Inkjet printing method and ink set

Abstract

To provide an inkjet printing method which satisfactorily reduces image quality disturbance by fuzz of a fabric.SOLUTION: An inkjet printing method includes a reaction liquid adhesion step of attaching reaction liquid containing a coagulant for aggregating a component in ink, and water to a fabric, a transparent ink adhesion step of attaching a transparent ink composition containing anionic resin particles which are reacted with the coagulant and aggregated, and water, to the fabric, and a color ink adhesion step of attaching a color ink composition containing a pigment, resin particles and water, to a region where the transparent ink composition of the fabric is attached, by an inkjet method, and has a pressure applying step of applying a pressure to the region where the reaction liquid of the fabric and the region where the transparent ink composition is attached, after the reaction liquid adhesion step and the transparent ink adhesion step, wherein the fabric is mounted on a mounting base, and the reaction liquid adhesion step, the transparent ink adhesion step, the pressure applying step, and the color ink adhesion step are performed without changing a relative positional relation between the fabric and the mounting base between the steps.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an inkjet textile printing method and an ink set. [Background technology]

[0002] BACKGROUND ART In textile printing using an inkjet ink composition containing a pigment as a coloring material (pigment textile printing), a technique has been known in the past in which a fabric is treated with a reaction liquid containing an aggregating agent that aggregates components in the ink in order to improve rub fastness and color development.

[0003] For example, Patent Document 1 describes an inkjet printing method for printing on a textile substrate, the inkjet printing method including, in the following order: a) providing the substrate; b) applying a pretreatment composition containing a polyvalent cation and / or an acid salt; c) applying by spraying a clear ink containing a polymer binder; d) applying by spraying a white ink; and e) applying by spraying a non-white colored ink. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2022-548985 Summary of the Invention [Problem to be solved by the invention]

[0005] However, there was some image quality degradation due to the fluffing of the fabric. [Means for solving the problem]

[0006] One aspect of the inkjet printing method according to the present invention comprises: a reaction liquid applying step of applying a reaction liquid containing water and an aggregating agent that aggregates components in the ink to the fabric; a transparent ink applying step of applying a transparent ink composition containing anionic resin particles that react with the aggregating agent and aggregate, and water, to the fabric; a colored ink applying step of applying a colored ink composition containing a pigment, resin particles, and water by an inkjet method onto the area of ​​the fabric to which the transparent ink composition has been applied; a pressure application step of applying pressure to an area of ​​the fabric to which the reaction liquid and the transparent ink composition have been applied, after the reaction liquid application step and the transparent ink application step; The fabric is placed on a mounting table, and the reaction liquid application process, the transparent ink application process, the pressure application process, and the colored ink application process are performed without changing the relative positional relationship between the fabric and the mounting table between each process.

[0007] One aspect of the ink set according to the present invention is An ink set for use in the inkjet printing method, The ink jet recording medium includes the reaction liquid, the transparent ink composition, and the colored ink composition. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a perspective view of an inkjet textile printing apparatus. [Figure 2] FIG. 1 is a schematic side view of an inkjet textile printing apparatus. [Figure 3] FIG. 2 is a diagram showing a state of a material to be printed and the material to be printed placed on a placing table. [Figure 4] FIG. 2 is a schematic diagram showing an example of the arrangement of nozzle rows of an inkjet head. [Figure 5] FIG. 1 is a schematic side view of a line printer. [Figure 6] Table 1 shows examples of compositions of the reaction liquid, the clear ink composition, and the colored ink composition. [Figure 7] Table 2 shows the recording conditions of the inkjet printing method according to each example and comparative example. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, embodiments of the present invention will be described. The embodiments described below are examples of the present invention. The present invention is not limited to the following embodiments, and includes various modified forms that are implemented within the scope of the present invention. Note that not all of the configurations described below are necessarily essential configurations of the present invention.

[0010] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In this specification, the term "inkjet method" refers to a droplet ejection method using an inkjet system. In this specification, "(meth)acrylic" refers to acrylic or methacrylic, and "(meth)acrylate" refers to acrylate or methacrylate.

[0011] 1. Inkjet printing method An inkjet textile printing method according to one embodiment of the present invention comprises: a reaction liquid applying step of applying a reaction liquid containing water and an aggregating agent that aggregates components in the ink to a fabric; a clear ink applying step of applying a transparent ink composition containing water and anionic resin particles that react with the aggregating agent to aggregate the components in the ink to the fabric; and a colored ink applying step of applying a colored ink composition containing a pigment, resin particles, and water by an inkjet method to an area of ​​the fabric to which the clear ink composition has been applied; the method further comprises a pressure applying step, after the reaction liquid applying step and the clear ink applying step, of applying pressure to the area of ​​the fabric to which the reaction liquid and the transparent ink composition have been applied; the fabric is placed on a mounting table; and the reaction liquid applying step, the clear ink applying step, the pressure applying step, and the colored ink applying step are carried out without changing the relative positional relationship between the fabric and the mounting table between each step.

[0012] Conventionally, in inkjet textile printing, a process of applying a reaction liquid that aggregates ink components to fabric has been performed to improve the color development of coloring materials. This process has typically been performed using a device or facility separate from the inkjet recording device, or has often been performed manually, requiring large equipment and complicated processes. Therefore, studies have been conducted on a mode in which the reaction liquid and ink are applied continuously within the same device. Such a mode would eliminate the need for separate devices or facilities and simplify the process.

[0013] However, when the reaction liquid and the ink are applied successively in the same device, it is not possible to prevent the fabric from becoming fluffed, and image quality is likely to be impaired.

[0014] In contrast, in the inkjet printing method according to this embodiment, the aggregating agent in the reaction liquid aggregates the components of the clear ink on the fabric, forming a highly viscous gel-like aggregate near the surface of the fabric. By applying pressure (wiping) to the fabric surface to which this aggregate has adhered using a rubber blade or the like, the viscosity of the gel-like aggregate fixes the nap in a flattened state. Then, colored ink is deposited on top of this, making it possible to form an image with reduced effects of nap on the printing surface.

[0015] Hereinafter, each step of the inkjet printing method according to this embodiment will be described.

[0016] 1.1 Reaction solution attachment process The inkjet printing method according to this embodiment includes: The method includes a reaction liquid applying step of applying a reaction liquid containing water to the fabric.

