorganic bases are preferred, and potassium hydroxide is more preferred.

[0117] The reaction solution may also use a single pH adjusting agent, or may use two or more in combination. In addition, the total content relative to the gross mass of the reaction solution when the pH adjusting agent is used is, for example, 0.05% by mass or more and 3.0% by mass or less, more preferably 0.1% by mass or more and 1.0% by mass or less.

[0118] <Surfactant>

[0119] The reaction solution may also contain a surfactant. The surfactant can be used to reduce the surface tension of the reaction solution, for example, to adjust and improve the permeability to the fabric. As the surfactant, any of nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used, and they can also be used in combination. In addition, among the surfactants, acetylene surfactants (acetylene glycol surfactants), silicone surfactants, and fluorine-based surfactants can be more preferably used, and silicone surfactants and acetylene surfactants can be further preferably used.

[0120] The acetylene surfactant (acetylene glycol surfactant) is not particularly limited, but examples thereof include Surfynol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, and DF110D (trade names, Air Products and Chemicals Inc.), Olfine B, Y, P, A, STG, SPC, E1004, E1010, PD-001, PD-002W, PD-003, PD-004, PD-005, EXP.4001, EXP.4036, EXP.4051, EXP.4123, EXP.4200, EXP.4300, AF-103, AF-104, AK-02, SK-14, AE-3 (trade names, manufactured by Nissin Chemical Industry Co., Ltd.), acetylene alcohol E00, E00P, E40, E100 (trade names, manufactured by Kawaken Fine Chemicals Co., Ltd.).

[0121] The silicone-based surfactant is not particularly limited, but preferably a polysiloxane-based compound is used. The polysiloxane-based compound is not particularly limited, but for example, a polyether-modified silicone is used. Examples of commercially available products of the polyether-modified organosiloxane include BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, and BYK-348 (trade names, manufactured by BYK), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6004, KF-6011, KF-6012, KF-6015, and KF-6017 (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0122] As the fluorine-based surfactant, a fluorine-modified polymer is preferably used, and a specific example thereof is BYK-340 (trade name, manufactured by BYK-Chemie Japan Ltd.).

[0123] The surfactant may be used alone or in combination of two or more.

[0124] The reaction liquid preferably contains a surfactant having an HLB value of 10 or more. In the case of a surfactant having an HLB value of 10 or more, the permeability of the reaction liquid to the fabric can be adjusted satisfactorily, and there is a tendency that the reaction liquid is more likely to stay near the surface of the fabric. As a result, there is a tendency that the color development property is more excellent.

[0125] In this specification, the "HLB value" (value of hydrophile and liophile balance) numerically represents the hydrophilicity / hydrophobicity balance of a compound. Here, the HLB value is a value calculated by the Griffin method and can be obtained by the following formula (1).

[0126] HLB value = 20 × total formula weight of hydrophilic part / molecular weight... (1)

[0127] Specific examples of surfactants having an HLB value of 10 or more according to the Griffin method are listed below.

[0128] Examples of acetylene-based surfactants (acetylene glycol-based surfactants) having an HLB value of 10 or more include Olfine E1010 (HLB value 12), E1020 (HLB value 15 to 16), EXP.4200 (HLB value 10 to 13), and EXP.4123 (HLB value 10 to 13) [trade name, manufactured by Nissin Chemical Industry Co., Ltd.].

[0129] Examples of the silicone surfactant having an HLB value of 10 or more include BYK-348 (HLB value 11) [trade name, manufactured by BYK], KF-6011 (HLB value 14.5), KF-6013 (HLB value 10), KF-6043 (HLB value 14.5), KF-643 (HLB value 14), KF-640 (HLB value 14), KF-351A (HLB value 12), KF-354L (HLB value 16) [trade name, manufactured by Shin-Etsu Silicone Co., Ltd.], FZ-2105 (HLB value 11), L-7604 (HLB value 13), FZ-2104 (HLB value 14) [trade name, manufactured by Dow Corning Toray Co., Ltd.], SILWET L-7604 (HLB value 13), SILWET L-7607N (HLB value 17), SILWET FZ-2104 (HLB value 14) or SILWET FZ-2161 (HLB value 20) [trade names, manufactured by Eureka Japan Co., Ltd.], etc.

[0130] The lower limit of the content of the surfactant is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, particularly preferably 0.7% by mass or more, based on the total mass of the reaction solution.

[0131] In addition, the upper limit of the content of the surfactant is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, and particularly preferably 1.5% by mass or less relative to the total mass of the reaction solution. If the content of the surfactant is within the above range, there is a tendency that the permeability of the reaction solution to the fabric can be easily and satisfactorily adjusted.

[0132] <Other ingredients>

[0133] The reaction solution may also contain additives such as preservatives / mildewproof agents, rust inhibitors, chelating agents, viscosity modifiers, solubilizers, antioxidants, etc. as needed. The content of such additives is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, and further preferably 0.1 to 1% by mass relative to the total amount of the reaction solution.

[0134] The reaction solution may contain a coloring material such as a pigment, but the amount is preferably 0.2% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.05% by mass or less, with a lower limit of 0% by mass, relative to the total mass of the reaction solution. The reaction solution preferably does not contain a coloring material.

[0135] <Physical properties>

[0136] From the viewpoint of reducing skin irritation, the pH of the reaction solution is preferably 2.0 or more, more preferably 3.0 or more, and further preferably 4.0 or more. From the same viewpoint, the upper limit of pH is preferably 11.5 or less, more preferably 10 or less, further preferably 7.0 or less, and particularly preferably 5.0 or less.

[0137] The viscosity of the reaction solution is preferably 1.0 to 10 mPa·s, more preferably 1.5 to 5.0 mPa·s, further preferably 2.0 to 4.0 mPa·s, and particularly preferably 2.5 to 3.5 mPa·s. In particular, if the viscosity is 3.0 mPa·s or more, there is a tendency to obtain better color development. If the viscosity is 5.0 mPa·s or less, there is a tendency to obtain better ejection stability. In addition, the viscosity can be measured using, for example, a viscoelasticity tester MCR-300 (product name) of Pysica.

[0138] The viscosity of the mixed solution obtained by mixing the reaction solution and the transparent ink composition described later in equal amounts is preferably 50 mPa·s or more, more preferably 100 mPa·s or more, further preferably 200 mPa·s or more, particularly preferably 300 mPa·s or more, and more particularly preferably 320 mPa·s or more. If the viscosity of the mixed solution is within the above range, the water absorption rate to the fabric is slowed down, and a transparent ink layer (resin layer) can be formed better near the surface of the fabric. As a result, the penetration of the colored ink into the fabric can be further suppressed, and there is a tendency to obtain better color development. In addition, the resin layer plays a more significant role as a bonding layer between the fabric and the colored ink layer, thereby having a tendency to obtain better friction fastness.

[0139] The upper limit of the viscosity of the mixed solution obtained by mixing equal amounts of the reaction solution and the transparent ink composition described later is not particularly limited, but is preferably 10000 mPa·s or less, more preferably 5000 mPa·s or less, particularly preferably 2500 mPa·s or less, and even more preferably 1000 mPa·s or less.

[0140] The surface tension of the reaction solution is preferably 25 to 40 mN / m, more preferably 25 to 35 mN / m, further preferably 27 to 35 mN / m, and particularly preferably 30 to 33 mN / m. In addition, the surface tension can be measured by the Wilhelmy method using, for example, a surface tensiometer (DY-300 manufactured by Kyowa Interface Science Co., Ltd.). The surface tension is preferably a measured value at 20°C.

[0141] 1.2 Transparent ink adhesion process

[0142] The inkjet printing method according to the present embodiment includes a clear ink attaching step in which a clear ink composition containing anionic resin particles and water is attached to a fabric by an inkjet method.

[0143] In addition, the transparent ink attaching step and the above-mentioned reaction liquid attaching step include step 1: applying the reaction liquid and the transparent ink composition to the same area of ​​the fabric by scanning the inkjet head once. In step 1, the minimum value of the total amount of the reaction liquid and the transparent ink composition attached per unit area and unit time is in the range of 34 mg / (s·inch 2 The method for step 1 is as described above, so the description is omitted.

[0144] 1.2.1 Transparent ink composition

[0145] The clear ink composition used in the clear ink adhesion step contains anionic resin particles and water.

[0146] Hereinafter, each component contained in the clear ink composition will be described.

[0147] <Anionic resin particles>

[0148] The transparent ink composition contains anionic resin particles. Similar to the function of the resin particles, the anionic resin particles have the function of serving as a so-called fixing resin to improve the adhesion of the ink attached to the fabric. The anionic resin particles are often processed in the form of an emulsion, but may also be in the form of a powder.

[0149] The “anionic resin particles” refer to resin particles having a negative charge as a whole, and preferably have one or more anionic groups selected from a carboxyl group, a sulfonic acid group, a phosphoric acid group, and the like.

[0150] Examples of the resin particles include resin particles composed of polyurethane resins, acrylic resins (including styrene-acrylic resins), fluorene resins, olefin resins, rosin-modified resins, terpene resins, polyester resins, amide resins, epoxy resins, vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, and ethylene vinyl acetate resins. Among them, polyurethane resins, acrylic resins, olefin resins, and polyester resins are preferred. In addition, the resin particles may be used alone or in combination of two or more.

[0151] Polyurethane resin is a general term for resins having polyurethane bonds. In addition to polyurethane bonds, polyether polyurethane resins having ether bonds in the main chain, polyester polyurethane resins having polyester bonds in the main chain, and polycarbonate polyurethane resins having carbonate bonds in the main chain may also be used. In addition, as the polyurethane resin, commercially available products can also be used, for example, Superflex 460, 460s, 840, E-4000 (trade names, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), RESAMINE D-1060, D-2020, D-4080, D-4200, D-6300, D-6455 (trade names, manufactured by Dainichi Seika Industries, Ltd.), Takelac WS-5100, WS-6021, W-512-A-6 (trade names, manufactured by Mitsui Chemicals Polyurethanes, Ltd.), Suncure 2710 (trade name, manufactured by LUBRIZOL Co., Ltd.), Permarine UA-150 (trade name, manufactured by Sanyo Chemical Industries, Ltd.), etc.

[0152] Acrylic resin is a general term for polymers obtained by polymerizing at least one acrylic monomer such as (meth)acrylic acid or (meth)acrylic ester as one component, and examples thereof include resins obtained from acrylic monomers, copolymers of acrylic monomers and monomers other than acrylic monomers, etc. For example, acrylic acid-ethylene resins, which are copolymers of acrylic monomers and ethylene monomers, etc., can be cited. In addition, for example, styrene, etc., can be cited as ethylene monomers.

[0153] As the acrylic monomer, acrylamide, acrylonitrile, etc. can also be used. The resin emulsion using acrylic resin as a raw material can also use commercial products, for example, it can also be selected from FK-854 (trade name, made by Chuo Rika Industry Co., Ltd.), Movinyl952B, 718A (trade name, made by Nippon Synthetic Chemical Industry Co., Ltd.), NipolLX852, LX874 (trade name, made by Nippon Zeon Co., Ltd.), etc.

[0154] Styrene-acrylic resins are copolymers obtained from styrene monomers and (meth)acrylic acid monomers, and examples thereof include styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylate copolymers, styrene-α-methylstyrene-acrylic acid copolymers, and styrene-α-methylstyrene-acrylic acid-acrylate copolymers. As the styrene-acrylic resin, commercially available products may be used. Examples thereof include Joncryl 62J, 7100, 390, 711, 511, 7001, 632, 741, 450, 840, 74J, HRC-1645J, 734, 852, 7600, 775, 537J, 1535, PDX-7630A, 352J, 352D, PDX-7145, 538J, 7640, 7641, 631, 790, 780, and 7610 (trade names, manufactured by BASF), Movinyl 966A and 975N (trade names, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and Vinyblan 2586 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0155] The olefin resin is a polymer having olefins such as ethylene, propylene, and butene in the structural skeleton, and a known resin can be appropriately selected for use. As the olefin resin, a commercially available product can be used, for example, Arrow Base CB-1200, CD-1200 (trade name, manufactured by Unitika Co., Ltd.) and the like can also be used.

[0156] The anionic resin particles are more preferably polyurethane resin or acrylic resin, and further preferably polyurethane resin. In this case, the friction fastness tends to be more excellent.

[0157] The glass transition temperature (Tg) of the resin particles is preferably -60°C or higher and 50°C or lower, more preferably -60°C or higher and 40°C or lower, and further preferably -30°C or higher and 10°C or lower. When the glass transition temperature (Tg) of the resin particles is within the above range, there is a tendency that the texture followability (hand feel) is better. The glass transition temperature is measured, for example, using a differential scanning calorimeter "DSC7000" manufactured by Hitachi High-Tech Industries, Ltd., in accordance with JIS K7121 (Method for measuring transition temperature of plastics).

[0158] The content (solid content concentration) of the anionic resin particles is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, further preferably 4 to 20% by mass, particularly preferably 6 to 15% by mass, and even more particularly preferably 8 to 12% by mass relative to the total amount of the transparent ink composition. When the content of the anionic resin particles is within the above range, there is a tendency that more excellent color development and friction fastness can be obtained.

[0159] <Water>

[0160] The clear ink composition contains water. As the water, the same water as that in the above-mentioned reaction liquid can be used.

[0161] The water content is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 50% by mass or more, relative to the total mass of the clear ink composition. The upper limit of the water content is not particularly limited, but, for example, is preferably 90% by mass or less, more preferably 70% by mass or less, and more preferably 60% by mass or less, relative to the total mass of the clear ink composition.

[0162] <Organic solvents>

[0163] The clear ink composition may contain an organic solvent. The type and content of the organic solvent may be the same as those of the above-mentioned reaction solution.

[0164] In the transparent ink composition, the organic solvent preferably includes alkanediols, alkylene glycol ethers and trialkylene glycol, more preferably includes 1,2-alkanediol, alkylene glycol ethers and trialkylene glycol, and further preferably includes propylene glycol, triethylene glycol monobutyl ether and triethylene glycol. When the organic solvent includes these solvents, the color development and friction fastness may be more excellent.

[0165] The content of the organic solvent is preferably 10 to 55% by mass, more preferably 15 to 45% by mass, further preferably 20 to 40% by mass, and particularly preferably 25 to 35% by mass relative to the total amount of the clear ink composition. When the content of the organic solvent is within the above range, the color development and friction fastness may be further improved.

[0166] <Surfactant>

[0167] The clear ink composition may contain a surfactant, and the type of the surfactant and the like may be the same as those of the above-mentioned reaction solution.

[0168] The lower limit of the content of the surfactant is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, and particularly preferably 0.3% by mass or more, based on the total mass of the clear ink composition.

[0169] In addition, the upper limit of the content of the surfactant is preferably 3% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, and particularly preferably 0.8% by mass or less, relative to the total mass of the transparent ink composition. When the content of the surfactant is within the above range, there is a tendency that the permeability of the transparent ink composition to the fabric can be easily and satisfactorily adjusted.

[0170] <Other ingredients>

[0171] The transparent ink composition may contain additives such as a pH adjuster, an antiseptic / mildew preventer, a rust preventer, a chelating agent, a viscosity adjuster, a solubilizing agent, and an antioxidant as required. When such additives are contained, the content is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, and even more preferably 0.1 to 1% by mass relative to the total amount of the transparent ink composition.

[0172] The transparent ink composition may contain a coloring material such as a pigment, but the amount is preferably 0.2% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.05% by mass or less, with the lower limit being 0% by mass, relative to the total mass of the transparent ink composition. The transparent ink composition preferably does not contain a coloring material.

[0173] <Physical properties>

[0174] From the viewpoint of reducing skin irritation, the pH of the transparent ink composition is preferably 2.0 or more, more preferably 5.0 or more, and even more preferably 7.0 or more. From the same viewpoint, the upper limit of the pH is preferably 11.5 or less, more preferably 10 or less, even more preferably 9.0 or less, and particularly preferably 8.0 or less.

[0175] The viscosity of the transparent ink composition is preferably 1.0 to 10 mPa·s, more preferably 1.5 to 5.0 mPa·s, further preferably 2.0 to 4.0 mPa·s, and particularly preferably 3.0 to 4.0 mPa·s. In particular, when the viscosity is 3.0 mPa·s or more, there is a tendency to obtain better color development. When the viscosity is 5.0 mPa·s or less, there is a tendency to obtain better ejection stability.

[0176] The surface tension of the clear ink composition is preferably 10 to 40 mN / m, more preferably 15 to 35 mN / m, further preferably 20 to 30 mN / m, and particularly preferably 20 to 27 mN / m.

[0177] 1.4 Color ink adhesion process

[0178] The inkjet printing method according to the present embodiment includes a colored ink attaching step in which a colored ink composition containing a pigment, resin particles, and water is attached to the region to which the clear ink composition is attached by an inkjet method.

[0179] The transparent ink composition attached in the above manner becomes a resin layer well formed near the surface of the fabric, thereby suppressing the penetration of the colored ink into the fabric and obtaining good color development. In addition, the resin layer functions as a bonding layer between the fabric and the colored ink layer, thereby obtaining good friction fastness.

[0180] 1.4.1 Simultaneous reaction liquid adhesion process

[0181] From the viewpoint of achieving more excellent color development, friction fastness, feel, etc., the reaction liquid attaching step described above is preferably performed simultaneously with the colored ink attaching step.

[0182] Here, the reaction liquid adhesion process and the colored ink adhesion process "simultaneously" means that the time difference from the last landing of the reaction liquid to the initial landing of the colored ink composition on the same area of ​​the cloth is within 10 seconds, more preferably within 5 seconds, further preferably within 3 seconds, and particularly preferably within 1 second.

[0183] More specifically, the reaction liquid attaching step and the color ink attaching step “simultaneously” may be a case where the reaction liquid attaching step and the color ink attaching step include the following step 3.

[0184] Step 3: Applying the reaction liquid and the colored ink composition to the same area of ​​the fabric by scanning the inkjet head once

[0185] The "scanning" in step 3 means moving the inkjet head relative to the recording area of ​​the cloth, and is the same as the "scanning" in step 1 described above.

[0186] Alternatively, in the case of a serial recording method, step 3 is performed multiple times, and the reaction liquid attachment step and the colored ink attachment step have a step 4: the fabric is transported in a direction intersecting the scanning direction, and step 4 is performed during the multiple executions of step 3. In this way, the reaction liquid and the colored ink composition can be applied to the same area of ​​the fabric multiple times.