[0017] 1.1.1 Adhesion pattern The means for applying the reaction liquid to the fabric is not particularly limited, and examples include dip coating, in which the fabric is immersed in the reaction liquid; roller coating, in which the reaction liquid is applied using a brush, roller, spatula, roll coater, or the like; spray coating, in which the reaction liquid is sprayed using a spray device, or the like; and inkjet coating, in which the reaction liquid is applied by an inkjet method. Among these, the inkjet method is preferred, and the reaction liquid application step and the transparent ink application step described below are preferably performed by the inkjet method. In this case, it is possible to selectively apply the reaction liquid and the transparent ink to the image-forming areas of the colored inks applied to the fabric in the colored ink application step described below, and it is possible to prevent processing marks from occurring in the non-image-forming areas.

[0018] The total coating amount of the reaction liquid and the transparent ink composition described below was 0.02 g / inch 2 It is preferable that the density is 0.05 g / inch or more. 2 More preferably, it is 0.07 g / inch or more. 2 More preferably, it is 0.10 g / inch or more. 2 When the total application amount is within the above range, the fluff fixing effect is further improved, and image quality disturbances due to fluffing of the fabric tend to be further reduced. The upper limit of the total coating amount is not particularly limited, but is preferably 1.0 g / inch. 2 Preferably less than 0.50g / inch 2 Less than 0.30g / inch is more preferable. 2 Less than 0.15g / inch is more preferable. 2 The following are particularly preferred:

[0019] The coating amount ratio of the reaction liquid to the transparent ink composition described below is preferably 1:10 to 10:1, more preferably 3:10 to 10:3, even more preferably 5:10 to 10:5, particularly preferably 7:10 to 10:7, and even particularly preferably 9:10 to 10:9. When the coating amount ratio is within the above range, the fluff fixing effect is further improved, and image quality disturbances due to fluffing of the fabric tend to be further reduced.

[0020] The time difference between the deposition of the reaction liquid and the deposition of the transparent ink composition described below in the same region of the fabric is preferably 30 seconds or less, more preferably 15 seconds or less, even more preferably 5 seconds or less, even more preferably 1 second or less, particularly preferably 0.5 seconds or less, and even particularly preferably 0.1 seconds or less. When the time difference is within the above range, image quality disturbance due to fabric fluffing can be further reduced, and color development tends to be better.

[0021] The reaction liquid applying step and the transparent ink applying step described below preferably include the following step 1. Step 1: Applying the reaction liquid and the transparent ink composition to the same area of ​​the fabric in one identical scan According to the application in step 1, the reaction liquid and the transparent ink composition can be applied to the fabric continuously in the same device by the inkjet method, which tends to further reduce image quality disturbances caused by fabric fluffing and also improve color development.

[0022] Here, "scanning" in step 1 refers to moving the inkjet head relative to the recording area on the fabric. In this case, the inkjet head may move relative to the fabric, or the fabric may move relative to the inkjet head. Furthermore, the relative positional relationship between the inkjet head and the fabric may change as both of them move.

[0023] Therefore, in the serial inkjet printing apparatus 1 shown in FIGS. 1 and 2, the "scanning" in step 1 is performed by scanning a carriage having an inkjet head 14. The recording is performed while the recording medium 13 moves in a scanning direction SD that intersects with the moving direction TD of the print-target material P placed on the placement table 7.

[0024] On the other hand, the "scanning" in step 1 may be performed in a line-type printer as shown in Fig. 5, in which the fabric moves relative to a line head 300 having a length corresponding to the width of the fabric in a direction intersecting the width direction. In line-type recording, the inkjet head (line head) is fixed and does not move during recording, and recording is performed in one scan.

[0025] The "length equivalent to the width of the fabric" does not necessarily mean that the width of the fabric and the length (width) of the line head are completely the same, but may be a length equal to or greater than the length equivalent to the width of the fabric, or may be a length equivalent to the width of the fabric (recorded width) onto which ink should be ejected (on which an image should be recorded).

[0026] 1.1.2 Reaction solution The reaction liquid used in the reaction liquid application step contains an aggregating agent that aggregates the components in the ink, and water. Each component contained in the reaction liquid will be described below.

[0027] 1.1.2.1 Flocculants The reaction liquid contains an aggregating agent that aggregates components in the ink. The aggregating agent acts on the dispersibility of components such as anionic resin particles contained in the clear ink composition and pigments and resin particles contained in the colored ink composition, thereby aggregating at least one of these components. The degree of aggregation of the dispersion by the aggregating agent varies depending on the type of aggregating agent and the target, and can be adjusted. This aggregating action can, for example, improve the color development and fixability of the image.

[0028] The reaction solution preferably contains one or more flocculants selected from the group consisting of organic acids, polyvalent metal salts, and cationic polymers, which may provide better resistance to friction and color development.

[0029] Suitable examples of the organic acid 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, pyridinecarboxylic acid, coumaric acid, thiophenecarboxylic acid, nicotinic acid, derivatives of these compounds, and salts thereof. The organic acids may be used singly or in combination of two or more. Note that salts of organic acids that are metal salts are included in the metal salts described below.

[0030] Polyvalent metal salts are compounds composed of divalent or higher metal ions and anions. Examples of divalent or higher metal ions include calcium, magnesium, copper, nickel, zinc, barium, aluminum, titanium, strontium, chromium, cobalt, and iron ions. Among the metal ions that compose these polyvalent metal salts, at least one of calcium ions and magnesium ions is preferred because they have excellent coagulation properties for ink components.

[0031] The anions constituting the polyvalent metal salts are inorganic or organic ions. Examples of such inorganic ions include chloride ions, bromide ions, iodide ions, formate ions, nitrate ions, sulfate ions, and hydroxide ions. Examples of organic ions include organic acid ions, such as carboxylate ions.

[0032] Specific examples of the polyvalent metal salt include calcium carbonate (heavy calcium carbonate and light 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, and aluminum lactate. These polyvalent metal salts may be used alone or in combination. Among these, at least one of magnesium sulfate, calcium formate, calcium nitrate, aluminum lactate, and calcium propionate is preferred because of their sufficient solubility in water. These metal salts may have water of hydration in their raw material form, such as magnesium sulfate heptahydrate and calcium nitrate tetrahydrate.

[0033] The cationic polymer refers to a polymer compound having a cationic group, and examples of the cationic polymer include cationic urethane resins, cationic olefin resins, cationic amine resins, and cationic amide resins. The cationic amine resin may be any resin having an amino group, and examples thereof include allylamine resin, polyamine resin, and quaternary ammonium salt polymer. Allylamine resins include those having a structure derived from an allyl group in the main skeleton of the resin. Polyamine resins include those having an amino group in the main skeleton of the resin. Quaternary ammonium salt polymers include resins having a quaternary ammonium salt in the structure. Among cationic polymers, cationic amine resins are preferred because they are not only highly reactive but also easily available.

[0034] The flocculants may be used alone or in combination of two or more.

[0035] From the viewpoint of achieving better color development and rubbing resistance, the lower limit of the content of the coagulant is, for example, preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, particularly preferably 3% by mass or more, and more particularly preferably 4% by mass or more, relative to the total amount of the reaction liquid. Furthermore, the upper limit of the content of the flocculant is not particularly limited, but for example, it is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, particularly preferably 8% by mass or less, and more particularly preferably 6% by mass or less, relative to the total amount of the reaction liquid.

[0036] In particular, the aggregating agent preferably contains an organic acid in an amount of 1 to 6 mass %, more preferably 1 to 5 mass %, and even more preferably 2 to 4 mass %, relative to the total amount of the reaction solution. In this case, the clear ink composition can be more effectively aggregated, the fluff fixing effect is further improved, and image quality degradation due to fluffing of the fabric tends to be further reduced.

[0037] 1.1.2.2 Water The reaction solution contains water. Examples of water include pure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water, as well as water with reduced ionic impurities such as ultrapure water. Furthermore, using water sterilized by ultraviolet irradiation or the addition of hydrogen peroxide can suppress the growth of bacteria and fungi when the reaction solution is stored for a long period of time.

[0038] The water content is preferably 40% by mass or more, more preferably 45% by mass or more, even 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 water content is not particularly limited, but is, for example, preferably 90% by mass or less, further 85% by mass or less, and more preferably 80% by mass or less, relative to the total amount of the reaction solution.

[0039] 1.1.2.3 Organic solvents The reaction liquid may contain an organic solvent, such as esters, alkylene glycol ethers, cyclic esters, amides, alcohols, and polyhydric alcohols.

[0040] Examples of esters include 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, Examples of the glycol monoacetates include propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and methoxybutyl acetate; and glycol diesters include ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, ethylene glycol acetate propionate, ethylene glycol acetate butyrate, diethylene glycol acetate butyrate, diethylene glycol acetate propionate, diethylene glycol acetate butyrate, propylene glycol acetate propionate, propylene glycol acetate butyrate, dipropylene glycol acetate butyrate, and dipropylene glycol acetate propionate.

[0041] The alkylene glycol ethers may be monoethers or diethers of alkylene glycol, and alkyl ethers are preferred. Specific examples 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, tripropylene glycol monobutyl ether, and the like. alkylene glycol monoalkyl 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, tripropylene glycol dimethyl ether, and alkylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and tripropylene glycol dimethyl ether.

[0042] Examples of cyclic esters include β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, β-butyrolactone, β-valerolactone, γ-valerolactone, β-hexanolactone, γ-hexanolactone, δ-hexanolactone, and β-hexanolactone. Examples include cyclic esters (lactones) such as butanolactone, γ-heptanolactone, δ-heptanolactone, ε-heptanolactone, γ-octanolactone, δ-octanolactone, ε-octanolactone, δ-nonalactone, ε-nonalactone, and ε-decanolactone, as well as compounds in which the hydrogen atom of the methylene group adjacent to the carbonyl group of these cyclic esters is substituted with an alkyl group having 1 to 4 carbon atoms.

[0043] Examples of the amides include cyclic amides and non-cyclic amides. Examples of the non-cyclic amides include alkoxyalkyl amides.

[0044] Examples of cyclic amides include lactams, such as pyrrolidones such as 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone.

[0045] Examples of 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, Examples of the propionamide include propionamide, 3-n-propoxy-N,N-diethylpropionamide, 3-n-propoxy-N,N-methylethylpropionamide, 3-iso-propoxy-N,N-dimethylpropionamide, 3-iso-propoxy-N,N-diethylpropionamide, 3-iso-propoxy-N,N-methylethylpropionamide, 3-tert-butoxy-N,N-dimethylpropionamide, 3-tert-butoxy-N,N-diethylpropionamide, 3-tert-butoxy-N,N-methylethylpropionamide, and N,N-dimethylisobutyric acid amide.

[0046] Examples of alcohols include compounds in which one hydrogen atom of an alkane has been substituted with a hydroxyl group. The alkane preferably has 10 or fewer carbon atoms, more preferably 6 or fewer carbon atoms, and even more preferably 3 or fewer carbon atoms. The alkane has 1 or more carbon atoms, preferably 2 or more carbon atoms. The alkane may be linear or branched. Examples of alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, 2-butanol, tert-butanol, iso-butanol, n-pentanol, 2-pentanol, 3-pentanol, and tert-pentanol, 2-phenoxyethanol, benzyl alcohol, and phenoxypropanol.

[0047] Polyhydric alcohols have two or more hydroxyl groups in the molecule and can be divided into, for example, alkanediols and polyols.

[0048] Examples of alkanediols include compounds in which an alkane is substituted with two hydroxyl groups, such as 1,2-alkanediol, which is a general term for compounds in which hydroxyl groups are substituted at the 1st and 2nd positions of an alkane, and alkanediols other than 1,2-alkanediol.

[0049] Examples of 1,2-alkanediols include ethylene glycol, 1,2-propanediol (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, and 1,2-decanediol. hexanediol, 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, and 3-ethyl-4-methyl-1,2-hexanediol.

[0050] Other alkanediols include, for example, 1,3-propanediol, 1,3-butylene glycol (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.

[0051] Examples of polyols include condensates in which two or more molecules of alkanediols are intermolecularly condensed via the hydroxyl groups thereof, and compounds having three or more hydroxyl groups.

[0052] Examples of condensates in which two or more molecules of alkanediols are intermolecularly condensed via the hydroxyl groups thereof include dialkylene glycols such as diethylene glycol and dipropylene glycol, and trialkylene glycols such as triethylene glycol and tripropylene glycol.

[0053] The compound having three or more hydroxyl groups is a compound having an alkane or polyether structure as a backbone and having three or more hydroxyl groups, such as glycerin, trimethylolethane, trimethylolpropane, 1,2,5-hexanetriol, 1,2,6-hexanetriol, pentaerythritol, and polyoxypropylenetriol.

[0054] The organic solvents may be used alone or in combination of two or more.

[0055] Among these, the organic solvent preferably contains an alkanediol, more preferably contains a 1,2-alkanediol, and particularly preferably contains propylene glycol. When the organic solvent contains these solvents, the color development and rub fastness may be more excellent.