[0187] The process 3 that is performed multiple times is 2 times or more, 3 times or more, or 4 times or more. The upper limit of process 3 is not particularly limited, but it may be less than 20 times, less than 15 times, or less than 10 times. In addition, when process 3 is performed n times (n is an integer greater than 2), process 4 is preferably performed n-1 times. It is preferred to alternately and repeatedly perform process 3 and process 4.

[0188] The colored ink attaching step may be performed by the same scanning as the above-mentioned clear ink attaching step, but is preferably performed by a different scanning.

[0189] When the colored ink attaching process and the transparent ink attaching process are performed by the same scan, the "scan" in the above-mentioned process 1 and the "scan" in the process 3 are the same scan, so the reaction liquid attaching process attached to the process 1 and the process 3 is the same process. That is, the reaction liquid, the transparent ink composition, and the colored ink composition are applied to the same area of ​​the cloth by one scan of the inkjet head. In this way, the recording speed can be increased. In addition, when the cloth is transported between scans, the above-mentioned process 2 and process 4 are the same process.

[0190] On the other hand, when the colored ink attaching step and the transparent ink attaching step are performed by different scans, the "scan" in the above-mentioned step 1 and the "scan" in the step 3 are different scans, and therefore, the reaction liquid attaching steps accompanying the steps 1 and 3 become different steps. In this case, a colored ink layer can be formed on the transparent ink layer (resin layer) that is formed more well, so the penetration of the colored ink into the cloth can be further suppressed, and therefore, there is a tendency to obtain better color rendering properties.

[0191] In step 3, the minimum value of the total amount of the reaction solution and the color ink composition deposited per unit area and unit time is preferably within a range of 50 mg / (s·inch 2 ) or more, more preferably 60 mg / (s·inch 2 ) or more, more preferably 70 mg / (s·inch 2 ) or more, particularly preferably 80 mg / (s·inch 2 ) or more, more preferably 90 mg / (s·inch 2 )above.

[0192] According to the inkjet printing method of this embodiment, even when the total adhesion amount of the reaction liquid and the ink increases as described above, the penetration of the colored ink into the cloth can be suppressed, and there is a tendency that good color development properties can be obtained.

[0193] The maximum value of the total amount of the reaction solution and the color ink composition deposited per unit area and unit time is not particularly limited, but is preferably 500 mg / (s·inch 2 ) or less, more preferably 400 mg / (s·inch 2 ) or less, more preferably 300 mg / (s·inch 2 ) or less, and more preferably 200 mg / (s·inch 2 ) or less, particularly preferably 150 mg / (s·inch 2 )the following.

[0194] When the maximum value is within the above range, the color development properties and the friction fastness tend to be better.

[0195] The total amount of the reaction solution and the color ink composition deposited per unit area and unit time can be appropriately adjusted by changing the printing area in one scan, the ink application amount, the carriage moving speed, the head driving frequency, and the like.

[0196] The printing area in one scan is preferably 3 to 30 inches, for example. 2 , more preferably 5 to 20 inches 2 , more preferably 7 to 15 inches 2 .

[0197] The amount of the reaction solution and the color ink composition applied in one scan is, for example, preferably 200 to 2000 mg, more preferably 400 to 1500 mg, and even more preferably 800 to 1000 mg.

[0198] The moving speed of the carriage in the serial method is, for example, preferably 6 to 40 inch / s, more preferably 6 to 30 inch / s, further preferably 6 to 20 inch / s, particularly preferably 8 to 17 inch / s, and even more particularly preferably 10 to 15 inch / s.

[0199] The ratio (A / C) of the amount of the reaction solution attached per unit area / unit time to the amount of the colored ink composition attached per unit area / unit time in step 3 is preferably 0.1 to 1.5, more preferably 0.2 to 1.0, further preferably 0.3 to 0.7, and particularly preferably 0.4 to 0.6. If the ratio (A / C) is within the above range, there is a tendency to form a resin layer better near the surface of the fabric, and the penetration of the colored ink into the fabric can be further suppressed, and there is a tendency to obtain better color development.

[0200] 1.4.2 Colored ink composition

[0201] The colored ink composition used in the colored ink attaching step contains a pigment, resin particles, and water.

[0202] Hereinafter, each component contained in the color ink composition will be described.

[0203] <Pigment>

[0204] The colored ink composition contains a pigment. As the pigment, for example, an inorganic pigment or an organic pigment can be used. In addition, the pigment is a kind of color material. As the color material, for example, a pigment and a dye can be mentioned.

[0205] The inorganic pigment is not particularly limited, but examples thereof include carbon blacks such as furnace black, lamp black, acetylene black, and channel black; and white pigments such as iron oxide, titanium oxide, zinc oxide, and silicon oxide.

[0206] Examples of carbon blacks include CI (Colour Index Generic Name) Pigment Black 1, 7, and 11. Commercially available carbon blacks may be used, such as No. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, and No. 2200B from Mitsubishi Chemical; Raven (registered trademark) 5750, 5250, 5000, 3500, 1255, and 700 from Columbia Carbon; Rega1 (registered trademark) 400R, 330R, and 660R from CABOT; Mogul (registered trademark) L, and Monarch (registered trademark) 700, 800, 880, 900, 1000, 1100, 1300, and 1400 from Degussa; and Color Black FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Printex (registered trademark) 35, U, V, 140U, SpecialBlack 6, 5, 4A, 4, etc.

[0207] Examples of white pigments include CI Pigment White 1 which is basic lead carbonate, CI Pigment White 4 composed of zinc oxide, CI Pigment White 5 composed of a mixture of zinc sulfide and barium sulfate, CI Pigment White 6 composed of titanium dioxide, CI Pigment White 6:1 composed of titanium dioxide containing other metal oxides, CI Pigment White 7 composed of zinc sulfide, CI Pigment White 18 composed of calcium carbonate, CI Pigment White 19 composed of clay, CI Pigment White 20 composed of titanium mica, CI Pigment White 21 composed of barium sulfate, CI Pigment White 22 composed of gypsum, CI Pigment White 26 composed of magnesium oxide / silicon dioxide, CI Pigment White 27 composed of silicon dioxide, and CI Pigment White 28 composed of anhydrous calcium silicate. Among these, CI Pigment White 6 is preferably used because it is excellent in color development and hiding properties.

[0208] The average particle diameter of the white pigment is preferably more than 100nm and less than 500nm, more preferably more than 50nm and less than 450nm, and further preferably more than 200nm and less than 400nm. By making the average particle diameter of the white pigment into this range, there is a trend that can ensure the ejection stability from the inkjet head. In addition, there is a trend that can improve the hiding property. In addition, in this specification, "average particle diameter" refers to the particle diameter at the time of cumulative distribution 50vol%, that is, volume-based particle size distribution, unless otherwise specified. The determination of the average particle diameter is measured by the dynamic light scattering method and the laser diffraction light method described in JIS Z8825. Specifically, a particle size distribution meter (for example, "MicrotrackUPA" Nikkiso Co., Ltd.) using the dynamic light scattering method as the measurement principle can be adopted.

[0209] Examples of organic pigments include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthraquinone pigments, indanthrone pigments, flavonanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perindolone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, isoindolinone pigments, azomethine pigments, and azo pigments.

[0210] Specific examples of organic pigments include the following.

[0211] Examples of cyan pigments include CI Pigment Blue 1, 2, 3, 15:3, 15:4, 15:34, 16, 22, and 60; and CI Vat Blue 4 and 60. Preferably, one or a mixture of two or more selected from the group consisting of CI Pigment Blue 15:3, 15:4, and 60 can be used.

[0212] Magenta pigments include CI Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57:1, 112, 122, 123, 168, 184, 202, CI Pigment Violet 19, etc. Preferably, one or a mixture of two or more selected from the group consisting of CI Pigment Red 122, 202 and 209, and CI Pigment Violet 19 can be exemplified.

[0213] Examples of the yellow pigment include CI Pigment Yellow 1, 2, 3, 12, 13, 14C, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 119, 110, 114, 128, 129, 138, 150, 151, 154, 155, 180, and 185. Preferably, one or a mixture of two or more selected from the group consisting of CI Pigment Yellow 74, 109, 110, 128, 138, 150, and 180 can be used.

[0214] Pigments of other colors may also be used, for example, orange pigments, green pigments, etc. may be mentioned.

[0215] The pigments may be used alone or in combination of two or more.

[0216] The pigment contained in the colored ink composition is preferably a white pigment. The colored ink composition (white ink) containing a white pigment is suitable for forming a white ink layer as a base layer, but a relatively large amount of white ink is required to be attached, so there is a tendency for the total amount of attached reaction liquid and ink to become larger, and it is particularly difficult to balance friction fastness and color development. In contrast, according to the inkjet printing method involved in this embodiment, even if it is a colored ink composition containing a white pigment, excellent friction fastness and color development are obtained.

[0217] The content of the pigment (especially the white pigment) is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, further preferably 4 to 20% by mass, particularly preferably 6 to 15% by mass, and even more particularly preferably 8 to 12% by mass relative to the total amount of the colored ink composition. If the content of the pigment is within the above range, the friction fastness can be improved, and there is a tendency to obtain better color development (whiteness).

[0218] The pigment may be dispersed using a pigment dispersant. Alternatively, the pigment may be dispersed using ozone, hypochlorous acid, fuming sulfuric acid, etc. to oxidize or sulfonate the pigment surface to form a self-dispersible pigment.

[0219] The pigment dispersant has the function of dispersing the pigment in the ink. The pigment dispersant may be water-soluble, but preferably is a substance that is not completely water-soluble, and is believed to disperse the pigment by partially or completely binding or adsorbing to the pigment to increase the hydrophilicity of the pigment surface.

[0220] The pigment dispersant is a polymer compound, and examples thereof include acrylic resins and their salts such as poly(meth)acrylic acid, (meth)acrylic acid-acrylonitrile copolymers, (meth)acrylic acid-(meth)acrylate copolymers, vinyl acetate-(meth)acrylate copolymers, vinyl acetate-(meth)acrylic acid copolymers, vinylnaphthalene-(meth)acrylic acid copolymers, styrene-(meth)acrylic acid copolymers, styrene-(meth)acrylic acid copolymers, styrene-(meth)acrylic acid-(meth)acrylate copolymers, styrene-α-methylstyrene-(meth)acrylic acid copolymers, and styrene-α-methylstyrene-(meth)acrylic acid-(meth)acrylate copolymers.

[0221] In addition, examples of pigment dispersants include maleic acid resins and their salts such as styrene-maleic acid copolymers, styrene-anhydrous maleic acid copolymers, vinyl naphthalene-maleic acid copolymers, and vinyl acetate-maleic acid polyester copolymers; polyurethane resins and their salts with or without a cross-linked structure; polyvinyl alcohols; and resins such as vinyl acetate-crotonic acid copolymers and their salts.

[0222] In addition, the acrylic resin may be a copolymer of an acrylic monomer and other monomers in addition to the polymer of the acrylic monomer (acrylic monomer) as described above. For example, an acrylic ethylene resin as a copolymer with an ethylene monomer as another monomer is also referred to as an acrylic resin. In addition, for example, a resin as a copolymer of a styrene monomer and an acrylic monomer among the above-mentioned styrene resins is also included in the acrylic resin. Furthermore, when referred to as an acrylic resin, its salt and its polyester are also included.

[0223] Examples of commercially available pigment dispersants include X-200, X-1, X-205, X-220, and X-228 (manufactured by Seikyo PMC Co., Ltd.), Nopco sparse (registered trademark) 6100 and 6110 (manufactured by San Nopco Co., Ltd.), Joncryl 67, 586, 611, 678, 680, 682, and 819 (manufactured by BASF), DISPERBYK-190 (manufactured by BYK Chemical Japan Ltd.), N-EA137, N-EA157, N-EA167, N-EA177, N-EA197D, N-EA207D, and E-EN10 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).

[0224] Examples of commercially available acrylic pigment dispersants include BYK-187, BYK-190, BYK-191, BYK-194N, and BYK-199 (manufactured by BYK-Chemie Co., Ltd.), Aron A-210, A6114, AS-1100, AS-1800, A-30SL, A-7250, and CL-2 (manufactured by Toagosei Co., Ltd.).

[0225] Examples of commercially available polyurethane pigment dispersants include BYK-182, BYK-183, BYK-184, and BYK-185 (manufactured by BYK-Chemie Co., Ltd.), TEGO Disperse 710 (manufactured by Evonic Tego Chemi), and Borchi (registered trademark) Gen 1350 (manufactured by OMG Borschers).

[0226] The pigment dispersant is preferably an anionic pigment dispersant. The “anionic pigment dispersant” refers to a pigment dispersant having a negative charge as a whole, and preferably has one or more anionic groups selected from a carboxyl group, a sulfonic acid group, a phosphoric acid group, and the like.

[0227] Preferably, at least one of the pigment in the colored ink composition and the resin particles described below is anionic. In this case, the coagulation effect by the coagulant is more excellent, so there is a tendency to obtain better color development and better friction fastness.

[0228] The anionic pigment means that the pigment as a whole has a negative charge, and preferably has one or more anionic groups selected from carboxyl groups, sulfonic acid groups, phosphoric acid groups, etc. The anionic group may be directly present on the surface of the pigment, or may be present via an anionic resin dispersant adsorbed or bonded to the pigment.

[0229] The pigment dispersant may be used alone or in combination of two or more. The total content of the pigment dispersant is preferably 0.1% by mass or more and 30% by mass or less relative to 100% by mass of the colored ink composition, more preferably 0.5% by mass or more and 25% by mass or less, further preferably 1% by mass or more and 20% by mass or less, and particularly preferably 1.5% by mass or more and 15% by mass or less. The content of the pigment dispersant is 0.1% by mass or more, thereby having a tendency to ensure the dispersion stability of the pigment. In addition, if the content of the pigment dispersant is 30% by mass or less, there is a tendency to suppress the viscosity of the colored ink composition to be smaller.

[0230] Furthermore, the weight average molecular weight of the pigment dispersant is more preferably not less than 500. By using such a pigment dispersant, there is a tendency that the odor is less and the dispersion stability of the pigment can be further improved.

[0231] When a pigment (particularly, a white pigment) is dispersed by a pigment dispersant, the ratio of the pigment to the pigment dispersant is preferably 10:1 to 1:10, and more preferably 4:1 to 1:3.

[0232] <Resin pellets>

[0233] The colored ink composition contains resin particles. The resin particles can be formed in the same manner as the “resin particles” of the anionic resin particles contained in the clear ink composition described above, and therefore, description thereof will be omitted.

[0234] The resin particles in the colored ink composition are preferably anionic. In this case, the coagulation effect by the coagulant is more excellent, so there is a tendency to obtain better color development and better friction fastness.

[0235] The resin particles in the colored ink composition are preferably polyurethane resin or acrylic resin, and more preferably polyurethane resin. In this case, there is a tendency for the friction fastness to be more excellent.

[0236] The glass transition temperature (Tg) of the resin particles in the colored ink composition is preferably -60°C to 50°C, more preferably -60°C to 40°C, and further preferably -30°C to 10°C. When the glass transition temperature (Tg) of the resin particles is within the above range, the texture followability (feel) tends to be better.

[0237] The content (solid content concentration) of the resin particles is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, further preferably 4 to 20% by mass, particularly preferably 6 to 15% by mass, and even more particularly preferably 8 to 12% by mass relative to the total amount of the colored ink composition. If the content of the resin particles is within the above range, there is a tendency to obtain better color development and friction fastness.

[0238] <Water>

[0239] The colored ink composition contains water. As the water, the same water as that of the above-mentioned reaction liquid can be used.

[0240] The water content is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 50% by mass or more, relative to the total mass of the colored ink composition. The upper limit of the water content is not particularly limited, but, for example, is preferably 90% by mass or less, and more preferably 70% by mass or less, relative to the total mass of the colored ink composition.

[0241] <Organic solvents>

[0242] The colored ink composition may contain an organic solvent. The type and content of the organic solvent may be the same as those of the above-mentioned reaction solution.

[0243] In the colored ink composition, the organic solvent preferably includes alkanediols, alkylene glycol ethers and trialkylene glycols, more preferably includes 1,2-alkanediol, alkylene glycol ethers and trialkylene glycols, and further preferably includes propylene glycol, triethylene glycol monobutyl ether and triethylene glycol. When the organic solvent includes these solvents, the color development and friction fastness are sometimes more excellent.

[0244] In addition, the colored ink composition preferably contains 3.0% by mass or more of an organic solvent having a normal boiling point of 250° C. or more, more preferably 4.0% by mass or more, and further preferably 5.0% by mass or more. The upper limit of the content is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.

[0245] When an organic solvent having a normal boiling point of 250°C or higher is contained in the above range, the nozzle of the inkjet head is moisturized, and there is a tendency to improve the ejection reliability (continuous printing stability). This method is particularly useful when condensation is easily generated in the nozzle and the reaction liquid and the colored ink composition are attached to the same area of ​​the fabric in the same scan.

[0246] In addition, examples of organic solvents having a normal boiling point of 250°C or higher include glycerin, polyethylene glycol monomethyl ether, etc. In addition, organic solvents having a normal boiling point of 250°C or higher are also referred to as humectants. Organic solvents having a normal boiling point of 250°C or higher are more preferably at a normal boiling point of 270°C or higher, and even more preferably at a normal boiling point of 280°C or higher.

[0247] The content of the organic solvent is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, further preferably 15 to 35% by mass, and particularly preferably 20 to 30% by mass relative to the total amount of the colored ink composition. If the content of the organic solvent is within the above range, the color development and friction fastness may be more excellent.

[0248] <Surfactant>

[0249] The colored ink composition may contain a surfactant, and the type of the surfactant and the like may be the same as that of the above-mentioned reaction solution.

[0250] The lower limit of the content of the surfactant is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, and particularly preferably 0.3% by mass or more, based on the total mass of the colored ink composition.

[0251] In addition, the upper limit of the content of the surfactant is preferably 3% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, and particularly preferably 0.8% by mass or less relative to the total mass of the colored ink composition. If the content of the surfactant is within the above range, there is a tendency that the permeability of the colored ink composition to the fabric can be easily and satisfactorily adjusted.

[0252] <Other ingredients>

[0253] The colored ink composition may contain additives such as a pH adjuster, a preservative / antifungal agent, a rust inhibitor, a chelating agent, a viscosity modifier, a solubilizing agent, and an antioxidant as needed. The content of such additives is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, and even more preferably 0.1 to 1% by mass relative to the total amount of the colored ink composition.