[0056] The content of the organic solvent is preferably 5 to 50 mass %, more preferably 10 to 40 mass %, further preferably 15 to 35 mass %, and particularly preferably 20 to 30 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 rub fastness may be better.

[0057] 1.1.2.4 Surfactants The reaction liquid may contain a surfactant. The surfactant can be used to reduce the surface tension of the reaction liquid and, for example, adjust and improve the permeability into fabric. As the surfactant, any of nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used, and these may also be used in combination. In addition, the surfactant Among these surfactants, acetylene-based surfactants (acetylene glycol-based surfactants), silicon-based surfactants, and fluorine-based surfactants can be more preferably used, and acetylene-based surfactants can be even more preferably used.

[0058] The acetylene-based surfactant (acetylene glycol-based 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). Examples of suitable acrylic acid esters include 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, and AE-3 (trade names, manufactured by Nissin Chemical Industry Co., Ltd.), and Acetylenol E00, E00P, E40, and E100 (trade names, manufactured by Kawaken Fine Chemicals Co., Ltd.).

[0059] The silicone surfactant is not particularly limited, but a polysiloxane compound is preferred, and the polysiloxane compound is not particularly limited, but for example, a polyether-modified organosiloxane is exemplified. Commercially available polyether-modified organosiloxanes include, for example, 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.).

[0060] As the fluorine-based surfactant, it is preferable to use a fluorine-modified polymer, and a specific example thereof is BYK-340 (trade name, manufactured by BYK Japan KK).

[0061] The surfactants may be used alone or in combination of two or more.

[0062] The reaction solution preferably contains a surfactant with an HLB value of 10 or more. When the surfactant has an HLB value of 10 or more, the permeability of the reaction solution into the fabric can be adjusted favorably, and the reaction solution tends to be more easily retained near the surface of the fabric. This tends to result in better color development.

[0063] As used herein, the term "HLB value" refers to the value of hydrophilicity and The HLB value is a numerical representation of the hydrophilic-hydrophobic balance of a compound. Here, the HLB value is a value calculated by the Griffin method and can be calculated using the following formula (1): HLB value = 20 × total formula weight of hydrophilic moieties / molecular weight (1)

[0064] Specific examples of surfactants having an HLB value of 10 or more according to the Griffin method are listed below.

[0065] Examples of acetylene surfactants (acetylene glycol surfactants) having an HLB value of 10 or more include Olfine E1010 (HLB value 12), E1020 (HLB value 15-16), EXP. 4200 (HLB value 10-13), and EXP. 4123 (HLB value 10-13) [trade names, manufactured by Nissin Chemical Industry Co., Ltd.].

[0066] Examples of silicone surfactants with an HLB value of 10 or more include BYK-348 (HLB (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 Examples include FZ-2104 (HLB value 14) and SILWET FZ-2161 (HLB value 20) (trade name, manufactured by Nippon Unicar Co., Ltd.).

[0067] 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, even more preferably 2.0% by mass or less, particularly preferably 1.5% by mass or less, and more particularly preferably 1.0% by mass or less, relative to the total amount of the reaction liquid. When the content of the surfactant is within the above range, particularly 2.0% by mass or less, the viscosity of the mixture when the reaction liquid and the clear ink are mixed tends to increase, the fluff fixing effect is further improved, and image quality disturbance due to fluffing of the fabric tends to be further reduced. The lower limit of the surfactant content 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, relative to the total amount of the reaction liquid.

[0068] 1.1.2.5 Other ingredients The reaction solution may contain additives such as pH adjusters, preservatives, antifungals, rust inhibitors, chelating agents, viscosity adjusters, solubilizing agents, antioxidants, etc. When such additives are contained, the content thereof is preferably 0.05 to 5 mass %, more preferably 0.1 to 3 mass %, and even more preferably 0.1 to 1 mass %, relative to the total amount of the reaction solution.

[0069] The pH adjuster is not particularly limited, but may be an appropriate combination of an acid, a base, a weak acid, or a weak base. Examples of acids and bases used in such combinations include inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid; inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium dihydrogen phosphate, disodium hydrogen phosphate, potassium carbonate, sodium carbonate, sodium bicarbonate, and ammonia; organic bases such as triethanolamine, diethanolamine, monoethanolamine, tripropanolamine, triisopropanolamine, diisopropanolamine, and trishydroxymethylaminomethane (THAM); and organic acids such as adipic acid, citric acid, succinic acid, lactic acid, and N,N-bis(2-hydroxybenzoic acid). Other examples of suitable buffers include N-(2-acetamido)-2-aminoethanesulfonic acid (BES), 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES), morpholinoethanesulfonic acid (MES), carbamoylmethyliminobisacetic acid (ADA), piperazine-1,4-bis(2-ethanesulfonic acid) (PIPES), N-(2-acetamido)-2-aminoethanesulfonic acid (ACES), cholamine hydrochloride, N-tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid (TES), acetamidoglycine, tricine, glycinamide, and Good's buffers such as bicine, phosphate buffer, citrate buffer, and Tris buffer. Among these, inorganic bases are preferred, and potassium hydroxide is more preferred.

[0070] The reaction solution may contain one or more pH adjusters, and the total content of the pH adjusters relative to the total amount of the reaction solution is, for example, from 0.05% to 3.0% by mass, and more preferably from 0.1% to 1.0% by mass.

[0071] The reaction liquid may contain a coloring material such as a pigment, but the amount of the coloring material is limited to 0.2 mass % of the total amount of the reaction liquid. % or less, more preferably 0.1% by mass or less, and even more preferably 0.05% by mass or less, the lower limit being 0% by mass. It is preferred that the reaction liquid does not contain a colorant.

[0072] 1.1.2.6 Physical Properties From the viewpoint of reducing skin irritation, the pH of the reaction solution is preferably 2.0 or higher, more preferably 3.0 or higher, and even more preferably 4.0 or higher. From the same viewpoint, the upper limit of the pH is preferably 11.5 or lower, more preferably 10 or lower, even more preferably 7.0 or lower, and particularly preferably 5.0 or lower.

[0073] The viscosity of the reaction solution at 20°C is preferably 1.0 to 10 mPa·s, more preferably 3.5 to 8.0 mPa·s, and even more preferably 2.0 to 4.0 mPa·s. In particular, a viscosity of 3.0 mPa·s or higher tends to result in better color development. A viscosity of 8.0 mPa·s or lower tends to result in better ejection stability. The viscosity can be measured using, for example, a viscoelasticity tester MCR-300 (product name) manufactured by Pysica.

[0074] The viscosity of a mixture obtained by mixing equal amounts of the reaction liquid and the transparent ink composition described below (for example, the viscosity after 3 minutes of mixing) at 20°C is preferably 50 mPa·s or more, more preferably 100 mPa·s or more, even more preferably 300 mPa·s or more, particularly preferably 500 mPa·s or more, and even particularly preferably 750 mPa·s or more. When the viscosity of the mixture is within the above range, the rate of water absorption into the fabric is slowed, making it possible to more effectively form a transparent ink layer (resin layer) near the surface of the fabric. This can further suppress the penetration of the colored ink into the fabric, tending to result in better color development. Furthermore, the resin layer functions better as a binder layer between the fabric and the colored ink layer, tending to result in better abrasion resistance. The upper limit of the viscosity of the mixture obtained by mixing equal amounts of the reaction liquid and the transparent ink composition described below is not particularly limited, but is preferably 10,000 mPa·s or less at 20°C, more preferably 5,000 mPa·s or less, particularly preferably 2,500 mPa·s or less, and even more particularly preferably 1,500 mPa·s or less.

[0075] In particular, it is preferable that the viscosity of the reaction liquid and the transparent ink composition described below is 3 to 8 mPa·s at 20° C., and that the viscosity of an equal mixture of the reaction liquid and the transparent ink composition described below is 50 mPa·s or greater at 20° C. In this case, better ejection stability is obtained, and the fluff fixing effect is further improved, tending to further reduce image quality disturbances caused by fluffing of the fabric.

[0076] The surface tension of the reaction solution is preferably 25 to 40 mN / m, more preferably 25 to 35 mN / m, even more preferably 27 to 35 mN / m, and particularly preferably 30 to 33 mN / m. 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 measured at 20°C.

[0077] 1.2 Transparent ink application process The inkjet printing method according to this embodiment includes a clear ink applying step of applying to fabric a clear ink composition containing water and anionic resin particles that react with an aggregating agent to aggregate.

[0078] 1.2.1 Adhesion pattern The means for attaching the transparent ink to the fabric can be the same as that for the reaction liquid described above. The total application amount and application amount ratio of the transparent ink composition, the time difference between the application of the reaction liquid and the application of the transparent ink composition to the same region of the fabric, and the application mode in step 1 and the like are also the same as those explained in the reaction liquid application step above, and therefore will not be explained here.

[0079] 1.2.2 Transparent ink composition The transparent ink composition used in the transparent ink application step contains water and anionic resin particles that react with an aggregating agent to aggregate. Each component of the transparent ink composition will be described below.

[0080] 1.2.2.1 Anionic resin particles The clear ink composition contains anionic resin particles. Similar to the function of resin particles, the anionic resin particles function as a fixing resin, improving the adhesion of ink applied to fabric. The anionic resin particles also react with the aggregating agent to form aggregates, thereby thickening the clear ink composition. The anionic resin particles are often handled in the form of an emulsion, but may also be in the form of a powder.

[0081] The term "anionic resin particles" refers to resin particles that have a negative charge as a whole, and preferably have one or more anionic groups selected from a carboxyl group, a sulfonic acid group, a phosphate group, and the like.

[0082] Examples of resin particles include resin particles made of urethane resin, acrylic resin (including styrene-acrylic resin), fluorene resin, olefin resin, rosin-modified resin, terpene resin, ester resin, amide resin, epoxy resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate resin, etc. Among these, urethane resin, acrylic resin, olefin resin, and ester resin are preferred. Furthermore, the resin particles may be used alone or in combination of two or more types.

[0083] Urethane resin is a general term for resins containing urethane bonds. Urethane resins may include polyether-type urethane resins containing ether bonds in the main chain, ester-type urethane resins containing ester bonds in the main chain, and carbonate-type urethane resins containing carbonate bonds in the main chain. Commercially available urethane resins may also be used, such as Superflex 460, 460s, 840, and E-4000 (trade names, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Rezamin D-1060, D-2020, D-4080, D-4200, D-6300, and D-6455 (trade names, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.), Takelac WS-5100, WS-6021, and W-512-A-6 (trade names, manufactured by Mitsui Chemicals Polyurethanes Inc.), Sancure 2710 (trade name, manufactured by Lubrizol), and Permarin UA-150 (trade name, manufactured by Sanyo Chemical Industries, Ltd.).

[0084] Acrylic resin is a general term for polymers obtained by polymerizing at least an acrylic monomer such as (meth)acrylic acid or a (meth)acrylic acid ester as one component. Examples include resins obtained from acrylic monomers and copolymers of acrylic monomers with other monomers. Examples include acrylic-vinyl resins, which are copolymers of acrylic monomers and vinyl monomers. Examples of vinyl monomers include styrene. Examples of acrylic monomers that can be used include acrylamide and acrylonitrile. Commercially available products may be used for the resin emulsion using acrylic resin as a raw material, such as FK-854 (trade name, manufactured by Chuo Rika Kogyo Co., Ltd.), Movinyl 952B and 718A (trade names, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and Nipol LX852 and LX874 (trade names, manufactured by Nippon Zeon Co., Ltd.).

[0085] Styrene-acrylic resins are obtained from styrene monomers and (meth)acrylic monomers. It is a copolymer, and examples thereof include styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylate copolymer, styrene-α-methylstyrene-acrylic acid copolymer, and styrene-α-methylstyrene-acrylic acid-acrylate copolymer. As the styrene-acrylic resin, commercially available products may be used, such as 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), Mowinyl 966A and 975N (trade names, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and Vinyblan 2586 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0086] The olefin resin is a polymer having an olefin such as ethylene, propylene, or butylene in its structural skeleton, and any known polymer can be appropriately selected and used. As the olefin resin, commercially available products can be used, such as Arrowbase CB-1200 and CD-1200 (trade names, manufactured by Unitika Ltd.).

[0087] The anionic resin particles are more preferably urethane resin or acrylic resin, and even more preferably urethane resin, which tends to provide better resistance to rubbing.

[0088] 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 even more 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, the fabric conformability (handle) tends to be better. The glass transition temperature is measured, for example, using a differential scanning calorimeter "DSC7000" manufactured by Hitachi High-Tech Science Corporation in accordance with JIS K7121 (Method for measuring transition temperature of plastics).