[0254] <Physical properties>

[0255] From the viewpoint of reducing skin irritation, the pH of the colored ink composition is preferably 2.0 or more, more preferably 5.0 or more, and further preferably 7.0 or more. From the same viewpoint, the upper limit of the pH is preferably 11.5 or less, more preferably 10 or less, further preferably 9.0 or less, and particularly preferably 8.0 or less.

[0256] The viscosity of the colored ink composition is preferably 1.0 to 10 mPa·s, more preferably 2.0 to 10 mPa·s, further preferably 3.0 to 8.0 mPa·s, and particularly preferably 4.0 to 6.0 mPa·s. In particular, when the viscosity is 4.0 mPa·s or more, there is a tendency to obtain better color development. When the viscosity is 6.0 mPa·s or less, there is a tendency to obtain better ejection stability.

[0257] The surface tension of the clear ink composition is preferably 10 to 40 mN / m, more preferably 15 to 35 mN / m, further preferably 20 to 30 mN / m, and particularly preferably 20 to 27 mN / m.

[0258] 1.5 Second transparent ink adhesion process

[0259] The inkjet printing method according to the present embodiment may include a second clear ink attaching step in which a second clear ink composition containing anionic resin particles and water is further attached by inkjet method to the region of the fabric to which the colored ink composition is attached.

[0260] Thus, the colored ink layer is coated with the second transparent ink, and thus the friction fastness is further improved. In particular, there is an effect that the discoloration caused by dry friction can be further suppressed.

[0261] The adhesion of the second clear ink composition in the second clear ink adhesion step can be performed by moving the inkjet head relative to the recording area on the fabric.

[0262] In the second transparent ink adhesion step, the reaction liquid and the second transparent ink composition may be applied to the same area of ​​the fabric by scanning the inkjet head once, as in the above transparent ink adhesion step. In this case, the method may be the same as in the above step 1, and the adhesion amount, etc. may also be the same.

[0263] The minimum value of the adhesion amount of the second transparent ink per unit area and unit time during one scan of the inkjet head is preferably within a range of 15 mg / (s·inch 2 ) or more, more preferably 20 mg / (s·inch 2 ) or more, more preferably 25 mg / (s·inch 2 ) or more, particularly preferably 30 mg / (s·inch 2 )above.

[0264] The maximum value of the adhesion amount of the second transparent ink per unit area and per unit time during one scan of the inkjet head is not particularly limited, but is preferably 150 mg / (s·inch 2 ) or less, more preferably 100 mg / (s·inch 2 ) or less, more preferably 75 mg / (s·inch 2 ) or less, particularly preferably 50 mg / (s·inch 2 )the following.

[0265] The total amount of the second ink composition deposited per unit area and per unit time can be appropriately adjusted by changing the printing area in one scan, the ink application amount, the carriage moving speed, the head driving frequency, and the like.

[0266] The printing area in one scan is preferably 3 to 30 inches, for example. 2 , more preferably 5 to 20 inches 2 , more preferably 7 to 15 inches 2 .

[0267] The amount of the second ink composition applied in one scan is, for example, preferably 50 to 500 mg, more preferably 100 to 400 mg, and even more preferably 200 to 350 mg.

[0268] The moving speed of the carriage in the serial method is, for example, preferably 6 to 40 inch / s, more preferably 6 to 30 inch / s, further preferably 6 to 20 inch / s, particularly preferably 8 to 17 inch / s, and even more particularly preferably 10 to 15 inch / s.

[0269] The second transparent ink composition is the same as the transparent ink composition described above, and therefore, the description thereof is omitted. As the second transparent ink composition, the same composition as the transparent ink composition described above may be used. By using the same composition, there is no need to separately provide a nozzle array, which is preferred in that the recording device can be miniaturized.

[0270] 1.6 Heating and drying process

[0271] The inkjet printing method according to the present embodiment may include a step of heating and drying the ink and the like adhered to the fabric (heating and drying step) after the aforementioned step of adhering the reaction solution and the ink.

[0272] The heat drying method is not particularly limited, and examples thereof include a conveyor type open hearth furnace, a normal pressure steam method, a high pressure steam method, a thermal curing method, etc. The heat source during the heat drying is not particularly limited, and for example, an infrared lamp or the like can be used.

[0273] The heating and drying temperature is preferably a temperature at which the resin particles that may be included in the ink melt and the medium such as water volatilizes. The heating and drying temperature is preferably, for example, 100°C or more and 250°C or less, more preferably 120°C or more and 230°C or less, further preferably 140°C or more and 200°C or less, and particularly preferably 150°C or more and 180°C or less. Here, the heating and drying temperature in the heating and drying step refers to the surface temperature of the image or the like formed on the cloth. The time for performing the heating and drying is not particularly limited, but, for example, is preferably 30 seconds or more and 20 minutes or less, and more preferably 2 minutes or more and 5 minutes or less.

[0274] 1.7 Other processes

[0275] The inkjet printing method of this embodiment may also include a step of washing the recorded cloth, a step of heating and drying again, etc. During washing, as required, a soaping treatment may be performed to wash away components such as ink that are not fixed to the cloth using hot soap solution.

[0276] 1.8 Inkjet Recording Device

[0277] An inkjet recording apparatus that can be applied to the inkjet printing method according to the present embodiment will be described.

[0278] As an example of an inkjet recording device, Figure 1 Figure 2 shows a perspective view of a serial printer. Figure 1As shown, the serial printer 20 includes a conveying unit 220 and a recording unit 230. The conveying unit 220 conveys the recording medium F supplied to the serial printer to the recording unit 230, and discharges the recorded recording medium to the outside of the serial printer. Specifically, the conveying unit 220 includes various paper feed rollers, and conveys the conveyed recording medium F along the conveying direction TD.

[0279] In addition, the recording unit 230 includes: a carriage 234 equipped with an inkjet head 231, wherein the inkjet head 231 has a nozzle for ejecting a reaction liquid to the recording medium F transported from the transport unit 220, a nozzle for ejecting a transparent ink composition, and a nozzle for ejecting a colored ink composition; and a carriage moving mechanism 235, which moves the carriage 234 along the scanning direction SD of the recording medium F.

[0280] Figure 2 An example of each nozzle array included in the nozzle surface of the inkjet head 231 is shown. Figure 2 In FIG. 1 , the inkjet head 231 has a plurality of nozzle rows A to H along the scanning direction SD. The nozzle rows are composed of a plurality of nozzles arranged in a direction (transport direction TD) intersecting the direction (scanning direction SD) in which the inkjet head 231 moves.

[0281] At this time, when the nozzle array ejecting the reaction liquid is projected along the scanning direction SD, at least a portion of the nozzle array ejecting the transparent ink composition is overlapped in the conveying direction TD, so that the above-mentioned step 1 (the reaction liquid and the transparent ink composition are applied to the same area of ​​the fabric by a single scan of the inkjet head) can be performed. Similarly, when the nozzle array ejecting the reaction liquid is projected along the scanning direction SD, at least a portion of the nozzle array ejecting the colored ink composition is overlapped in the conveying direction TD, so that the above-mentioned step 3 (the reaction liquid and the colored ink composition are applied to the same area of ​​the fabric by a single scan of the inkjet head) can be performed.

[0282] The ink etc. ejected from each nozzle row can be appropriately selected, but for example, it is preferred to select rows A to B as nozzle rows for ejecting reaction liquid, rows C to D as nozzle rows for ejecting clear ink composition, and rows E to H as nozzle rows for ejecting colored ink composition.

[0283] In the case of a serial printer, the inkjet head 231 has a length smaller than the width of the recording medium, and the head performs recording while moving in a scanning direction SD intersecting the conveying direction TD of the recording medium F. In addition, in the serial printer, the head 231 is mounted on a carriage 234 that moves in a predetermined direction, and the head moves along with the movement of the carriage, thereby ejecting the ink composition and the reaction liquid on the recording medium. The recording medium may be conveyed between scans.

[0284] In addition, the inkjet device is not limited to the above-mentioned serial printer, and may be a line printer. Figure 3 As another example of an inkjet recording device, a schematic side view of a line printer is shown. Figure 3 As shown, the line printer 1 includes a supply unit 100 , a transport mechanism 200 that transports a recording medium in a transport direction, a line head 300 that ejects ink onto the recording medium to make it adhere, a control unit 500 , and a discharge unit 700 .

[0285] The conveying mechanism is a mechanism for conveying the recording medium along the conveying direction. Figure 3 In the embodiment, a roll-shaped recording medium F is supplied from a supply unit 100 to a conveying mechanism 200, and the conveying mechanism 200 is configured to be able to convey the recording medium F supplied from the supply unit 100 to a line head 300. Specifically, the conveying mechanism 200 includes a first paper feed roller 201 and a second paper feed roller 202, and is configured to be able to convey the supplied recording medium F to the line head 300 on the downstream side of the conveying direction. As a conveying method of the conveying mechanism 200, a conventionally known method can be appropriately used, and one or more rollers or a belt conveyed by rollers can also be used.

[0286] The line printer 1 includes a line head 300 having a length corresponding to the width of the recording medium F. The line head 300 may be composed of a plurality of line nozzles. Figure 3 , the line head 300 includes a first line head 310, a second line head 320, a third line head 330, and a fourth line head 340. When there is no need to distinguish between the first line head 310, the second line head 320, the third line head 330, and the fourth line head 340, they are simply referred to as the line head 300.

[0287] The line head 300 has: a cavity for containing a reaction liquid, a transparent ink composition, and a colored ink composition (ink, etc.); a discharge drive unit provided for each cavity; and a nozzle for discharging ink, etc. The cavity, the discharge drive unit provided for each cavity, and the nozzle may be independent of each other, and a plurality of them may be provided on one head. The discharge drive unit may be formed by using an electro-mechanical conversion element such as a piezoelectric element that changes the volume of the cavity by mechanical deformation, an electron-heat conversion element that generates bubbles in the ink by generating heat and discharges the bubbles, etc.

[0288] The structure of the line head 300 is preferably such that, for example, the reaction liquid is ejected from the first line head 310 and the transparent ink composition is ejected from the second line head 320. In this way, the above-mentioned step 1 can be appropriately performed. In addition, it is preferred that the reaction liquid is ejected from the third line head 330 and the colored ink composition is ejected from the fourth line head 340. In this way, the reaction liquid attachment step and the colored ink attachment step can be easily performed simultaneously.

[0289] In a line printer, the head does not (almost) move but is fixed, and recording is performed by a single scan of the inkjet head. Line printers have an advantage over serial printers in that they have a faster recording speed.

[0290] 2. Ink set

[0291] An ink set according to one embodiment of the present invention is an ink set used in the above-mentioned inkjet printing method, and includes the above-mentioned reaction liquid, the above-mentioned clear ink composition, and the above-mentioned colored ink composition.

[0292] According to the ink set according to the present embodiment, good color development and friction fastness can be obtained. The reaction liquid, the clear ink composition, and the colored ink composition included in the ink set are as described above, and therefore, description thereof will be omitted.

[0293] Hereinafter, a second embodiment of the present invention will be described. The embodiment described below is a method for illustrating an example of the present invention. The present invention is not limited by the following embodiment, and also includes various modified modes implemented within the scope of not changing the gist of the present invention. In addition, not all of the following descriptions are necessary structures of the present invention.

[0294] In the present specification, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as a lower limit and an upper limit.

[0295] In this specification, the "inkjet method" refers to a droplet ejection method based on the inkjet method.

[0296] In the present specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid, and "(meth)acrylate" means acrylate or methacrylate.

[0297] 1. Inkjet printing and dyeing method

[0298] An inkjet printing method according to one embodiment of the present invention comprises: a reaction liquid attaching step of attaching a reaction liquid containing a coagulant and water for coagulating components in ink to a fabric; a transparent ink attaching step of attaching a transparent ink composition containing anionic resin particles and water that react with the coagulant and coagulate to the fabric; and a colored ink attaching step of attaching a colored ink composition containing a pigment, resin particles, and water to a region of the fabric to which the transparent ink composition is attached by an inkjet method, and after the reaction liquid attaching step and the transparent ink attaching step, a pressure imparting step of imparting pressure to the region of the fabric to which the reaction liquid and the transparent ink composition are attached, the fabric is placed on a mounting table, and the reaction liquid attaching step, the transparent ink attaching step, the pressure imparting step, and the colored ink attaching step are performed in a manner that does not change the relative positional relationship between the fabric and the mounting table between the steps.

[0299] In the past, in order to improve the color development of the color material in inkjet printing, a reaction liquid that condenses the components of the ink is attached to the cloth. This treatment usually uses a device or equipment different from the inkjet recording device or is often a manual operation, so large equipment and complicated processes are required. Therefore, the following method is studied: the reaction liquid and the ink are continuously attached in the same device. If this method is used, it is not necessary to use other devices and equipment, and the process can be simplified.

[0300] However, when the reaction liquid and the ink are continuously attached in the same device, the fuzzing of the fabric cannot be suppressed, and image quality is likely to be deteriorated.

[0301] In contrast, according to the inkjet printing method of this embodiment, the coagulant in the reaction liquid coagulates the components of the transparent ink on the cloth, thereby forming a high-viscosity gel-like coagulant near the surface of the cloth. By applying pressure (friction) to the cloth surface to which the coagulant is attached using a rubber scraper or the like, the cloth is fixed in a state where the fuzz is pressed down by the viscosity of the gel-like coagulant. Furthermore, colored ink is attached thereto, thereby enabling image formation to be performed with the influence of the fuzz on the printing surface reduced.

[0302] Hereinafter, each step of the inkjet printing method according to the present embodiment will be described.

[0303] 1.1 Reaction solution adhesion process

[0304] The inkjet textile printing method according to the present embodiment includes a reaction liquid adhering step of making a reaction liquid containing a coagulant for coagulating components in ink and water adhere to a fabric.

[0305] 1.1.1 Attachment method

[0306] The means for attaching the reaction liquid to the fabric is not particularly limited, but examples thereof include: immersion coating in which the fabric is immersed in the reaction liquid, roller coating in which the reaction liquid is attached using a brush, a roller, a spatula, a roller coater, etc., spray coating in which the reaction liquid is sprayed by a spray device, etc., and inkjet coating in which the reaction liquid is attached by an inkjet method. Among these, coating by an inkjet method is preferred, and the reaction liquid attachment step and the transparent ink attachment step described later are preferably performed by an inkjet method. In this case, the reaction liquid and the transparent ink can be selectively attached to the image forming area of ​​the colored ink attached to the fabric by the colored ink attachment step described later, and the generation of processing marks in the non-image forming area can be suppressed.

[0307] The total coating amount of the reaction solution and the clear ink composition described below is preferably 0.02 g / inch 2 More preferably 0.05 g / inch 2 More preferably, 0.07 g / inch 2 Above, particularly preferably 0.10 g / inch 2 When the total coating amount is within the above range, the fuzz fixing effect is further improved, and there is a tendency that the image quality disturbance caused by the fuzz of the fabric can be further reduced.

[0308] The upper limit of the total coating amount is not particularly limited, but is preferably 1.0 g / inch 2 Below, more preferably 0.50g / inch 2 Below, more preferably 0.30g / inch 2 Below, particularly preferably 0.15 g / inch 2 the following.

[0309] The coating amount ratio of the reaction liquid to the transparent ink composition described later is preferably 1:10 to 10:1, more preferably 3:10 to 10:3, further preferably 5:10 to 10:5, particularly preferably 7:10 to 10:7, and even more particularly preferably 9:10 to 10:9. If the coating amount ratio is within the above range, the fuzz fixing effect is further improved, and there is a tendency to further reduce the disturbance of image quality caused by the fuzz of the fabric.

[0310] The time difference between the adhesion of the reaction liquid and the transparent ink composition described later in the same area of ​​the fabric is preferably within 30 seconds, more preferably within 15 seconds, further preferably within 5 seconds, further preferably within 1 second, particularly preferably within 0.5 seconds, and further preferably within 0.1 seconds. If the time difference is within the above range, the image quality disturbance caused by the fuzzing of the fabric can be further reduced, and there is a tendency that the color development can be further improved.

[0311] It is preferred that the reaction liquid adhesion step and the clear ink adhesion step described later include the following step 1.

[0312] Step 1: Applying the reaction liquid and the transparent ink composition to the same area of ​​the fabric in one scan

[0313] According to the coating in step 1, the reaction liquid and the clear ink composition can be continuously applied to the fabric in the same device by the inkjet method, and the image quality disturbance caused by the fuzzing of the fabric can be further reduced, and the color development property tends to be further improved.

[0314] Here, "scanning" in step 1 means moving the inkjet head relative to the recording area on the fabric. In this case, the inkjet head may be moved relative to the fabric, or the fabric may be moved relative to the inkjet head. In addition, the relative positional relationship between the inkjet head and the fabric may be changed by moving both the inkjet head and the fabric.

[0315] Therefore, the "scanning" in step 1 is, for example, Fig. 9 , Fig.10 In the serial inkjet printing apparatus 1 shown, the carriage 13 having the inkjet head 14 performs recording while moving in the scanning direction SD intersecting with the moving direction TD of the printing target material P placed on the stage 7 .

[0316] On the other hand, the "scanning" in step 1 can also be done in Fig.13 In the line printer shown in the figure, the cloth is recorded while being relatively moved in a direction intersecting the width direction relative to the line head 300 having a length equivalent to the width of the cloth. In line recording, the inkjet head (line head) does not move during recording but is fixed, and recording is performed by one scan.

[0317] "The length equivalent to the width of the cloth" is not limited to the case where the width of the cloth is completely consistent with the length (width) of the line head, but can also be a length greater than the length equivalent to the width of the cloth, or a length equivalent to the width of the cloth on which the ink should be ejected (the image should be recorded) (the recorded width).

[0318] 1.1.2 Reaction solution

[0319] The reaction liquid used in the reaction liquid attachment step contains a coagulant for coagulating the components in the ink and water. Hereinafter, each component contained in the reaction liquid will be described.

[0320] 1.1.2.1 Coagulant

[0321] The reaction liquid contains a coagulant for coagulating the components in the ink. The coagulant has the following function: by acting on the dispersibility of the components such as the anionic resin particles contained in the transparent ink composition and the pigment and resin particles contained in the colored ink composition, at least one of these components is coagulated. The degree of coagulation of the dispersion by the coagulant varies depending on the type of the coagulant and the object, and can be adjusted. By such a coagulation action, for example, the color development and fixability of the image can be improved.

[0322] The reaction solution preferably contains, as a coagulant, at least one selected from, for example, an organic acid, a polyvalent metal salt, and a cationic polymer. If such a coagulant is used, friction fastness and color development may be further improved.

[0323] Preferred examples of organic acids include poly(meth)acrylic acid, formic acid, acetic acid, propionic acid, glycolic acid, oxalic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, citric acid, tartaric acid, lactic acid, pyruvic acid, pyrrolidonecarboxylic acid, pyronecarboxylic acid, pyrrolecarboxylic acid, furancarboxylic acid, picolinic acid, coumaric acid, thiophenecarboxylic acid, nicotinic acid, or derivatives of compounds thereof or salts thereof.

[0324] The organic acid may be used alone or in combination of two or more. In addition, a substance that is both a salt of an organic acid and a metal salt is included in the metal salt described below.

[0325] The polyvalent metal salt is a compound composed of a metal ion having a valence of two or more and an anion. Examples of the metal ion having a valence of two or more include ions of calcium, magnesium, copper, nickel, zinc, barium, aluminum, titanium, strontium, chromium, cobalt, and iron. From the viewpoint of excellent coagulation of the components of the ink, at least one of a calcium ion and a magnesium ion is also preferred among the metal ions constituting the polyvalent metal salt.

[0326] Anions constituting the polyvalent metal salt are inorganic ions or organic ions. Examples of such inorganic ions include chloride ions, bromide ions, iodide ions, formate ions, nitrate ions, sulfate ions, hydroxide ions, etc. Examples of organic ions include organic acid ions, such as carboxylic acid ions.

[0327] As a specific example of the above-mentioned polyvalent metal salt, calcium carbonate, calcium formate, calcium nitrate, calcium chloride, calcium sulfate, magnesium sulfate, calcium hydroxide, magnesium chloride, magnesium carbonate, barium sulfate, barium chloride, zinc carbonate, zinc sulfide, aluminum silicate, calcium silicate, magnesium silicate, copper nitrate, calcium acetate, magnesium acetate, aluminum acetate, calcium propionate, magnesium propionate, aluminum propionate, calcium lactate, magnesium lactate, aluminum lactate, etc. such as heavy calcium carbonate and light calcium carbonate can be cited. These polyvalent metal salts can also be used alone or in combination of two or more. From the viewpoint of being able to obtain sufficient solubility in water, among these, at least any one of magnesium sulfate, calcium formate, calcium nitrate, aluminum lactate, and calcium propionate is preferred. In addition, these metal salts can also be metal salts having hydration water in the raw material form such as magnesium sulfate heptahydrate and calcium nitrate tetrahydrate.

[0328] Cationic polymers refer to polymer compounds having a cationic group. Examples of cationic polymers include cationic polyurethane resins, cationic olefin resins, cationic amine resins, and cationic amide resins.

[0329] The cationic amine resin may be any resin having an amino group, and examples thereof include allylamine resins, polyamine resins, and quaternary ammonium salt polymers.

[0330] As allylamine resin, there can be mentioned resins having a structure derived from allyl groups in the main skeleton of the resin. As polyamine resin, there can be mentioned resins having amino groups in the main skeleton of the resin. As quaternary ammonium salt polymer, there can be mentioned resins having quaternary ammonium salts in the structure. Among cationic polymers, cationic amine resins are not only excellent in reactivity, but also easy to obtain, and therefore are preferred.

[0331] The coagulants may be used alone or in combination of two or more.

[0332] From the viewpoint of better color development and friction fastness, the lower limit of the content of the coagulant is preferably 0.5 mass % or more, more preferably 1 mass % or more, further preferably 2 mass % or more, particularly preferably 3 mass % or more, and even more preferably 4 mass % or more, relative to the total amount of the reaction solution.

[0333] The upper limit of the content of the coagulant is not particularly limited, but is, for example, preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, particularly preferably 8% by mass or less, and even more preferably 6% by mass or less, relative to the total amount of the reaction solution.

[0334] In particular, the coagulant contains an organic acid, preferably 1 to 6% by mass of the organic acid relative to the total amount of the reaction solution, more preferably 1 to 5% by mass of the organic acid, and still more preferably 2 to 4% by mass of the organic acid. In this case, the transparent ink composition can be more effectively coagulated, the fluff fixing effect is further improved, and there is a tendency to further reduce the disturbance of image quality caused by the fluffing of the fabric.

[0335] 1.1.2.2 Water

[0336] The reaction solution contains water. Examples of water include pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water, and water containing ionic impurities such as ultrapure water. In addition, if water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, the generation of bacteria and fungi can be suppressed when the reaction solution is stored for a long time.

[0337] The content of water is preferably 40% by mass or more, more preferably 45% by mass or more, more preferably 50% by mass or more, and particularly preferably 60% by mass or more relative to the total amount of the reaction solution. The upper limit of the content of water is not particularly limited, but for example, it is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less relative to the total amount of the reaction solution.

[0338] 1.1.2.3 Organic solvents

[0339] The reaction liquid may contain an organic solvent. Examples of the organic solvent include esters, alkylene glycol ethers, cyclic esters, amides, alcohols, and polyols.

[0340] Examples of the esters include glycol monoacetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and methoxybutyl acetate; and glycol diesters such as ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, ethylene glycol diacetate propionate, ethylene glycol butyric acid acetate, diethylene glycol butyric acid acetate, diethylene glycol propionate acetate, diethylene glycol butyric acid acetate, propylene glycol propionate acetate, propylene glycol butyric acid acetate, dipropylene glycol butyric acid acetate, and dipropylene glycol propionate acetate.

[0341] The alkylene glycol ethers may be monoethers or diethers of alkylene glycols, and are preferably alkyl ethers. Specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, and tripropylene glycol monobutyl ether. Alkylene glycol monoalkyl ethers; and alkylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol methyl butyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and tripropylene glycol dimethyl ether.

[0342] Examples of the cyclic esters include cyclic esters (lactones) such as β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, β-butyrolactone, β-valerolactone, γ-valerolactone, β-caprolactone, γ-caprolactone, δ-caprolactone, β-heptanolactone, γ-heptanolactone, δ-heptanolactone, ε-heptanolactone, γ-octanolactone, δ-octanolactone, ε-octanolactone, δ-nonanolactone, ε-nonanolactone, and ε-decanolactone, and compounds wherein the hydrogen of the methylene group adjacent to the carbonyl group thereof is substituted with an alkyl group having 1 to 4 carbon atoms.

[0343] Examples of the amides include cyclic amides, non-cyclic amides, etc. Examples of the non-cyclic amides include alkoxyalkylamides, etc.

[0344] Examples of the cyclic amides include lactams, and examples of the lactams include pyrrolidones such as 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone.

[0345] Examples of the alkoxyalkylamides include 3-methoxy-N,N-dimethylpropionamide, 3-methoxy-NN-diethylpropionamide, 3-methoxy-N,N-methylethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-diethylpropionamide, 3-ethoxy-N,N-methylethylpropionamide, 3-n-butoxy-N,N-dimethylpropionamide, 3-n-butoxy-N,N-diethylpropionamide, 3-n-but ... -n-propoxy-N,N-dimethylpropionamide, 3-n-propoxy-N,N-diethylpropionamide, 3-n-propoxy-N,N-methylethylpropionamide, 3-isopropoxy-N,N-dimethylpropionamide, 3-isopropoxy-N,N-diethylpropionamide, 3-isopropoxy-N,N-methylethylpropionamide, 3-tert-butoxy-N,N-dimethylpropionamide, 3-tert-butoxy-N,N-diethylpropionamide, 3-tert-butoxy-N,N-methylethylpropionamide, N,N-dimethylisobutyramide, etc.

[0346] Examples of alcohols include compounds in which one hydrogen atom of an alkane is replaced by a hydroxyl group. The alkane is preferably a structure having 10 or less carbon atoms, more preferably a structure having 6 or less carbon atoms, and more preferably a structure having 3 or less carbon atoms. The alkane has 1 or more carbon atoms, preferably 2 or more carbon atoms. The alkane may be a straight chain type or a branched chain type. Examples of alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert-butanol, isobutanol, n-pentanol, 2-pentanol, 3-pentanol, tert-pentanol, 2-phenoxyethanol, benzyl alcohol, phenoxypropanol, and the like.

[0347] Polyols have a structure having two or more hydroxyl groups in a molecule. Polyols can be divided into, for example, alkanediols and polyols.

[0348] Examples of alkanediols include compounds in which an alkane is substituted with two hydroxyl groups. Examples of alkanediols include 1,2-alkanediol, which is a general term for compounds in which the 1- and 2-positions of an alkane are substituted with hydroxyl groups, and other alkanediols other than 1,2-alkanediol.

[0349] Examples of 1,2-alkanediols include ethylene glycol, 1,2-propylene glycol (propylene glycol), 1,2-butanediol (1,2BD), 1,2-pentanediol (1,2PD), 1,2-hexanediol (1,2HD), 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 3-methyl-1,2-butanediol, 3-methyl-1,2-pentanediol, 4-methyl-1,2-pentanediol, 3,4-dimethyl-1,2- Pentanediol, 3-ethyl-1,2-pentanediol, 4-ethyl-1,2-pentanediol, 3-methyl-1,2-hexanediol, 4-methyl-1,2-hexanediol, 5-methyl-1,2-hexanediol, 3,4-dimethyl-1,2-hexanediol, 3,5-dimethyl-1,2-hexanediol, 4,5-dimethyl-1,2-hexanediol, 3-ethyl-1,2-hexanediol, 4-ethyl-1,2-hexanediol, 3-ethyl-4-methyl-1,2-hexanediol, and the like.

[0350] Examples of other alkanediols include 1,3-propanediol, 1,3-butanediol (also known as 1,3-butanediol), 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2,4-pentanediol, 2-methyl-1,3-propanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,3-pentanediol, 3-methyl-1,5-pentanediol, 2-methylpentane-2,4-diol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, and 2-methyl-2-propyl-1,3-propanediol.

[0351] Examples of the polyols include condensates obtained by intermolecular condensation of two or more molecules of alkanediols at hydroxyl groups, and compounds having three or more hydroxyl groups.

[0352] Examples of the condensate obtained by intermolecular condensation of two or more molecules of alkanediols at a hydroxyl group include dialkylene glycols such as diethylene glycol and dipropylene glycol; and trialkylene glycols such as triethylene glycol and tripropylene glycol.

[0353] The compound having three or more hydroxyl groups is a compound having three or more hydroxyl groups with an alkane or polyether structure as a skeleton. Examples of the compound having three or more hydroxyl groups include glycerol, trimethylolethane, trimethylolpropane, 1,2,5-hexanetriol, 1,2,6-hexanetriol, pentaerythritol, and polyoxypropylenetriol.

[0354] The organic solvent may be used alone or in combination of two or more.

[0355] Among these, the organic solvent preferably contains alkanediols, more preferably contains 1,2-alkanediol, and particularly preferably contains propylene glycol. When the organic solvent contains these solvents, the color development property and friction fastness may be more excellent.

[0356] The content of the organic solvent is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, further preferably 15 to 35% by mass, and particularly preferably 20 to 30% by mass relative to the total amount of the reaction solution. When the content of the organic solvent is within the above range, the color development and friction fastness may be further improved.

[0357] 1.1.2.4 Surfactants

[0358] The reaction solution may also contain a surfactant. The surfactant can be used to reduce the surface tension of the reaction solution, for example, to adjust and improve the permeability to the fabric. As the surfactant, any of nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used, and they can also be used in combination. In addition, among the surfactants, acetylene surfactants (acetylene glycol surfactants), silicone surfactants, and fluorine-based surfactants can be more preferably used, and acetylene surfactants can be further preferably used.

[0359] The acetylene surfactant (acetylene glycol surfactant) is not particularly limited, but examples thereof include Surfynol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, DF110D (trade name, Air Products and Chemicals Inc.), Olfine B, Y, P, A, STG, SPC, E1004, E1010, PD-001, PD-002W, PD-003, PD-004, PD-005, EXP.4001, EXP.4036, EXP.4051, EXP.4123, EXP.4200, EXP.4300, AF-103, AF-104, AK-02, SK-14, AE-3 (trade names, manufactured by Nissin Chemical Industry Co., Ltd.), acetylene alcohol E00, E00P, E40, E100 (trade names, manufactured by Kawaken Fine Chemicals Co., Ltd.).

[0360] The silicone-based surfactant is not particularly limited, but preferably a polysiloxane-based compound is used. The polysiloxane-based compound is not particularly limited, but for example, a polyether-modified silicone is used. Examples of commercially available products of the polyether-modified organosiloxane include BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, and BYK-348 (trade names, manufactured by BYK), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6004, KF-6011, KF-6012, KF-6015, and KF-6017 (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0361] As the fluorine-based surfactant, a fluorine-modified polymer is preferably used, and a specific example thereof is BYK-340 (trade name, manufactured by BYK-Chemie Japan Ltd.).

[0362] The surfactant may be used alone or in combination of two or more.

[0363] The reaction liquid preferably contains a surfactant having an HLB value of 10 or more. In the case of a surfactant having an HLB value of 10 or more, the permeability of the reaction liquid into the fabric can be adjusted satisfactorily, and there is a tendency that the reaction liquid is more likely to stay near the surface of the fabric. As a result, there is a tendency that the color development property is more excellent.

[0364] In this specification, the "HLB value" (value of hydrophile and liophile balance) numerically represents the hydrophilicity / hydrophobicity balance of a compound. Here, the HLB value is a value calculated by the Griffin method and can be obtained by the following formula (1).

[0365] HLB value = 20 × total formula weight of hydrophilic part / molecular weight... (1)

[0366] Specific examples of surfactants having an HLB value of 10 or more according to the Griffin method are listed below.

[0367] Examples of acetylene-based surfactants (acetylene glycol-based surfactants) having an HLB value of 10 or more include Olfine E1010 (HLB value 12), E1020 (HLB value 15 to 16), EXP.4200 (HLB value 10 to 13), and EXP.4123 (HLB value 10 to 13) [trade name, manufactured by Nissin Chemical Industry Co., Ltd.].

[0368] Examples of the silicone surfactant having an HLB value of 10 or more include BYK-348 (HLB value 11) [trade name, manufactured by BYK], KF-6011 (HLB value 14.5), KF-6013 (HLB value 10), KF-6043 (HLB value 14.5), KF-643 (HLB value 14), KF-640 (HLB value 14), KF-351A (HLB value 12), KF-354L (HLB value 16) [trade name, manufactured by Shin-Etsu Silicone Co., Ltd.], FZ-2105 (HLB value 11), L-7604 (HLB value 13), FZ-2104 (HLB value 14) [trade name, manufactured by Dow Corning Toray Co., Ltd.], SILWET L-7604 (HLB value 13), SILWET L-7607N (HLB value 17), SILWET FZ-2104 (HLB value 14) or SILWET FZ-2161 (HLB value 20) [trade names, manufactured by Eureka Japan Co., Ltd.], etc.

[0369] When the reaction liquid contains a surfactant, the content of the surfactant is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, further preferably 2.0% by mass or less, particularly preferably 1.5% by mass or less, and even more particularly preferably 1.0% by mass or less, relative to the total amount of the reaction liquid. If the content of the surfactant is within the above range, especially 2.0% by mass or less, the viscosity of the mixed liquid when the reaction liquid and the transparent ink are mixed tends to be high, the fluff fixing effect is further improved, and there is a tendency to further reduce the disturbance of the image quality caused by the fluffing of the cloth.

[0370] The lower limit of the content of the surfactant is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, based on the total amount of the reaction solution.

[0371] 1.1.2.5 Other ingredients

[0372] The reaction solution may also contain additives such as pH adjusters, preservatives / mildew preventers, rust preventers, chelating agents, viscosity modifiers, solubilizers, antioxidants, etc. as needed. The content of such additives is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, and further preferably 0.1 to 1% by mass relative to the total amount of the reaction solution.

[0373] The pH adjuster is not particularly limited, and examples thereof include an acid, a base, and an appropriate combination of a weak acid and a weak base.

[0374] Examples of acids and bases used in such a combination include sulfuric acid, hydrochloric acid, nitric acid, etc. as inorganic acids; lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium dihydrogen phosphate, disodium hydrogen phosphate, potassium carbonate, sodium carbonate, sodium bicarbonate, ammonia, etc. as inorganic bases; triethanolamine, diethanolamine, monoethanolamine, tripropanolamine, triisopropanolamine, diisopropanolamine, trishydroxymethylaminomethane (THAM), etc. as organic bases; adipic acid, citric acid, succinic acid, lactic acid, N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid, etc. as organic acids can also be used. (BES), 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES), morpholinoethanesulfonic acid (MES), carbamoyl iminodiacetic acid (ADA), piperazine-1,4-bis(2-ethanesulfonic acid) (PIPES), N-(2-acetylamino)-2-aminoethanesulfonic acid (ACES), choline hydrochloride, N-tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid (TES), acetamido glycine, glycine, glycine amide, Good buffer such as bis(hydroxyethyl)glycine, phosphate buffer, citrate buffer, Tris buffer, etc. Among these, inorganic bases are preferred, and potassium hydroxide is more preferred.

[0375] The reaction solution can also use a single pH adjusting agent, or two or more can be used in combination. In addition, the total content relative to the total amount of the reaction solution when the pH adjusting agent is used is, for example, 0.05% by mass or more and 3.0% by mass or less, more preferably 0.1% by mass or more and 1.0% by mass or less.

[0376] The reaction solution may contain a coloring material such as a pigment, but the amount is preferably 0.2% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.05% by mass or less, with the lower limit being 0% by mass. The reaction solution preferably does not contain a coloring material.

[0377] 1.1.2.6 Physical properties

[0378] From the viewpoint of reducing skin irritation, the pH of the reaction solution is preferably 2.0 or more, more preferably 3.0 or more, and further preferably 4.0 or more. From the same viewpoint, the upper limit of pH is preferably 11.5 or less, more preferably 10 or less, further preferably 7.0 or less, and particularly preferably 5.0 or less.