[0089] The content (solids concentration) of the anionic resin particles is preferably 1 to 30 mass % relative to the total amount of the transparent ink composition, more preferably 2 to 25 mass %, even more preferably 4 to 20 mass %, particularly preferably 6 to 15 mass %, and even more particularly preferably 8 to 12 mass %. When the content of the anionic resin particles is within the above range, better color development and rub fastness tend to be obtained.

[0090] 1.2.2.2 Water The transparent ink composition contains water. As the water, the same water as that used in the reaction liquid described above can be used.

[0091] The water content is preferably 20% by mass or more, more preferably 30% by mass or more, even 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. There is no particular upper limit to the water content, but for example, it is preferably 90% by mass or less, even more preferably 70% by mass or less, and even more preferably 60% by mass or less, relative to the total amount of the clear ink composition.

[0092] 1.2.2.3 Organic solvents The transparent ink composition may contain an organic solvent. The type and content of the organic solvent may be the same as those of the reaction liquid described above.

[0093] In the transparent ink composition, the organic solvent preferably contains an alkanediol, an alkylene glycol ether, and a trialkylene glycol, and more preferably contains a 1,2-alkanediol, an alkylene glycol ether, and a trialkylene glycol. Preferably, the organic solvent contains propylene glycol, triethylene glycol monobutyl ether, and triethylene glycol. When the organic solvent contains these solvents, the color development and rub fastness may be more excellent.

[0094] The content of the organic solvent is preferably 10 to 55% by mass, more preferably 15 to 45% by mass, even more preferably 20 to 40% by mass, and particularly preferably 25 to 35% by mass, relative to the total amount of the transparent ink composition. When the content of the organic solvent is within the above range, the color development and rub fastness may be superior.

[0095] 1.2.2.4 Surfactants The transparent ink composition may contain a surfactant. The type of surfactant may be the same as that of the reaction liquid described above. The transparent ink composition preferably contains a silicone surfactant as the surfactant.

[0096] The lower limit of the surfactant content is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and particularly preferably 0.3% by mass or more, relative to the total amount of the transparent ink composition. Furthermore, the upper limit of the surfactant content relative to the total amount of the transparent ink composition is preferably 3% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.8% by mass or less. If the surfactant content is within this range, it tends to be easier to adjust the permeability of the transparent ink composition into fabrics in a preferred manner.

[0097] 1.2.2.5 Other ingredients The clear ink composition may contain additives such as pH adjusters, preservatives, antifungals, rust inhibitors, chelating agents, viscosity adjusters, solubilizing agents, antioxidants, etc. When such additives are contained, the content thereof is preferably 0.1 to 5 mass %, more preferably 0.1 to 3 mass %, and even more preferably 0.1 to 1 mass %, relative to the total amount of the clear ink composition.

[0098] The transparent ink composition may also contain a coloring material such as a pigment, but the content of the coloring material 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, of the total amount of the transparent ink composition, with the lower limit being 0% by mass. Preferably, the transparent ink composition does not contain a coloring material.

[0099] 1.2.2.6 Physical Properties From the viewpoint of reducing skin irritation, the pH of the clear ink composition is preferably 2.0 or higher, more preferably 5.0 or higher, and even more preferably 7.0 or higher. From the same viewpoint, the upper limit of the pH is preferably 11.5 or lower, more preferably 10 or lower, even more preferably 9.0 or lower, and particularly preferably 8.0 or lower.

[0100] The viscosity of the transparent ink composition at 20°C is preferably 1.0 to 10 mPa·s, more preferably 1.5 to 8 mPa·s, even more preferably 3.0 to 8.0 mPa·s, even more preferably 3.0 to 5.0 mPa·s, and particularly preferably 3.0 to 4.0 mPa·s. In particular, a viscosity of 3.0 mPa·s or higher tends to provide better color development. A viscosity of 8.0 mPa·s or lower tends to provide better ejection stability.

[0101] The surface tension of the transparent ink composition at 20°C is preferably 10 to 40 mN / m, more preferably 15 to 35 mN / m, even more preferably 20 to 30 mN / m, and particularly preferably 20 to 27 mN / m.

[0102] 1.3 Colored ink application process The inkjet textile printing method according to this embodiment includes a colored ink applying step of applying, by inkjet printing, a colored ink composition containing a pigment, resin particles, and water onto the area of ​​the fabric to which the clear ink composition has been applied. The transparent ink composition applied in the above manner forms a resin layer well formed near the surface of the fabric, which can inhibit the penetration of the colored ink into the fabric and tends to provide good color development. Furthermore, the resin layer functions as a binder layer between the fabric and the colored ink layer, which tends to provide good abrasion resistance.

[0103] 1.3.1 Adhesion pattern The amount of the colored ink composition applied is 0.01 to 1 g / inch 2 It is preferable that the density is 0.03 to 0.5 g / inch. 2 More preferably, it is 0.05 to 0.3 g / inch. 2 More preferably, the density is 0.07 to 0.15 g / inch. 2 It is particularly preferred that:

[0104] The total amount of the reaction liquid, the transparent ink composition, and the colored ink composition adhered was 100 mg / inch 2It is preferable that the concentration is 120 mg / inch or more. 2 More preferably, it is 150 mg / inch or more. 2 More preferably, it is 180 mg / inch or more. 2 It is particularly preferable that the value is 200 mg / inch or more. 2 If the total amount of adhesion is within the above range, the total amount of the reaction liquid and ink to be adhered is relatively large, which makes it difficult to achieve both rubbing fastness and color developability, but the inkjet printing method according to this embodiment tends to be able to obtain good rubbing fastness and color developability. The upper limit of the total amount of adhesion is not particularly limited, but is preferably 500 mg / inch. 2 It is preferable that the concentration is less than 300 mg / inch. 2 More preferably, it is 250 mg / inch or less. 2 It is even more preferable that:

[0105] 1.3.2 Colored ink composition The color ink composition used in the color ink application step contains a pigment, resin particles, and water. Each component contained in the color ink composition will be described below.

[0106] 1.3.2.1 Pigments The colored ink composition contains a pigment. Examples of the pigment that can be used include inorganic pigments and organic pigments. A pigment is a type of coloring material. Examples of the coloring material include pigments and dyes.

[0107] The inorganic pigment is not particularly limited, but examples thereof include carbon blacks such as CI Pigment Black 6 (lamp black, vegetable black), CI Pigment Black 7 (furnace black, channel black, thermal black, acetylene black), CI Pigment Black 8 (charcoal black), and CI Pigment Black 10 (graphite); and white pigments such as iron oxide, titanium oxide, zinc oxide, and silica.

[0108] Examples of carbon black include No. 2300, 900, MCF88, No. 20B, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, and No. 2200B manufactured by Mitsubishi Chemical Corporation. Examples of carbon black include Color Black FW1, FW2, FW2V, FW18, FW200, S150, S160, and S170 manufactured by Degussa Corporation, Pretex 35, U, V, and 140U, and Special Black 6, 5, 4A, 4, and 250. Examples of carbon black include Conductex SC, Raven 1255, 5750, 5250, 5000, 3500, 1255, and 700 manufactured by Columbia Carbon Corporation. Examples of carbon black include Regal 400R, 330R, and 660R, Mogul L, and Monarch 700, 800, 880, and 900 manufactured by Cabot Corporation. , 1000, 1100, 1300, 1400, Elftex 12, etc.

[0109] Examples of white pigments include CI Pigment White 1, which is basic lead carbonate, CI Pigment White 4, which is made of zinc oxide, CI Pigment White 5, which is made of a mixture of zinc sulfide and barium sulfate, CI Pigment White 6, which is made of titanium dioxide, CI Pigment White 6:1, which is made of titanium dioxide containing other metal oxides, CI Pigment White 7, which is made of zinc sulfide, CI Pigment White 18, which is made of calcium carbonate, CI Pigment White 19, which is made of clay, CI Pigment White 20, which is made of titanium mica, CI Pigment White 21, which is made of barium sulfate, CI Pigment White 22, which is made of gypsum, CI Pigment White 26, which is made of magnesium oxide and silicon dioxide, CI Pigment White 27, which is made of silicon dioxide, and CI Pigment White 28, which is made of anhydrous calcium silicate. Among these, CI Pigment White 6, which has excellent color development and hiding power, is preferably used.

[0110] The average particle size of the white pigment is preferably 100 nm to 500 nm, more preferably 50 nm to 450 nm, and even more preferably 200 nm to 400 nm. By setting the average particle size of the white pigment within this range, ejection stability from the inkjet head tends to be ensured. It also tends to improve hiding power. In this specification, unless otherwise specified, "average particle size" refers to the volume-based particle size distribution, which is the particle size at a cumulative distribution of 50 vol%. The average particle size is measured by the dynamic light scattering method or laser diffraction method described in JIS Z8825. Specifically, a particle size distribution analyzer based on the dynamic light scattering method (e.g., "Microtrac UPA" manufactured by Nikkiso Co., Ltd.) can be used.

[0111] Examples of organic pigments include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, isoindolinone pigments, azomethine pigments, and azo pigments.

[0112] Specific examples of organic pigments include the following:

[0113] Examples of cyan pigments include CI Pigment Blue 1, 2, 3, 15:3, 15:4, 15:34, 16, 22, 60, etc.; CI Vat Blue 4, 60, etc., and 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 exemplified.

[0114] Examples of magenta pigments include CI Pigment Red 5, 7, 12, 48(Ca), 48(Mn), 57(Ca), 57:1, 112, 122, 123, 168, 184, 202, and CI Pigment Violet 19. Preferred examples include one or a mixture of two or more pigments selected from the group consisting of CI Pigment Red 122, 202, and 209, and CI Pigment Violet 19.

[0115] Examples of yellow pigments 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. Preferred examples include 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. Cut.

[0116] Pigments of other colors can also be used, such as orange pigments and green pigments.

[0117] The pigments may be used alone or in combination of two or more.

[0118] The pigment contained in the colored ink composition is preferably a white pigment. A colored ink composition (white ink) containing a white pigment is suitable for forming a white ink layer as a base layer, but since a relatively large amount of white ink needs to be deposited, the total amount of reaction liquid and ink to be deposited tends to be larger, making it particularly difficult to achieve both abrasion fastness and color developability. In contrast, the inkjet printing method according to this embodiment tends to provide excellent abrasion fastness and color developability even when using a colored ink composition containing a white pigment.

[0119] The content of the pigment (particularly, white pigment) relative to the total amount of the colored ink composition is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, even more preferably 4 to 20% by mass, particularly preferably 6 to 15% by mass, and more particularly preferably 8 to 12% by mass. When the content of the pigment is within the above range, it tends to be possible to improve the abrasion fastness and obtain better color development (whiteness).

[0120] The pigment may be dispersed using a pigment dispersant, or may be dispersed as a self-dispersing pigment by oxidizing or sulfonating the pigment surface with ozone, hypochlorous acid, fuming sulfuric acid, or the like.

[0121] The pigment dispersant has the function of dispersing the pigment in the ink. The pigment dispersant may be water-soluble, but is preferably one that is not completely water-soluble, and is thought to disperse the pigment by partially or completely bonding to or adsorbing to the pigment and increasing the hydrophilicity of the pigment surface.

[0122] The pigment dispersant is a polymer compound, and examples thereof include acrylic resins and salts thereof, such as poly(meth)acrylic acid, (meth)acrylic acid-acrylonitrile copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, vinyl acetate-(meth)acrylic acid ester copolymer, vinyl acetate-(meth)acrylic acid copolymer, vinylnaphthalene-(meth)acrylic acid copolymer, styrene-(meth)acrylic acid copolymer, styrene-(meth)acrylic acid copolymer, styrene-(meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-α-methylstyrene-(meth)acrylic acid copolymer, and styrene-α-methylstyrene-(meth)acrylic acid-(meth)acrylic acid ester copolymer.

[0123] Examples of pigment dispersants include maleic acid-based resins such as styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinylnaphthalene-maleic acid copolymer, and vinyl acetate-maleic acid ester copolymer, and salts thereof; urethane-based resins and salts thereof, which may or may not have a crosslinked structure; polyvinyl alcohols; and resins such as vinyl acetate-crotonic acid copolymer and salts thereof.

[0124] In addition to the polymers of acrylic monomers (acrylic monomers) described above, acrylic resins may also be copolymers of acrylic monomers with other monomers. For example, acrylic vinyl resins, which are copolymers with vinyl monomers as other monomers, are also referred to as acrylic resins. Furthermore, among the styrene resins described above, copolymers of styrene monomers and acrylic monomers are also included in the acrylic resin category. Furthermore, the term acrylic resin also includes its salts and esterified products.