[0379] The viscosity of the reaction solution is preferably 1.0 to 10 mPa·s at 20°C, more preferably 3.5 to 8.0 mPa·s, and further preferably 2.0 to 4.0 mPa·s. In particular, if the viscosity is 3.0 mPa·s or more, there is a tendency to obtain better color development. If the viscosity is 8.0 mPa·s or less, there is a tendency to obtain better ejection stability. In addition, the viscosity can be measured using, for example, a viscoelasticity tester MCR-300 (product name) of Pysica.

[0380] The viscosity of the mixed solution obtained by mixing the reaction solution and the transparent ink composition described later in equal amounts (for example, the viscosity 3 minutes after the mixing) is preferably 50 mPa·s or more at 20°C, more preferably 100 mPa·s or more, further preferably 300 mPa·s or more, particularly preferably 500 mPa·s or more, and more particularly preferably 750 mPa·s or more. If the viscosity of the mixed solution is within the above range, the water absorption rate into the fabric is slowed down, and a transparent ink layer (resin layer) can be formed better near the surface of the fabric. As a result, the penetration of the colored ink into the fabric can be further suppressed, and there is a tendency to obtain better color development. In addition, the resin layer plays a more significant role as a bonding layer between the fabric and the colored ink layer, thereby having a tendency to obtain better friction fastness.

[0381] In addition, the upper limit of the viscosity of the mixed solution obtained by mixing equal amounts of the reaction solution and the transparent ink composition described later is not particularly limited, but is preferably 10000 mPa·s or less at 20°C, more preferably 5000 mPa·s or less, particularly preferably 2500 mPa·s or less, and even more preferably 1500 mPa·s or less.

[0382] In particular, the viscosity of the reaction liquid and the transparent ink composition described later is 3 to 8 mPa·s at 20° C., and the viscosity of the equal-volume mixture of the reaction liquid and the transparent ink composition described later is preferably 50 mPa·s or more at 20° C. In this case, better ejection stability is obtained, and there is a tendency that the fuzz fixing effect is further improved and the image quality disturbance caused by the fuzz of the fabric can be further reduced.

[0383] The surface tension of the reaction solution is preferably 25 to 40 mN / m, more preferably 25 to 35 mN / m, further preferably 27 to 35 mN / m, and particularly preferably 30 to 33 mN / m. In addition, the surface tension can be measured by the Wilhelmy method using, for example, a surface tensiometer (DY-300 manufactured by Kyowa Interface Science Co., Ltd.). The surface tension is preferably a measured value at 20°C.

[0384] 1.2 Transparent ink adhesion process

[0385] The inkjet printing method according to the present embodiment includes a clear ink attaching step of attaching a clear ink composition containing anionic resin particles that react with a coagulant and coagulant and water to a cloth.

[0386] 1.2.1 Attachment method

[0387] The unit for attaching the transparent ink to the fabric can be the same as the reaction liquid described above. In addition, the total coating amount / coating amount ratio of the reaction liquid and the transparent ink composition, the time difference between the adhesion of the reaction liquid and the transparent ink composition to the same area of ​​the fabric, and the adhesion method of step 1 are also as described in the reaction liquid adhesion step described above, so the description is omitted.

[0388] 1.2.2 Transparent ink composition

[0389] The clear ink composition used in the clear ink adhesion step contains anionic resin particles that react with a coagulant to coagulate, and water. Hereinafter, each component contained in the clear ink composition will be described.

[0390] 1.2.2.1 Anionic resin particles

[0391] The transparent ink composition contains anionic resin particles. Similar to the function of the resin particles, the anionic resin particles have a function as a so-called fixing resin that improves the adhesion of the ink attached to the cloth. In addition, the anionic resin particles also have a function of reacting with the above-mentioned coagulant to coagulate and increase the viscosity of the transparent ink composition. The anionic resin particles are often processed in the form of an emulsion, but they can also be in the form of a powder.

[0392] The “anionic resin particles” refer to resin particles having a negative charge as a whole, and preferably have one or more anionic groups selected from a carboxyl group, a sulfonic acid group, a phosphoric acid group, and the like.

[0393] Examples of the resin particles include resin particles composed of polyurethane resins, acrylic resins (including styrene-acrylic resins), fluorene resins, olefin resins, rosin-modified resins, terpene resins, polyester resins, amide resins, epoxy resins, vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, and ethylene vinyl acetate resins. Among them, polyurethane resins, acrylic resins, olefin resins, and polyester resins are preferred. In addition, the resin particles may be used alone or in combination of two or more.

[0394] Polyurethane resin is a general term for resins having polyurethane bonds. In addition to polyurethane bonds, polyether polyurethane resins having ether bonds in the main chain, polyester polyurethane resins having polyester bonds in the main chain, and polycarbonate polyurethane resins having carbonate bonds in the main chain may also be used. In addition, as the polyurethane resin, commercially available products can also be used, for example, Superflex 460, 460s, 840, E-4000 (trade names, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), RESAMINE D-1060, D-2020, D-4080, D-4200, D-6300, D-6455 (trade names, manufactured by Dainichi Seika Industries, Ltd.), Takelac WS-5100, WS-6021, W-512-A-6 (trade names, manufactured by Mitsui Chemicals Polyurethanes, Ltd.), Suncure 2710 (trade name, manufactured by LUBRIZOL Co., Ltd.), Permarine UA-150 (trade name, manufactured by Sanyo Chemical Industries, Ltd.), etc.

[0395] Acrylic resin is a general term for polymers obtained by polymerizing at least one acrylic monomer such as (meth)acrylic acid or (meth)acrylic ester as one component, and examples thereof include resins obtained from acrylic monomers, copolymers of acrylic monomers and monomers other than acrylic monomers, etc. For example, acrylic acid-ethylene resins, which are copolymers of acrylic monomers and ethylene monomers, etc., can be cited. In addition, for example, styrene, etc., can be cited as ethylene monomers.

[0396] As the acrylic monomer, acrylamide, acrylonitrile, etc. can also be used. The resin emulsion using acrylic resin as a raw material can also use commercial products, for example, it can also be selected from FK-854 (trade name, made by Chuo Rika Industry Co., Ltd.), Movinyl952B, 718A (trade name, made by Nippon Synthetic Chemical Industry Co., Ltd.), NipolLX852, LX874 (trade name, made by Nippon Zeon Co., Ltd.), etc.

[0397] Styrene-acrylic resins are copolymers obtained from styrene monomers and (meth)acrylic acid monomers, and examples thereof include styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylate copolymers, styrene-α-methylstyrene-acrylic acid copolymers, and styrene-α-methylstyrene-acrylic acid-acrylate copolymers. As the styrene-acrylic resin, commercially available products may be used. Examples thereof include Joncryl 62J, 7100, 390, 711, 511, 7001, 632, 741, 450, 840, 74J, HRC-1645J, 734, 852, 7600, 775, 537J, 1535, PDX-7630A, 352J, 352D, PDX-7145, 538J, 7640, 7641, 631, 790, 780, and 7610 (trade names, manufactured by BASF), Movinyl 966A and 975N (trade names, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and Vinyblan 2586 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0398] The olefin resin is a polymer having olefins such as ethylene, propylene, and butene in the structural skeleton, and a known resin can be appropriately selected for use. As the olefin resin, a commercially available product can be used, for example, Arrow Base CB-1200, CD-1200 (trade name, manufactured by Unitika Co., Ltd.) and the like can also be used.

[0399] The anionic resin particles are more preferably polyurethane resin or acrylic resin, and more preferably polyurethane resin. In this case, the friction fastness tends to be more excellent.

[0400] The glass transition temperature (Tg) of the resin particles is preferably -60°C or higher and 50°C or lower, more preferably -60°C or higher and 40°C or lower, and further preferably -30°C or higher and 10°C or lower. When the glass transition temperature (Tg) of the resin particles is within the above range, there is a tendency that the texture followability (hand feel) is better. The glass transition temperature is measured, for example, using a differential scanning calorimeter "DSC7000" manufactured by Hitachi High-Tech Industries, Ltd., in accordance with JIS K7121 (Method for measuring transition temperature of plastics).

[0401] The content (solid content concentration) of the anionic resin particles is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, further preferably 4 to 20% by mass, particularly preferably 6 to 15% by mass, and even more particularly preferably 8 to 12% by mass relative to the total amount of the transparent ink composition. When the content of the anionic resin particles is within the above range, there is a tendency that more excellent color development and friction fastness can be obtained.

[0402] 1.2.2.2 Water

[0403] The clear ink composition contains water. As the water, the same water as that in the above-mentioned reaction liquid can be used.

[0404] The water content is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 50% by mass or more, relative to the total amount of the clear ink composition. The upper limit of the water content is not particularly limited, but for example, is preferably 90% by mass or less, more preferably 70% by mass or less, and more preferably 60% by mass or less, relative to the total amount of the clear ink composition.

[0405] 1.2.2.3 Organic solvents

[0406] The clear ink composition may contain an organic solvent. The type and content of the organic solvent may be the same as those of the above-mentioned reaction solution.

[0407] In the transparent ink composition, the organic solvent preferably includes alkanediols, alkylene glycol ethers and trialkylene glycol, more preferably includes 1,2-alkanediol, alkylene glycol ethers and trialkylene glycol, and further preferably includes propylene glycol, triethylene glycol monobutyl ether and triethylene glycol. When the organic solvent includes these solvents, the color development and friction fastness may be more excellent.

[0408] The content of the organic solvent is preferably 10 to 55% by mass, more preferably 15 to 45% by mass, further preferably 20 to 40% by mass, and particularly preferably 25 to 35% by mass relative to the total amount of the clear ink composition. When the content of the organic solvent is within the above range, the color development and friction fastness may be further improved.

[0409] 1.2.2.4 Surfactants

[0410] The clear ink composition may contain a surfactant. The type of the surfactant and the like may be the same as those of the above-mentioned reaction solution. The clear ink composition preferably contains a silicone-based surfactant as the surfactant.

[0411] The lower limit of the content of the surfactant is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, and particularly preferably 0.3% by mass or more, based on the total amount of the clear ink composition.

[0412] In addition, the upper limit of the content of the surfactant is preferably 3% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, and particularly preferably 0.8% by mass or less, relative to the total amount of the transparent ink composition. When the content of the surfactant is within the above range, there is a tendency that the permeability of the transparent ink composition to the fabric can be easily and satisfactorily adjusted.

[0413] 1.2.2.5 Other ingredients

[0414] The transparent ink composition may contain additives such as a pH adjuster, an antiseptic / mildew preventer, a rust preventer, a chelating agent, a viscosity adjuster, a solubilizing agent, and an antioxidant as required. When such additives are contained, the content is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, and even more preferably 0.1 to 1% by mass relative to the total amount of the transparent ink composition.

[0415] The transparent ink composition may also contain a coloring material such as a pigment, but the amount thereof is preferably 0.2% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.05% by mass or less, with the lower limit being 0% by mass. The transparent ink composition preferably does not contain a coloring material.

[0416] 1.2.2.6 Physical properties

[0417] From the viewpoint of reducing skin irritation, the pH of the transparent ink composition is preferably 2.0 or more, more preferably 5.0 or more, and even more preferably 7.0 or more. From the same viewpoint, the upper limit of the pH is preferably 11.5 or less, more preferably 10 or less, even more preferably 9.0 or less, and particularly preferably 8.0 or less.

[0418] The viscosity of the transparent ink composition is preferably 1.0 to 10 mPa·s at 20° C., more preferably 1.5 to 8 mPa·s, further preferably 3.0 to 8.0 mPa·s, further preferably 3.0 to 5.0 mPa·s, and particularly preferably 3.0 to 4.0 mPa·s. In particular, when the viscosity is 3.0 mPa·s or more, there is a tendency to obtain better color development. When the viscosity is 8.0 mPa·s or less, there is a tendency to obtain better ejection stability.

[0419] The surface tension of the clear ink composition at 20° C. is preferably 10 to 40 mN / m, more preferably 15 to 35 mN / m, further preferably 20 to 30 mN / m, particularly preferably 20 to 27 mN / m.

[0420] 1.3 Color ink adhesion process

[0421] The inkjet printing method according to the present embodiment includes a colored ink attaching step in which a colored ink composition containing a pigment, resin particles, and water is attached to a region of a cloth to which a transparent ink composition is attached by an inkjet method.

[0422] The transparent ink composition attached in the above manner becomes a resin layer well formed near the surface of the fabric, so that the penetration of the colored ink into the fabric can be suppressed, and there is a tendency to obtain good color development. In addition, the resin layer functions as a bonding layer between the fabric and the colored ink layer, and there is a tendency to obtain good friction fastness.

[0423] 1.3.1 Attachment method

[0424] The coating amount of the colored ink composition is preferably 0.01 to 1 g / inch 2 , more preferably 0.03 to 0.5 g / inch 2 , more preferably 0.05 to 0.3 g / inch 2 , particularly preferably 0.07 to 0.15 g / inch 2 .

[0425] In addition, the total amount of the reaction solution, the clear ink composition, and the colored ink composition deposited is preferably 100 mg / inch. 2 More than 120 mg / inch 2 More preferably, 150 mg / inch 2 Above, particularly preferably 180 mg / inch 2 More preferably, 200 mg / inch 2 If the total amount of adhesion is within the above range, the total amount of the adhered reaction liquid and ink is relatively large, so it is easy to become difficult to balance friction fastness and color development. However, as long as it is the inkjet printing method involved in this embodiment, there is a tendency to obtain good friction fastness and color development.

[0426] The upper limit of the total amount of adhesion is not particularly limited, but is preferably 500 mg / inch 2 Below, more preferably 300 mg / inch 2 Below, more preferably 250 mg / inch 2 the following.

[0427] 1.3.2 Colored ink composition

[0428] The colored ink composition used in the colored ink attaching step contains a pigment, resin particles, and water. Hereinafter, each component contained in the colored ink composition will be described.

[0429] 1.3.2.1 Pigments

[0430] The colored ink composition contains a pigment. As the pigment, for example, an inorganic pigment or an organic pigment can be used. In addition, the pigment is a kind of color material. As the color material, for example, a pigment and a dye can be mentioned.

[0431] There are no particular restrictions on the inorganic pigment, but examples thereof include carbon blacks such as CI Pigment Black 6 (lamp black, oil black), CI Pigment Black 7 (furnace black, channel black, thermal black, acetylene black), CI Pigment Black 8 (carbon black), and CI Pigment Black 10 (graphite); and white pigments such as iron oxide, titanium oxide, zinc oxide, and silicon oxide.

[0432] Examples of carbon black include No. 2300, 900, MCF88, No. 20B, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, No. 2200B, etc. manufactured by Mitsubishi Chemical Corporation. Examples include Color Black FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Pretex 35, U, V, 140U, Special Black 6, 5, 4A, 4, 250, etc. manufactured by Degussa. Examples include Conductex SC, Raven 1255, 5750, 5250, 5000, 3500, 1255, 700, etc. manufactured by Columbia Carbon Corporation. Examples include Regal 400R, 330R, 660R, Mogul L, Monarch 700, 800, 880, 900, 1000, 1100, 1300, 1400, and Elftex 12 manufactured by Cabot Corporation.

[0433] Examples of white pigments include CI Pigment White 1 which is basic lead carbonate, CI Pigment White 4 composed of zinc oxide, CI Pigment White 5 composed of a mixture of zinc sulfide and barium sulfate, CI Pigment White 6 composed of titanium dioxide, CI Pigment White 6:1 composed of titanium dioxide containing other metal oxides, CI Pigment White 7 composed of zinc sulfide, CI Pigment White 18 composed of calcium carbonate, CI Pigment White 19 composed of clay, CI Pigment White 20 composed of titanium mica, CI Pigment White 21 composed of barium sulfate, CI Pigment White 22 composed of gypsum, CI Pigment White 26 composed of magnesium oxide / silicon dioxide, CI Pigment White 27 composed of silicon dioxide, and CI Pigment White 28 composed of anhydrous calcium silicate. Among these, CI Pigment White 6 is preferably used because it is excellent in color development and hiding properties.

[0434] The average particle diameter of the white pigment is preferably more than 100nm and less than 500nm, more preferably more than 50nm and less than 450nm, and further preferably more than 200nm and less than 400nm. By making the average particle diameter of the white pigment into this range, there is a trend that can ensure the ejection stability from the inkjet head. In addition, there is a trend that can improve the hiding property. In addition, in this specification, "average particle diameter" refers to the particle diameter at the time of cumulative distribution 50vol%, that is, volume-based particle size distribution, unless otherwise specified. The determination of the average particle diameter is measured by the dynamic light scattering method and the laser diffraction light method described in JIS Z8825. Specifically, a particle size distribution meter (for example, "MicrotrackUPA" Nikkiso Co., Ltd.) using the dynamic light scattering method as the measurement principle can be adopted.

[0435] Examples of organic pigments include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthraquinone pigments, indanthrone pigments, flavonanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perindolone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, isoindolinone pigments, azomethine pigments, and azo pigments.

[0436] Specific examples of organic pigments include the following.

[0437] Examples of cyan pigments include CI Pigment Blue 1, 2, 3, 15:3, 15:4, 15:34, 16, 22, and 60; and CI Vat Blue 4 and 60. Preferably, one or a mixture of two or more selected from the group consisting of CI Pigment Blue 15:3, 15:4, and 60 can be used.

[0438] Magenta pigments include CI Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57:1, 112, 122, 123, 168, 184, 202, CI Pigment Violet 19, etc. Preferably, one or a mixture of two or more selected from the group consisting of CI Pigment Red 122, 202 and 209, and CI Pigment Violet 19 can be exemplified.

[0439] Examples of the yellow pigment include CI Pigment Yellow 1, 2, 3, 12, 13, 14C, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 119, 110, 114, 128, 129, 138, 150, 151, 154, 155, 180, and 185. Preferably, one or a mixture of two or more selected from the group consisting of CI Pigment Yellow 74, 109, 110, 128, 138, 150, and 180 can be used.

[0440] Pigments of other colors may also be used, for example, orange pigments, green pigments, etc. may be mentioned.

[0441] The pigments may be used alone or in combination of two or more.

[0442] The pigment contained in the colored ink composition is preferably a white pigment. The colored ink composition (white ink) containing a white pigment is suitable for forming a white ink layer as a base layer, but a relatively large amount of white ink is required to be attached, so there is a tendency for the total amount of attached reaction liquid and ink to become larger, and it is particularly difficult to balance friction fastness and color development. In contrast, according to the inkjet printing method involved in this embodiment, even if it is a colored ink composition containing a white pigment, there is a tendency to obtain excellent friction fastness and color development.

[0443] The content of the pigment (especially the white pigment) is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, further preferably 4 to 20% by mass, particularly preferably 6 to 15% by mass, and even more particularly preferably 8 to 12% by mass relative to the total amount of the colored ink composition. If the content of the pigment is within the above range, the friction fastness can be improved, and there is a tendency to obtain better color development (whiteness).

[0444] The pigment may be dispersed using a pigment dispersant. Alternatively, the pigment may be dispersed using ozone, hypochlorous acid, fuming sulfuric acid, etc. to oxidize or sulfonate the pigment surface to form a self-dispersible pigment.

[0445] The pigment dispersant has the function of dispersing the pigment in the ink. The pigment dispersant may be water-soluble, but preferably is a substance that is not completely water-soluble, and is believed to disperse the pigment by partially or completely binding or adsorbing to the pigment to increase the hydrophilicity of the pigment surface.

[0446] The pigment dispersant is a polymer compound, and examples thereof include acrylic resins and their salts such as poly(meth)acrylic acid, (meth)acrylic acid-acrylonitrile copolymers, (meth)acrylic acid-(meth)acrylate copolymers, vinyl acetate-(meth)acrylate copolymers, vinyl acetate-(meth)acrylic acid copolymers, vinylnaphthalene-(meth)acrylic acid copolymers, styrene-(meth)acrylic acid copolymers, styrene-(meth)acrylic acid copolymers, styrene-(meth)acrylic acid-(meth)acrylate copolymers, styrene-α-methylstyrene-(meth)acrylic acid copolymers, and styrene-α-methylstyrene-(meth)acrylic acid-(meth)acrylate copolymers.

[0447] In addition, examples of pigment dispersants include maleic acid resins and their salts such as styrene-maleic acid copolymers, styrene-anhydrous maleic acid copolymers, vinyl naphthalene-maleic acid copolymers, and vinyl acetate-maleic acid polyester copolymers; polyurethane resins and their salts with or without a cross-linked structure; polyvinyl alcohols; and resins such as vinyl acetate-crotonic acid copolymers and their salts.

[0448] In addition, the acrylic resin may be a copolymer of an acrylic monomer and other monomers in addition to being a polymer of the acrylic monomer (acrylic monomer) as described above. For example, an acrylic ethylene resin as a copolymer with an ethylene monomer as another monomer is also referred to as an acrylic resin. In addition, for example, a resin as a copolymer of a styrene monomer and an acrylic monomer among the above-mentioned styrene resins is also included in the acrylic resin. Furthermore, when referred to as an acrylic resin, its salt and its polyester are also included.

[0449] Examples of commercially available pigment dispersants include X-200, X-1, X-205, X-220, and X-228 (manufactured by Seikyo PMC Co., Ltd.), Nopco sparse (registered trademark) 6100 and 6110 (manufactured by San Nopco Co., Ltd.), Joncryl 67, 586, 611, 678, 680, 682, and 819 (manufactured by BASF), DISPERBYK-190 (manufactured by BYK Chemical Japan Ltd.), N-EA137, N-EA157, N-EA167, N-EA177, N-EA197D, N-EA207D, and E-EN10 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).

[0450] Examples of commercially available acrylic pigment dispersants include BYK-187, BYK-190, BYK-191, BYK-194N, and BYK-199 (manufactured by BYK-Chemie Co., Ltd.), Aron A-210, A6114, AS-1100, AS-1800, A-30SL, A-7250, and CL-2 (manufactured by Toagosei Co., Ltd.).

[0451] Examples of commercially available polyurethane pigment dispersants include BYK-182, BYK-183, BYK-184, and BYK-185 (manufactured by BYK-Chemie Co., Ltd.), TEGO Disperse 710 (manufactured by Evonic Tego Chemi), and Borchi (registered trademark) Gen 1350 (manufactured by OMG Borschers).

[0452] The pigment dispersant is preferably an anionic pigment dispersant. The “anionic pigment dispersant” refers to a pigment dispersant having a negative charge as a whole, and preferably has one or more anionic groups selected from a carboxyl group, a sulfonic acid group, a phosphoric acid group, and the like.

[0453] Preferably, at least one of the pigment in the colored ink composition and the resin particles described below is anionic. In this case, the coagulation effect by the coagulant is more excellent, so there is a tendency to obtain better color development and better friction fastness.

[0454] The anionic pigment means that the pigment as a whole has a negative charge, and preferably has one or more anionic groups selected from carboxyl groups, sulfonic acid groups, phosphoric acid groups, etc. The anionic group may be directly present on the surface of the pigment, or may be present via an anionic resin dispersant adsorbed or bonded to the pigment.

[0455] The pigment dispersant may be used alone or in combination of two or more. The total content of the pigment dispersant is preferably 0.1% by mass or more and 30% by mass or less relative to 100% by mass of the colored ink composition, more preferably 0.5% by mass or more and 25% by mass or less, further preferably 1% by mass or more and 20% by mass or less, and particularly preferably 1.5% by mass or more and 15% by mass or less. The content of the pigment dispersant is 0.1% by mass or more, thereby having a tendency to ensure the dispersion stability of the pigment. In addition, if the content of the pigment dispersant is 30% by mass or less, there is a tendency to suppress the viscosity of the colored ink composition to be smaller.

[0456] Furthermore, the weight average molecular weight of the pigment dispersant is more preferably not less than 500. By using such a pigment dispersant, there is a tendency that the odor is less and the dispersion stability of the pigment can be further improved.

[0457] When a pigment (particularly, a white pigment) is dispersed by a pigment dispersant, the ratio of the pigment to the pigment dispersant is preferably 10:1 to 1:10, and more preferably 4:1 to 1:3.

[0458] 1.3.2.2 Resin particles

[0459] The colored ink composition contains resin particles. The resin particles can be formed in the same manner as the “resin particles” of the anionic resin particles contained in the clear ink composition described above, and therefore, description thereof will be omitted.

[0460] The resin particles in the colored ink composition are preferably anionic. In this case, the coagulation effect by the coagulant is more excellent, so there is a tendency to obtain better color development and better friction fastness.

[0461] The resin particles in the colored ink composition are preferably polyurethane resin or acrylic resin, and more preferably polyurethane resin. In this case, there is a tendency for the friction fastness to be more excellent.

[0462] The glass transition temperature (Tg) of the resin particles in the colored ink composition is preferably -60°C to 50°C, more preferably -60°C to 40°C, and further preferably -30°C to 10°C. When the glass transition temperature (Tg) of the resin particles is within the above range, the texture followability (feel) tends to be better.

[0463] The content (solid content concentration) of the resin particles is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, further preferably 4 to 20% by mass, particularly preferably 6 to 15% by mass, and even more particularly preferably 8 to 12% by mass relative to the total amount of the colored ink composition. If the content of the resin particles is within the above range, there is a tendency to obtain better color development and friction fastness.

[0464] 1.3.2.3 Water

[0465] The colored ink composition contains water. As the water, the same water as that of the above-mentioned reaction liquid can be used.

[0466] The water content is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 50% by mass or more, relative to the total amount of the aqueous colored ink composition. The upper limit of the water content is not particularly limited, but, for example, is preferably 90% by mass or less, and more preferably 70% by mass or less, relative to the total amount of the colored ink composition.

[0467] 1.3.2.4 Organic solvents

[0468] The colored ink composition may contain an organic solvent. The type and content of the organic solvent may be the same as those of the above-mentioned reaction solution.

[0469] In the colored ink composition, the organic solvent preferably includes alkanediols, alkylene glycol ethers and trialkylene glycols, more preferably includes 1,2-alkanediol, alkylene glycol ethers and trialkylene glycols, and further preferably includes propylene glycol, triethylene glycol monobutyl ether and triethylene glycol. When the organic solvent includes these solvents, the color development and friction fastness are sometimes more excellent.

[0470] In addition, the colored ink composition preferably contains 3.0% by mass or more of an organic solvent having a normal boiling point of 250° C. or more, more preferably 4.0% by mass or more, and further preferably 5.0% by mass or more. The upper limit of the content is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.

[0471] When an organic solvent having a normal boiling point of 250° C. or higher is contained within the above range, the nozzles of the inkjet head are moisturized, and there is a tendency that ejection reliability (continuous printing stability) can be further improved.

[0472] In addition, examples of organic solvents having a normal boiling point of 250°C or higher include glycerin, polyethylene glycol monomethyl ether, etc. In addition, organic solvents having a normal boiling point of 250°C or higher are also referred to as humectants. Organic solvents having a normal boiling point of 250°C or higher are more preferably at a normal boiling point of 270°C or higher, and even more preferably at a normal boiling point of 280°C or higher.

[0473] The content of the organic solvent is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, further preferably 5 to 20% by mass, and particularly preferably 7 to 17% by mass relative to the total amount of the colored ink composition. If the content of the organic solvent is within the above range, the color development and friction fastness may be further improved.

[0474] 1.3.2.5 Surfactants

[0475] The colored ink composition may contain a surfactant. The type of the surfactant and the like may be the same as those of the above-mentioned reaction solution. The colored ink composition preferably contains a silicone-based surfactant as the surfactant.

[0476] The lower limit of the content of the surfactant is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, and particularly preferably 0.3% by mass or more, based on the total amount of the colored ink composition.

[0477] In addition, the upper limit of the content of the surfactant is preferably 3% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, and particularly preferably 0.8% by mass or less relative to the total amount of the colored ink composition. If the content of the surfactant is within the above range, there is a tendency that the permeability of the colored ink composition to the fabric can be easily and satisfactorily adjusted.

[0478] 1.3.2.6 Other ingredients

[0479] The colored ink composition may contain additives such as a pH adjuster, a preservative / antifungal agent, a rust inhibitor, a chelating agent, a viscosity modifier, a solubilizing agent, and an antioxidant as needed. The content of such additives is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, and even more preferably 0.1 to 1% by mass relative to the total amount of the colored ink composition.

[0480] 1.3.2.7 Physical properties

[0481] From the viewpoint of reducing skin irritation, the pH of the colored ink composition is preferably 2.0 or more, more preferably 5.0 or more, and further preferably 7.0 or more. From the same viewpoint, the upper limit of the pH is preferably 11.5 or less, more preferably 10 or less, further preferably 9.0 or less, and particularly preferably 8.0 or less.

[0482] The viscosity of the colored ink composition is preferably 1.0 to 10 mPa·s at 20°C, more preferably 2.0 to 10 mPa·s, further preferably 3.0 to 8.0 mPa·s, and particularly preferably 4.0 to 6.0 mPa·s. In particular, when the viscosity is 4.0 mPa·s or more, there is a tendency to obtain better color development. When the viscosity is 6.0 mPa·s or less, there is a tendency to obtain better ejection stability.

[0483] The surface tension of the colored ink composition at 20° C. is preferably 10 to 40 mN / m, more preferably 15 to 35 mN / m, further preferably 20 to 30 mN / m, and particularly preferably 20 to 27 mN / m.

[0484] 1.4 Pressure application process

[0485] The inkjet printing method according to the present embodiment includes a pressure applying step of applying pressure to the region of the fabric to which the reaction liquid and the clear ink composition have adhered, after the reaction liquid adhering step and the clear ink adhering step.

[0486] The pressure applying means is not particularly limited as long as it can apply pressure to the fuzz in the region where the reaction liquid and the transparent ink composition of the cloth are attached, and examples thereof include a method of applying pressure without contact with the cloth and a method of applying pressure in direct contact with the cloth.

[0487] As the non-contact application of pressure to the cloth, for example, there is the application of pressure by blowing air with a blower or the like.

[0488] Examples of the pressure applying means that directly contacts the cloth include a pressure applying means based on surface contact and a pressure applying means based on line contact.

[0489] As the application of pressure by surface contact, for example, there is the application of pressure by a surface of a plate or the like.

[0490] As the application of pressure by line contact, for example, there is mentioned application of pressure by a roller, a doctor blade, or the like.

[0491] The pressure imparting step is preferably carried out by direct contact between the cloth and the pressure imparting unit, and more preferably by line contact between the cloth and the pressure imparting unit. In this case, each step including the pressure imparting step can be easily carried out in the same device, which can further simplify the steps.

[0492] The pressure applied in the pressure applying step is not particularly limited as long as it can overwhelm the fluff of the cloth. For example, it is preferably 1000 Pa or less, more preferably 100 Pa or less, further preferably 10 Pa or less, particularly preferably 1 Pa or less, more particularly preferably 0.1 Pa or less, more preferably 0.01 Pa or less, and even more particularly preferably 0.001 Pa or less.

[0493] The pressure applying step is preferably performed before the above-mentioned colored ink attaching step. In this case, there is a tendency that the fluff fixing effect is further improved and the image quality disturbance due to the fluffing of the cloth can be further reduced.

[0494] Furthermore, the pressure applying step is preferably performed within 30 minutes, more preferably within 20 minutes, further preferably within 10 minutes, particularly preferably within 5 minutes, and even more particularly preferably within 1 minute after the above-mentioned transparent ink attaching step. In this case, the transparent ink is not completely dried and is in the state of a gel-like coagulation body, so that the fuzz is easily fixed in a state where it is collapsed by viscosity, which has a tendency to further improve the fuzz fixing effect and further reduce the image quality disturbance caused by the fuzz of the cloth.

[0495] 1.5 Fabric Positions Between Processes

[0496] The fabric is placed on the mounting table, and the reaction solution attaching step, the transparent ink attaching step, the pressure imparting step, and the colored ink attaching step are performed without changing the relative positional relationship between the fabric and the mounting table. Thus, each step can be performed continuously, and the steps can be simplified.

[0497] As the form of the fabric used in the inkjet printing method involved in this embodiment, for example, cloth, clothing, other clothing, etc. Cloth includes woven fabrics, knitted fabrics, non-woven fabrics, etc. Clothing and other clothing include not only sewn T-shirts, handkerchiefs, scarves, towels, handbags, cloth bags, curtains, sheets, bedspreads, wallpapers and other supplies, but also cloth before and after cutting as a component before sewing. As their forms, they can be listed as long strips wound in a roll, cut into a specified size, and product-shaped forms.

[0498] As materials constituting the fabric, for example, natural fibers such as cotton, linen, wool, and silk; synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, and polyurethane; biodegradable fibers such as polylactic acid, etc., and blended fibers thereof may also be used. Among these materials, fabrics made of cotton, polyester, or blends of cotton and polyester are preferred because they are easily available.

[0499] The fabric is preferably a fabric with fluff. In particular, from the viewpoint of being able to enjoy the effect of the present invention more, it is preferred that the fabric has fluff in which fibers fly out from the fiber bundle constituting the fabric, and the length of the fluff in the vertical direction between the surface including the fiber bundle and the apex of the fluff is preferably 50 μm or more, more preferably 100 μm or more. Such a fabric is more likely to have the problem of image quality disturbance caused by the fluff. In contrast, according to the inkjet printing method involved in this embodiment, even when such a fabric is used, it is possible to reduce the influence caused by the fluff on the printing surface and perform image formation.

[0500] The length can be measured using a known device such as a digital microscope (KEYENCE, VHX-5000), or the length can be obtained by taking the average value (arithmetic mean) of a plurality of hairs (eg, 10 points).

[0501] In addition, "fiber bundle" refers to a structure formed by bundling multiple fibers, and has a substantially circular cross-section. In addition, "fluff" refers to the ends of short fibers standing up from the surface of the fiber bundle, and the ends of short fibers present inside the fiber bundle are not called fluff.

[0502] In addition, the fabric is preferably L * a * b * Brightness L in the color system * The value is below 70. *The value may be 60 or less, or 50 or less. In printing and dyeing on such fabrics, in order to obtain excellent color development, white ink (base) and color ink are sometimes used as a colored ink composition. If the white ink is exposed on the surface of the fabric due to fuzzing, the image quality is likely to be significantly disturbed. In contrast, according to the inkjet printing method involved in this embodiment, even when such fabrics are used, the influence of fuzzing on the printing surface can be reduced and an image can be formed.

[0503] In addition, L * The value can be measured using a known colorimeter, and can be measured using, for example, Spectrolino (Gretag).

[0504] In addition, L * The fabric having a value of 70 or less may be, for example, a colored fabric that has been previously colored with a dye or the like. Examples of the dye that has been previously colored with the fabric include water-soluble dyes such as acid dyes and basic dyes, disperse dyes used in combination with a dispersant (surfactant), reactive dyes, and the like. As a method for coloring the fabric with a dye, a known method may be adopted depending on the material and form of the fabric.

[0505] 1.6 Heating and drying process

[0506] The inkjet printing method according to the present embodiment may include a step of heating and drying the ink or the like adhered to the cloth (heating and drying step) after the aforementioned color ink adhering step.

[0507] The heat drying method is not particularly limited, and examples thereof include a conveyor type open hearth furnace, a normal pressure steam method, a high pressure steam method, a thermal curing method, etc. The heat source during heat drying is not particularly limited, and for example, an infrared lamp or the like can be used.

[0508] The heating and drying temperature is preferably a temperature at which the resin particles that may be included in the ink melt and the medium such as water volatilizes. The heating and drying temperature is preferably, for example, 100°C or more and 250°C or less, more preferably 120°C or more and 230°C or less, further preferably 140°C or more and 200°C or less, and particularly preferably 150°C or more and 180°C or less. Here, the heating and drying temperature in the heating and drying step refers to the surface temperature of the image or the like formed on the cloth. The time for performing the heating and drying is not particularly limited, but, for example, is preferably 30 seconds or more and 20 minutes or less, and more preferably 2 minutes or more and 5 minutes or less.

[0509] 1.7 Other processes

[0510] The inkjet printing method of this embodiment may also include a step of washing the recorded cloth, a step of heating and drying again, etc. During washing, as required, a soaping treatment may be performed to wash away components such as ink that are not fixed to the cloth using hot soap solution.

[0511] 1.8 Inkjet printing and dyeing device

[0512] An inkjet printing apparatus that can be applied to the inkjet printing method according to the present embodiment will be described.

[0513] Fig. 9 is a perspective view of the appearance of the inkjet printing and dyeing device 1, Fig.10 is a schematic diagram of the conveying path of the printed workpiece of the inkjet printing and dyeing device 1, Fig.11 1 and 2 are diagrams showing the state of the workpiece P and the workpiece P placed on the placement table 7 .

[0514] like Fig. 9 As shown in the figure, the inkjet printing device 1 has the following structure: a guide table 8 is provided at the bottom of the device body 2, and a mounting table 7 is moved in the moving direction TD (TD) of the printed workpiece P by a guide portion 8a formed on the guide table 8. Fig.10 Guide in the direction of arrow A).

[0515] The mounting table 7 is a smooth table for mounting the printed workpiece P. Fig.11 As shown in FIG. 1 , the printed workpiece P is placed on the placement surface 7a ( Fig.11 The printed workpiece P is shown as an example of a T-shirt), and the loading platform 7 carrying the printed workpiece P is moved in the conveying direction A, so that the printed workpiece P can pass through the printing and dyeing execution unit 5. In addition, the illustration and description of the driving mechanism for driving the loading platform 7 are omitted in this specification. According to the above content, the loading platform 7 and the driving mechanism driving it constitute a moving unit that moves the printed workpiece P.

[0516] In addition, the mounting table 7 may be detachable from the apparatus main body 2. Thus, the mounting table 7 can be removed from the apparatus main body 2 and transported while the workpiece P is mounted on the mounting table 7, or the mounting table 7 can be attached to a heating device prepared separately from the apparatus main body 2 to heat the workpiece P.

[0517] The inkjet head 14 constituting the printing execution unit 5 is an inkjet head of a known structure having a plurality of nozzle arrays having a plurality of nozzles for ejecting a reaction liquid, a nozzle for ejecting a transparent ink composition, and a nozzle for ejecting a colored ink composition. The inkjet head 14 is mounted in a direction ( Fig. 9 Scanning direction SD: Fig.10 A carriage 13 is reciprocatingly driven (in the front and back directions of the paper).

[0518] Fig.12 An example of each nozzle array included in the nozzle surface of the inkjet head 14 is shown. Fig.12 In the figure, the inkjet head 14 has a plurality of nozzle rows A to H along the scanning direction SD. The nozzle rows are composed of a plurality of nozzles arranged along a direction (moving direction TD of the workpiece P) intersecting the direction (scanning direction SD) in which the inkjet head 14 moves.

[0519] At this time, the arrangement is such that when the nozzle array that ejects the reaction liquid is projected along the scanning direction SD, at least a portion of the nozzle array that ejects the transparent ink composition overlaps with the nozzle array that ejects the transparent ink composition in the moving direction TD of the printed workpiece P, thereby enabling the above-mentioned step 1 (applying the reaction liquid and the transparent ink composition to the same area of ​​the cloth with a single scan of the inkjet head) to be performed.

[0520] The ink etc. ejected from each nozzle row can be appropriately selected, but for example, it is preferred that rows A to B be selected as the reaction liquid, rows C to D be selected as the clear ink composition, and rows E to H be selected as the nozzle rows ejecting the color ink composition.

[0521] In the case of a serial printer, the inkjet head 14 has a length smaller than the width of the workpiece P, and the inkjet head 14 performs recording while moving in a scanning direction SD intersecting the moving direction TD of the workpiece P. In addition, in the serial printer, the inkjet head 14 is mounted on a carriage 13 that moves in a predetermined direction, and the inkjet head 14 moves along with the movement of the carriage 13, thereby ejecting ink and reaction liquid on the workpiece P. The workpiece P may be moved between scans.

[0522] In addition, the inkjet printing device is not limited to the above-mentioned serial printer, and may be a line printer. Fig.13 As another example of the inkjet printing device, a schematic side view of a line printer is shown. The line printer can have the same structure as a serial printer except for the printing execution unit 5 .

[0523] The line printer has a line head 300 having a length corresponding to the width of the printed workpiece P. The line head 300 may also be composed of a plurality of line heads. The line head 300 has a cavity for containing a reaction liquid, a transparent ink composition, and a colored ink composition (ink, etc.); a discharge drive unit provided for each cavity; and a nozzle for discharging ink, etc. The cavity, the discharge drive unit provided for each cavity, and the nozzle may be independent of each other, and a plurality of them may be provided on one head. The discharge drive unit may be formed using an electro-mechanical conversion element such as a piezoelectric element that changes the volume of the cavity by mechanical deformation, an electron-thermal conversion element that generates bubbles in the ink and discharges it by generating heat, and the like.

[0524] In a line printer, the head does not (almost) move but is fixed, and recording is performed by a single scan of the inkjet head. Line printers have an advantage over serial printers in that the recording speed is fast.

[0525] like Fig.10 As shown, the inkjet printing apparatus 1 includes a pressure applying unit 10. The pressure applying unit 10 applies pressure to a region of the workpiece P to which the reaction liquid and the clear ink composition have adhered by the inkjet head 14. Fig.10 The pressure imparting unit 10 shown is a structure (e.g., a roller, a scraper, etc.) that imparts pressure by linear contact with the printed workpiece P, but may also be a structure that imparts pressure through a surface of a plate, etc., or a structure that imparts pressure by air supply based on a blower, etc.

[0526] The control unit 16 is a control unit that controls a drive mechanism (not shown) for driving the stage 7 , a drive mechanism (not shown) for driving the carriage 13 , and a drive mechanism (not shown) for driving the inkjet head 14 .

[0527] Hereinafter, an example of the order of the above-mentioned steps of the inkjet printing method according to the present embodiment using the inkjet printing apparatus 1 will be described. First, the mounting table 7 on which the workpiece P is mounted is moved from the setting position ( Fig.10 Left side of the center) moves in the direction of T1 to the initial position of the ink coating process ( Fig.10 Next, the stage 7 moves in the direction of T2, while the inkjet head 14 causes the reaction liquid and the transparent ink composition to adhere, and the reaction liquid adhesion step and the transparent ink adhesion step are performed. Thereafter, the stage 7 further moves in the direction of T2, while the pressure applying unit 10 applies pressure to the workpiece P, and returns to the set position ( Fig.10 Next, the mounting table 7 on which the workpiece P is placed is moved from the setting position ( Fig.10 The left side of the center) moves again in the direction of T1 to the initial position of the ink coating process ( Fig.10 Then, the stage 7 moves in the direction T2 while the inkjet head 14 causes the colored ink composition to adhere, thereby performing a colored ink adhesion step. Between these steps, a series of actions are performed without removing the printed workpiece P from the stage 7.

[0528] 2. Ink set

[0529] An ink set according to one embodiment of the present invention is an ink set used in the above-mentioned inkjet printing method, and includes the above-mentioned reaction solution, a clear ink composition, and a colored ink composition.

[0530] According to the ink set according to the present embodiment, it is possible to form an image with reduced influence of fuzzing on the printing surface. The reaction liquid, the clear ink composition, and the color ink composition included in the ink set are as described above, and therefore, description thereof will be omitted.

[0531] In the present invention, an "ink set" is an ink set that combines a reaction liquid, a transparent ink composition, and a colored ink composition. An ink set is a set of inks that are mixed and used in a set. The colored ink composition included in the ink set may be only one, or may be two or more. The same applies to the reaction liquid and the transparent ink composition included in the ink set.

[0532] 3. Examples of the first embodiment

[0533] Hereinafter, the first embodiment of the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. % below refers to mass unless otherwise specified.

[0534] 3.1 Preparation of Reaction Solution, Transparent Ink Composition and Colored Ink Composition

[0535] Each component was placed in a container in a manner to form the composition of Table 1, mixed and stirred, and further filtered using a 5 μm membrane filter to obtain a reaction solution, a transparent ink composition, and a colored ink composition in each example. In addition, the numerical values ​​of each component shown in each example in the table represent mass % unless otherwise specified. In addition, the mass % of the pigment and resin particles in Table 1 represents the solid content concentration, and ion exchange water was added so that the total mass of the composition becomes 100 mass %.

[0536] In addition, as a pigment, a pigment dispersion prepared in advance by the following process was used. As a pigment, CI pigment white 6 (specific gravity: 4.2g / mL) was used, and as a pigment dispersant, an anionic resin dispersant was used. Specifically, a styrene-acrylic resin synthesized using 55% by mass of styrene, 20% by mass of acrylic acid, and 30% by mass of methyl methacrylate was used. 1 part by mass of dispersant and 10 parts by mass of ion exchange water were mixed with respect to 3 parts by mass of pigment, and the obtained mixture was pre-mixed, and then a bead mill disperser (UAM-015 manufactured by Kotobuki Industry Co., Ltd.) was used to disperse zirconium oxide beads with a diameter of 0.03mm at a peripheral speed of 10m / s and a liquid temperature of 30°C for 15 minutes, and the coarse particles were centrifuged by a centrifugal separator (Model-3600 manufactured by Kuboyama Shoji Co., Ltd.) to obtain a dispersion of titanium oxide.

[0537] Supplementary explanations are provided for the items recorded in Table 1-1.

[0538] Takelac WS-6021 (trade name, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.)

[0539] BYK-348 (trade name, manufactured by BYK)

[0540] Olfine E1010 (trade name, manufactured by Nissin Chemical Industry Co., Ltd.)

[0541] The viscosity was measured in an environment of 20° C. using a viscoelasticity tester MCR-300 (trade name, manufactured by Pysica Corporation).

[0542] The surface tension was measured by confirming the surface tension when a platinum plate was wetted with the reaction solution or the ink in an environment of 25° C. using an automatic surface tensiometer CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.).

[0543] 3.2 Recording conditions

[0544] The reaction solution, the transparent ink composition, and the colored ink composition obtained by the above-mentioned modulation were used to perform the inkjet printing method of each Example and each Comparative Example based on the following conditions and the conditions described in Tables 1-2 to 1-4. In addition, Table 1-2 records the process of forming a resin layer (process a), Table 1-3 records the process of forming a white ink layer (process b), Table 1-4 records the process of coating treatment (process c) and the drying process (process d), and recording was performed continuously according to the recording conditions in the order of processes a, b, c, and d.

[0545] Printing machine: SC-F2200 (Seiko Epson) modified machine

[0546] Drying: The fabric was dried at 160° C. for 3 minutes using a conveyor type open-hearth oven (Fusion R 36-6-4 manufactured by M&R Co.).

[0547] Fabric: 100% cotton, black T-shirt (Printstar), L in the colored part * Value 12

[0548] 〔Coating conditions〕

[0549] Image resolution: 1200×600dpi

[0550] · Programming Duty of each column: 100%

[0551] CR (slide) moving speed: 6-40 inch / s

[0552] Head drive frequency: 3-60kHz

[0553] ·Coating amount adjustment: Adjust by CR moving speed and driving frequency

[0554] As the head nozzle structure, it becomes Figure 2 In the structure shown, rows A to B serve as nozzle rows for ejecting the reaction liquid, rows C to D serve as nozzle rows for ejecting the clear ink composition, and rows E to H serve as nozzle rows for ejecting the color ink composition.

[0555] In Table 1-2, "simultaneous" in "printing time difference between reaction liquid and clear ink" means that the reaction liquid and the clear ink composition were applied to the same area of ​​the fabric by one scanning of the inkjet head.

[0556] In Table 1-3, "landing time difference" is "simultaneous", which means that the reaction liquid attaching step and the color ink attaching step are performed simultaneously. More specifically, it means that the reaction liquid and the color ink composition are applied to the same area of ​​the fabric in one scan of the inkjet head.

[0557] The viscosity of the reaction liquid and transparent ink equal mixed solution described in Table 1-5 is obtained by dropping the reaction liquid and the transparent ink composition in equal amounts on the non-rotating plate in a symmetrical manner about the center of the non-rotating plate in a measuring section composed of a disk-shaped non-rotating plate and a disk-shaped rotating plate of a rheometer (Antonpaar, MCR302e) and measuring the viscosity of the reaction liquid and the transparent ink composition at a shear rate of 50 [s -1 ] and the viscosity of the liquid is measured 10 seconds after the start of the plate rotation to obtain the viscosity.

[0558] 3.3 Evaluation methods

[0559] 3.3.1 Whiteness determination (color rendering)

[0560] In the printed products obtained by the inkjet printing method according to each of the Examples and Comparative Examples, L * The image quality (whiteness) is determined based on the following criteria.

[0561] (Judgment Criteria)

[0562] Good: L * 85[-] and above

[0563] Bad: L * Less than 85[-]

[0564] 3.3.2 Hand feel

[0565] The printed fabric obtained by the inkjet printing method according to each embodiment and each comparative example was cut into a size of 20×20 cm, and the tension-curvature curve was measured under the conditions of a shear tension of 10 gf / cm and a shear angle of ±8° using a tensile shear tester KE-S-FB1-A (product name of Kato Tech). The shear hardness [gf / (cm·deg)] was calculated based on the linear regression between the curvatures of 0.5° to 2.5° in the measured tension-curvature curve. In addition, the shear hardness was calculated in the same manner as the printed fabric for cotton cloth (Printstar 00085-CVT, the same cloth used in each embodiment) to which the reaction liquid composition and the ink composition were not applied. The absolute value of the difference between the shear hardness of the printed fabric and the shear hardness of the cotton cloth was calculated, and the feel was evaluated according to the following evaluation criteria.

[0566] (Judgment Criteria)

[0567] A: The absolute value of the difference in shear hardness is 3.5 or less

[0568] B: The absolute value of the difference in shear hardness is more than 3.5 and less than -5.0

[0569] C: Over 5.0

[0570] 3.3.3 Friction firmness test

[0571] With respect to the printed and dyed products obtained by the above-mentioned inkjet printing method involved in each embodiment and each comparative example, the friction fastness was evaluated according to the following dry friction standard or wet friction standard based on the dry test or wet test specified in the "Test method for color fastness to friction" in JIS L 0849. In addition, the test was performed by the friction tester method. The evaluation was performed by using Article 10 (determination of color fastness) of JIS L 0801 cited in JIS L0849 and determining the contamination level by the visual method.

[0572] (Based on dry friction)

[0573] AA: The friction fastness is above level 3-4 (intermediate level) and below level 4.

[0574] A: The friction fastness is above level 2-3 (intermediate level) and below level 3.

[0575] B: The friction fastness is 1-2 level (intermediate level) or higher and 2 level or lower.

[0576] C: Friction fastness is level 1 or less.

[0577] (Wet friction benchmark)

[0578] AA: The friction fastness is above level 3-4 (intermediate level) and below level 4.

[0579] A: The friction fastness is above level 2-3 (intermediate level) and below level 3.

[0580] B: The friction fastness is 1-2 level (intermediate level) or higher and 2 level or lower.

[0581] C: Friction fastness is level 1 or less.

[0582] 3.3.4 Continuous printing stability of white ink

[0583] The colored ink composition (white ink) used in each embodiment and each comparative example is filled in an ink cartridge of SC-F2200 (manufactured by Seiko Epson Corporation). Next, after confirming that the ink is ejected from all nozzles, printing is performed continuously for 1 minute. The coating conditions are the same as those described above. Until the ink coating is completed, the evaluation is performed in an environment of a temperature of 25.0°C and a relative humidity of 40.0%. After printing, the number of nozzles that have produced abnormal ejection is confirmed. This test is performed 3 times, and the average value of the 3 times is used to determine the continuous printing stability according to the following criteria.

[0584] (Judgment Criteria)

[0585] AA: After continuous ejection, no missing prints or disturbances were observed.

[0586] A: After continuous ejection, one or more but two or less nozzles have missing prints or disturbances.

[0587] 3.4 Evaluation results

[0588] The evaluation results are shown in Tables 1 to 5. The inkjet printing method comprises: a reaction liquid attachment step, in which a reaction liquid containing a coagulant for coagulating the components in the ink and water is attached to the fabric by an inkjet method; a transparent ink attachment step, in which a transparent ink composition containing anionic resin particles and water is attached to the fabric by an inkjet method; and a colored ink attachment step, in which a colored ink composition containing pigment, resin particles, and water is attached to the area to which the transparent ink composition is attached by an inkjet method. The reaction liquid attachment step and the transparent ink attachment step have the following step 1: Step 1: Applying the reaction liquid and the transparent ink composition to the same area of ​​the fabric by a single scan of the inkjet head. In the step 1, the minimum value of the total amount of the reaction liquid and the transparent ink composition attached per unit area and unit time is in the range of 34 mg / (s·inch 2 ) As above, each embodiment of the inkjet printing method has excellent color rendering and friction fastness.

[0589] On the other hand, in the inkjet printing method according to each comparative example that does not satisfy the above-mentioned configuration, at least one of the color development property and the friction fastness is deteriorated.

[0590] Although not described in the table, even when printing satisfying the above-mentioned structure was performed in a line printer, the obtained printed material was excellent in color development and friction fastness.

[0591] The following contents are derived from the above-mentioned first embodiment.

[0592] One embodiment of the inkjet printing method comprises: a reaction liquid attaching step, in which a reaction liquid containing a coagulant for coagulating components in ink and water is attached to a fabric by an inkjet method; a transparent ink attaching step, in which a transparent ink composition containing anionic resin particles and water is attached to a fabric by an inkjet method; and a colored ink attaching step, in which a colored ink composition containing a pigment, resin particles, and water is attached to a region to which the transparent ink composition is attached by an inkjet method, wherein the reaction liquid attaching step and the transparent ink attaching step have the following step 1, and in the step 1, the minimum value of the total amount of the reaction liquid and the transparent ink composition attached per unit area and unit time is in the range of 34 mg / (s·inch 2 )above.

[0593] Step 1: Applying the reaction solution and the transparent ink composition to the same area of ​​the fabric by scanning the inkjet head once

[0594] In one embodiment of the inkjet printing method, the step 1 may be performed a plurality of times, the reaction solution attaching step and the clear ink attaching step may include the following step 2, and the step 2 may be performed between the plurality of steps 1.

[0595] In any aspect of the inkjet printing method described above, the pigment may be a white pigment.

[0596] In any aspect of the inkjet printing method, the viscosity of a mixed solution obtained by mixing equal amounts of the reaction solution and the clear ink composition may be 50 mPa·s or more.

[0597] In any one of the aspects of the inkjet printing method, the reaction solution attaching step and the color ink attaching step may be performed simultaneously.

[0598] In any one of the aspects of the inkjet printing method, the colored ink attaching step may be performed by the scanning different from the clear ink attaching step.

[0599] Any one of the above-mentioned inkjet printing methods may include a second transparent ink attaching step in which a second transparent ink composition containing anionic resin particles and water is further attached to the area of ​​the above-mentioned fabric to which the above-mentioned colored ink composition is attached by an inkjet method.

[0600] In any aspect of the inkjet printing method, at least one of the pigment and the resin particles in the colored ink composition may be anionic.

[0601] In any aspect of the inkjet printing method, the resin particles in the colored ink composition may be polyurethane resin or acrylic resin.

[0602] In any aspect of the inkjet printing method, the colored ink composition may further contain 3.0 mass % or more of an organic solvent having a normal boiling point of 250° C. or more.

[0603] Alternatively, in any one of the above-mentioned inkjet printing methods, the above-mentioned fabric may be L * Below 75, it is cotton, polyester or a blend of cotton and polyester.

[0604] In any aspect of the inkjet printing method described above, the pH of the reaction solution may be 2.0 or higher.

[0605] In any one of the above-mentioned inkjet printing methods, in the area on the fabric to which the reaction liquid, the transparent ink composition, and the colored ink composition are attached, the total amount of the reaction liquid, the transparent ink composition, and the colored ink composition attached is 100 mg / inch. 2 above.

[0606] One embodiment of the ink set is an ink set used in the inkjet printing method of any of the above embodiments, and comprises the above reaction solution, the above clear ink composition, and the above colored ink composition.

[0607] 3. Second Implementation Example

[0608] Hereinafter, the second embodiment of the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. % below refers to mass unless otherwise specified.

[0609] 3.1 Preparation of Reaction Solution, Transparent Ink Composition and Colored Ink Composition

[0610] Each component was placed in a container in such a manner as to form the composition of Table 2-1, mixed and stirred, and further filtered using a 5 μm membrane filter to obtain a reaction solution, a transparent ink composition, and a colored ink composition of each example. In addition, the numerical values ​​of each component shown in each example in the table represent mass % unless otherwise specified. In addition, the mass % of the pigment and resin particles in Table 2-1 represents the solid content concentration, and ion exchange water is added so that the total mass of the composition becomes 100 mass %.

[0611] In addition, as a pigment, a pigment dispersion prepared in advance by the following process was used. As a pigment, CI Pigment White 6 (specific gravity: 4.2 g / mL) as titanium oxide was used, and as a pigment dispersant, an anionic resin dispersant was used. Specifically, a styrene-acrylic resin synthesized using 55% by mass of styrene, 20% by mass of acrylic acid, and 30% by mass of methyl methacrylate was used. 1 part by mass of dispersant and 10 parts by mass of ion exchange water were mixed with respect to 3 parts by mass of pigment, and the obtained mixture was pre-mixed, and then a bead mill disperser (UAM-015 manufactured by Kotobuki Industry Co., Ltd.) was used to disperse zirconium oxide beads with a diameter of 0.03 mm at a peripheral speed of 10 m / s and a liquid temperature of 30°C for 15 minutes, and the coarse particles were centrifuged by a centrifugal separator (Model-3600 manufactured by Kuboyama Shoji Co., Ltd.) to obtain a dispersion of titanium oxide.

[0612] Supplementary explanations are provided for the items recorded in Table 2-1.

[0613] Takelac WS-6021 (trade name, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.)

[0614] BYK-348 (trade name, manufactured by BYK)

[0615] Olfine E1010 (trade name, manufactured by Nissin Chemical Industry Co., Ltd.)

[0616] The viscosity was measured in an environment of 20° C. using a viscoelasticity tester MCR-300 (trade name, manufactured by Pysica Corporation).

[0617] The surface tension was measured by confirming the surface tension when a platinum plate was wetted with the reaction solution or the ink in an environment of 20° C. using an automatic surface tensiometer CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.).

[0618] 3.2 Recording conditions

[0619] Using the reaction solution, the clear ink composition, and the colored ink composition prepared as described above, the inkjet printing method according to each of the Examples and Comparative Examples was performed under the following conditions and the conditions described in Table 2-2.

[0620] Printing machine: SC-F2200 (Seiko Epson, serial type) modified machine

[0621] Drying: The fabric was dried at 160° C. for 3 minutes using a conveyor type open-hearth oven (Fusion R 36-6-4 manufactured by M&R Co.).

[0622] Fabric: 100% cotton, black T-shirt (Printstar), L in the colored part * Value 20, the average height of the villi exceeds 50μm

[0623] Image resolution: 1200×600dpi

[0624] · Programming Duty of each column: 100%

[0625] As the head nozzle structure, it becomes Fig.12 In the structure shown, rows A to B serve as nozzle rows for ejecting the reaction liquid, rows C to D serve as nozzle rows for ejecting the clear ink composition, and rows E to H serve as nozzle rows for ejecting the color ink composition.

[0626] The cloth was placed on the platen and printed without being removed from the platen between the steps of attaching the reaction solution and the transparent ink, applying pressure with a squeegee, and attaching the white ink.

[0627] In Examples 1 to 12, the white ink adhesion process was performed after the reaction liquid and the transparent ink adhesion process and the pressure application process by the scraper. In Comparative Example 1, the white ink adhesion process was performed after the reaction liquid and the transparent ink adhesion process. In all Examples, after the white ink adhesion process, drying was performed under the above conditions to obtain printed products.

[0628] In Table 2-2, regarding the presence or absence of scraping (rubbing), "yes" in Examples 2 and 3 means that the scraping (rubbing) was performed by a rubber rubbing machine, and "yes" in Example 2 means that the scraping (rubbing) was performed by a rubber roller.

[0629] The "mixed liquid viscosity" described in Table 2-2 was measured by dropping the reaction liquid and the transparent ink composition in equal amounts on the non-rotating plate in a manner symmetrical about the center of the non-rotating plate in a measuring section consisting of a disk-shaped non-rotating plate and a disk-shaped rotating plate of a rheometer (Anton Paar, MCR302e) at a shear rate of 50 [s -1 ] and the viscosity of the liquid is measured 10 seconds after the start of the plate rotation to obtain the viscosity.

[0630] The average value of the fuzz height was determined by measuring the height of fibers (fuzz) protruding from the surface of the fabric using the 3D observation function of a digital microscope (KEYENCE, VHX-5000), and the height was taken as the average value of fuzz at 10 points.

[0631] In Table 2-2, "landing time difference (reaction liquid / clear ink)" is the time difference between the adhesion of the reaction liquid and the adhesion of the clear ink composition in the same area of ​​the fabric, and the unit is seconds.

[0632] Examples 1 to 6, 9 to 12, and Comparative Example 1 were performed by attaching the reaction liquid and the clear ink composition to the fabric in one scan, while Examples 7 and 8 were performed by attaching the reaction liquid and then attaching the clear ink composition in a different scan.

[0633] In Table 2-2, "time difference from application of two liquids to scraping (rubbing)" indicates the time difference from adhesion of the clear ink composition to scraping.

[0634] 3.3 Evaluation methods

[0635] 3.3.1 Color rendering

[0636] In the printed products obtained by the inkjet printing method according to each of the Examples and Comparative Examples, L * The color rendering property was determined by the following criteria:

[0637] (Judgment Criteria)

[0638] A+: L * More than 90

[0639] A: L * 80 or more but less than 90

[0640] B:L * 75 or more but less than 80

[0641] C:L * Less than 75

[0642] 3.3.2 Image quality changes

[0643] In the printed products obtained by the inkjet printing method according to each of the Examples and Comparative Examples, the surface layer (white ink layer) was visually observed and the image quality was judged to be deteriorated according to the following criteria.

[0644] (Judgment Criteria)

[0645] A: There is no exposure of the medium surface (cotton) due to fluffing in the white ink layer (surface layer).

[0646] B: The surface layer (cotton) of the medium is slightly exposed due to fluffing in the white ink layer (surface layer).

[0647] C: The surface layer (cotton) of the medium is exposed due to fluff in the white ink layer (surface layer).

[0648] 3.3.3Wh cracks in the ink layer

[0649] In the printed products obtained by the inkjet printing method according to each of the Examples and Comparative Examples, the surface layer (white ink layer) was visually observed and cracks were determined based on the following criteria.

[0650] (Judgment Criteria)

[0651] A: No cracks

[0652] B: Slight cracks

[0653] C: There are cracks

[0654] 3.4 Evaluation results

[0655] The evaluation results are shown in Table 2-2. The inkjet printing method comprises: a reaction liquid attachment step, in which a reaction liquid containing a coagulant and water for coagulating the components in the ink is attached to the fabric; a transparent ink attachment step, in which a transparent ink composition containing anionic resin particles and water that react with the coagulant and coagulate is attached to the fabric; and a colored ink attachment step, in which a colored ink composition containing a pigment, resin particles, and water is attached to the area of ​​the fabric to which the transparent ink composition is attached by an inkjet method, and after the reaction liquid attachment step and the transparent ink attachment step, there is a pressure imparting step for imparting pressure to the area of ​​the fabric to which the reaction liquid and the transparent ink composition are attached, the fabric is placed on a mounting table, and the reaction liquid attachment step, the transparent ink attachment step, the pressure imparting step, and the colored ink attachment step are performed in a manner that the relative positional relationship between the fabric and the mounting table is not changed between the steps, and each embodiment of the inkjet printing method can well reduce the influence caused by the fuzzing of the printing surface to form an image.

[0656] On the other hand, in the inkjet printing method according to the comparative example that does not satisfy the above-mentioned configuration, it is not possible to form an image while satisfactorily reducing the influence of the fuzzing of the printing surface.

[0657] The following contents are derived from the above-mentioned second embodiment.

[0658] One mode of the inkjet printing method comprises: a reaction liquid attaching step of attaching a reaction liquid containing a coagulant and water for coagulating components in ink to a fabric; a transparent ink attaching step of attaching a transparent ink composition containing anionic resin particles and water that react with the above-mentioned coagulant and coagulate to the above-mentioned fabric; and a colored ink attaching step of attaching a colored ink composition containing pigment, resin particles and water to a region of the above-mentioned fabric to which the above-mentioned transparent ink composition is attached by an inkjet method, and after the above-mentioned reaction liquid attaching step and the above-mentioned transparent ink attaching step, there is a pressure applying step of applying pressure to the region of the above-mentioned fabric to which the above-mentioned reaction liquid and the above-mentioned transparent ink composition are attached, the above-mentioned fabric is placed on a mounting table, and the above-mentioned reaction liquid attaching step, the above-mentioned transparent ink attaching step, the above-mentioned pressure applying step, and the above-mentioned colored ink attaching step are performed in a manner that the relative positional relationship between the above-mentioned fabric and the above-mentioned mounting table is not changed between each step.

[0659] In one aspect of the inkjet printing method, a time difference between adhesion of the reaction solution and adhesion of the clear ink composition to the same region of the cloth may be within 30 seconds.

[0660] In any one of the aspects of the inkjet printing method, the reaction solution attaching step and the clear ink attaching step may include the following step 1.

[0661] Step 1: Applying the reaction solution and the transparent ink composition to the same area of ​​the fabric by one scanning operation

[0662] Alternatively, in any of the above-mentioned inkjet printing methods, the viscosity of the above-mentioned reaction liquid and the above-mentioned transparent ink composition is 3 to 8 mPa·s at 20°C, and the viscosity of an equal amount of the mixture of the above-mentioned reaction liquid and the above-mentioned transparent ink composition is greater than 50 mPa·s at 20°C.

[0663] In any one of the above-mentioned inkjet printing methods, the total coating amount of the reaction solution and the clear ink composition may be 0.02 g / inch. 2 above.

[0664] In any one of the aspects of the inkjet printing method, the coating amount ratio of the reaction solution to the clear ink composition may be 1:10 to 10:1.

[0665] In any one of the aspects of the inkjet printing method described above, the cloth may be a cloth having nap.

[0666] Alternatively, in any of the above-mentioned inkjet printing methods, the L of the above-mentioned fabric may be * a * b *Brightness L in the color system * The value is below 70.

[0667] In any aspect of the inkjet printing method described above, the pigment may be a white pigment.

[0668] In any aspect of the inkjet printing method, the coagulant may contain an organic acid, and the organic acid may be contained in an amount of 1 to 6% by mass based on the total amount of the reaction solution.

[0669] In any one of the aspects of the inkjet printing method, the pressure applying step may be performed by direct contact between the cloth and a pressure applying unit.

[0670] In any aspect of the inkjet printing method, the reaction solution may contain a surfactant, and a content of the surfactant may be 2.0% by mass or less based on the total amount of the reaction solution.

[0671] In any one of the aspects of the inkjet printing method, the pressure applying step may be performed before the color ink attaching step.

[0672] In any aspect of the inkjet printing method, the pressure applying step may be performed within 30 minutes after the clear ink attaching step.

[0673] In any one of the aspects of the inkjet printing method, the reaction solution attaching step and the clear ink attaching step may be performed by an inkjet method.

[0674] In any aspect of the inkjet printing method described above, the pH of the reaction solution may be 2.0 or higher.

[0675] In any one of the above-mentioned inkjet printing methods, the total amount of the reaction solution, the transparent ink composition, and the colored ink composition deposited is 100 mg / inch. 2 above.

[0676] One embodiment of an ink set is an ink set used in the inkjet printing method of any of the above embodiments, and comprises the above reaction solution, the above clear ink composition, and the above colored ink composition.

[0677] The present invention is not limited to the above-mentioned embodiments, and various modifications are possible. For example, the present invention includes a structure that is substantially the same as the structure described in the embodiments, such as a structure with the same function, method and result, or a structure with the same purpose and effect. In addition, the present invention includes a structure in which a non-essential part of the structure described in the embodiments is replaced. In addition, the present invention includes a structure that can have the same effect as the structure described in the embodiments, or a structure that can achieve the same goal. In addition, the present invention includes a structure in which the structure described in the embodiments is supplemented with a known technology.

Claims

1. An inkjet printing and dyeing method, characterized in that: have: a reaction liquid attaching step of attaching a reaction liquid containing a coagulant for coagulating components in the ink and water to the fabric by an inkjet method; a transparent ink attaching step of attaching a transparent ink composition containing anionic resin particles and water to a fabric by an inkjet method; and The colored ink attaching step is to attach a colored ink composition containing a pigment, resin particles and water to the area to which the transparent ink composition is attached by an inkjet method. The reaction liquid attaching step and the transparent ink attaching step include the following step 1: In the step 1, the minimum value of the total amount of the reaction solution and the clear ink composition deposited per unit area and unit time is in the range of 34 mg / (s·inch 2 )above, Step 1: Applying the reaction solution and the transparent ink composition to the same area of ​​the fabric by scanning the inkjet head once.

2. The inkjet printing and dyeing method according to claim 1, characterized in that: Carry out the step 1 multiple times, The reaction liquid attaching step and the transparent ink attaching step include the following step 2, The step 2 is performed between the steps 1 being performed multiple times, Step 2: The cloth is conveyed in a direction intersecting the scanning direction.

3. The inkjet printing and dyeing method according to claim 1 or 2, characterized in that: The pigment is a white pigment.

4. The inkjet printing and dyeing method according to claim 1 or 2, characterized in that: The viscosity of the mixed solution obtained by mixing equal amounts of the reaction solution and the clear ink composition is 50 mPa·s or more.

5. The inkjet printing and dyeing method according to claim 1 or 2, characterized in that: The reaction liquid attaching step and the colored ink attaching step are performed simultaneously.

6. The inkjet printing and dyeing method according to claim 1 or 2, characterized in that: The colored ink attaching step is performed by the scanning different from the clear ink attaching step.

7. The inkjet printing and dyeing method according to claim 1 or 2, characterized in that: The method further comprises a second clear ink attaching step of attaching a second clear ink composition containing anionic resin particles and water by an inkjet method to the region of the fabric to which the color ink composition has been attached.

8. The inkjet printing and dyeing method according to claim 1 or 2, characterized in that: At least one of the pigment and the resin particles in the colored ink composition is anionic.

9. The inkjet printing and dyeing method according to claim 1 or 2, characterized in that: The resin particles in the colored ink composition are polyurethane resin or acrylic resin.

10. The inkjet printing and dyeing method according to claim 1 or 2, characterized in that: The colored ink composition further contains 3.0 mass % or more of an organic solvent having a normal boiling point of 250° C. or more.

11. The inkjet printing and dyeing method according to claim 1 or 2, characterized in that: The cloth is L * Below 75, it is cotton, polyester or a blend of cotton and polyester.

12. The inkjet printing and dyeing method according to claim 1 or 2, characterized in that: The pH of the reaction solution is above 2.

0.

13. The inkjet printing and dyeing method according to claim 1 or 2, characterized in that: In the area of ​​the fabric to which the reaction liquid, the clear ink composition, and the colored ink composition are attached, the total amount of the reaction liquid, the clear ink composition, and the colored ink composition attached is 100 mg / inch 2 above.

14. An ink set, characterized in that: The ink set is used for the inkjet printing method according to claim 1, The invention comprises the reaction liquid, the transparent ink composition and the colored ink composition.

15. An inkjet printing method, characterized in that: have: a reaction liquid adhering step of making a reaction liquid containing a coagulant for coagulating components in the ink and water adhere to the fabric; a transparent ink attaching step of attaching a transparent ink composition containing anionic resin particles that react with the coagulant and coagulate and water to the fabric; as well as a colored ink attaching step of attaching a colored ink composition containing a pigment, resin particles and water to the area of ​​the fabric to which the transparent ink composition is attached by an inkjet method; After the reaction liquid attaching step and the clear ink attaching step, there is a pressure applying step of applying pressure to the region of the fabric to which the reaction liquid and the clear ink composition are attached, The cloth is placed on a mounting table, and the reaction liquid attaching step, the transparent ink attaching step, the pressure applying step, and the colored ink attaching step are performed without changing the relative positional relationship between the cloth and the mounting table between the steps.

16. The inkjet printing method according to claim 15, characterized in that: The time difference between the adhesion of the reaction liquid and the adhesion of the clear ink composition in the same region of the cloth is within 30 seconds.

17. The inkjet printing method according to claim 15, characterized in that: The reaction liquid attaching step and the transparent ink attaching step include the following step 1: Step 1: Applying the reaction solution and the transparent ink composition to the same area of ​​the fabric by one and the same scanning.

18. The inkjet printing method according to claim 15, characterized in that: The viscosity of the reaction solution and the transparent ink composition is 3 to 8 mPa·s at 20° C. The viscosity of a mixed solution of equal amounts of the reaction solution and the clear ink composition is 50 mPa·s or more at 20° C.

19. The inkjet printing method according to claim 15, characterized in that: The total coating amount of the reaction solution and the transparent ink composition is 0.02 g / inch 2 above.

20. An ink set, characterized in that: The ink set for the inkjet printing method according to claim 15, The invention comprises the reaction liquid, the transparent ink composition and the colored ink composition.

Images