[0125] Commercially available pigment dispersants include, for example, X-200, X-1, X-205, X-220, and X-228 (manufactured by Seiko PMC Co., Ltd.), Nopcosperse (registered trademark) 6100 and 6110 (manufactured by San Nopco Ltd.), Joncryl 67, 586, 611, 678, 680, 682, and 819 (manufactured by BASF), DISPERBYK-190 (manufactured by BYK Japan KK), N-EA137, N-EA157, N-EA167, N-EA177, N-EA197D, N-EA207D, and E-EN10 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).

[0126] 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.), and the like.

[0127] Commercially available urethane 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).

[0128] The pigment dispersant is preferably an anionic pigment dispersant. The term "anionic pigment dispersant" refers to a pigment dispersant that has a negative charge as a whole, and preferably has one or more anionic groups selected from a carboxyl group, a sulfonic acid group, a phosphate group, etc.

[0129] It is preferable that at least one of the pigment and the resin particles described below in the colored ink composition is anionic. In this case, the aggregating action of the aggregating agent is more excellent, and therefore better color development and better rub fastness tend to be obtained. The term "anionic pigment" means that the pigment as a whole has a negative charge, and preferably has one or more anionic groups selected from a carboxyl group, a sulfonic acid group, a phosphate group, etc. The anionic groups may be present directly on the pigment surface, or may be present via an anionic resin dispersant adsorbed or bonded to the pigment.

[0130] The pigment dispersants may be used alone or in combination of two or more. The total content of the pigment dispersants is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 25% by mass or less, even more 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, relative to 100% by mass of the colored ink composition. A pigment dispersant content of 0.1% by mass or more tends to ensure pigment dispersion stability. Furthermore, a pigment dispersant content of 30% by mass or less tends to reduce the viscosity of the colored ink composition.

[0131] Furthermore, the weight average molecular weight of the pigment dispersant is more preferably at least 500. Use of such a pigment dispersant tends to result in less odor and further improved dispersion stability of the pigment.

[0132] When a pigment (particularly a white pigment) is dispersed using a pigment dispersant, the ratio of pigment to pigment dispersant is preferably 10:1 to 1:10, and more preferably 4:1 to 1:3.

[0133] 1.3.2.2 Resin particles The colored ink composition contains resin particles. The resin particles can be in the same form as the anionic resin particles contained in the transparent ink composition described above, and therefore a description thereof will be omitted.

[0134] The resin particles in the colored ink composition are preferably anionic, since the aggregating action of the aggregating agent is more excellent, and therefore better color development and abrasion resistance tend to be obtained.

[0135] The resin particles in the colored ink composition are preferably a urethane resin or an acrylic resin, and more preferably a urethane resin, which tends to provide better abrasion resistance.

[0136] The glass transition temperature (Tg) of the resin particles in the colored ink composition is preferably −60° C. or higher and 50° C. or lower, more preferably −60° C. or higher and 40° C. or lower, and even more preferably −30° C. or higher and 10° C. When the glass transition temperature (Tg) of the resin particles is within the above range, the conformability to fabric (hand feel) tends to be better.

[0137] The content of the resin particles (solids concentration) relative to the total amount of the colored ink composition is preferably 1 to 30 mass %, more preferably 2 to 25 mass %, even more preferably 4 to 20 mass %, particularly preferably 6 to 15 mass %, and more particularly preferably 8 to 12 mass %. When the content of the resin particles is within the above range, better color development and rub fastness tend to be obtained.

[0138] 1.3.2.3 Water The colored ink composition contains water. As the water, the same water as that used in the reaction liquid described above can be used.

[0139] The water content is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more, relative to the total amount of the colored ink composition. There is no particular upper limit to the water content, but it is, for example, preferably 90% by mass or less, and even more preferably 70% by mass or less, relative to the total amount of the colored ink composition.

[0140] 1.3.2.4 Organic solvents 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 reaction liquid described above.

[0141] In the colored ink composition, the organic solvent preferably contains an alkanediol, an alkylene glycol ether, and a trialkylene glycol, more preferably a 1,2-alkanediol, an alkylene glycol ether, and a trialkylene glycol, and even more preferably propylene glycol, triethylene glycol monobutyl ether, and triethylene glycol. When the organic solvent contains these solvents, the color development and rub fastness may be superior.

[0142] The colored ink composition preferably further contains 3.0% by mass or more, more preferably 4.0% by mass or more, and even more preferably 5.0% by mass or more of an organic solvent having a normal boiling point of 250° C. or higher. There is no particular upper limit to the content, but it is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. When the 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 kept moist, which tends to improve the ejection reliability (continuous printing stability).

[0143] Examples of organic solvents with a standard boiling point of 250°C or higher include glycerin and polyethylene glycol monomethyl ether. Organic solvents with a standard boiling point of 250°C or higher are also called humectants. The organic solvent with a standard boiling point of 250°C or higher more preferably has a standard boiling point of 270°C or higher, and even more preferably has a standard boiling point of 280°C or higher.

[0144] The content of the organic solvent is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, even more preferably 5 to 20% by mass, and particularly preferably 7 to 17% by mass, relative to the total amount of the color ink composition. When the content of the organic solvent is within the above range, better color development and rub fastness may be achieved.

[0145] 1.3.2.5 Surfactants The color ink composition may contain a surfactant. The type of surfactant may be the same as that of the reaction liquid described above. The color ink composition preferably contains a silicone surfactant as the surfactant.

[0146] The lower limit of the surfactant content is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and particularly preferably 0.3% by mass or more, relative to the total amount of the colored ink composition. The upper limit of the surfactant content is preferably 3% by mass or less, more preferably 2% by mass or less, even more 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. When the surfactant content is within this range, it tends to be easier to adjust the permeability of the colored ink composition into fabrics in a preferable manner.

[0147] 1.3.2.6 Other ingredients The color ink composition may contain additives such as pH adjusters, preservatives, antifungals, rust inhibitors, chelating agents, viscosity adjusters, solubilizing agents, antioxidants, etc. When such additives are contained, the content thereof is preferably 0.1 to 5 mass %, more preferably 0.1 to 3 mass %, and even more preferably 0.1 to 1 mass %, relative to the total amount of the color ink composition.

[0148] 1.3.2.7 Physical Properties From the viewpoint of reducing skin irritation, the pH of the colored ink composition is preferably 2.0 or higher, more preferably 5.0 or higher, and even more preferably 7.0 or higher. From the same viewpoint, the upper limit of the pH is preferably 11.5 or lower, more preferably 10 or lower, even more preferably 9.0 or lower, and particularly preferably 8.0 or lower.

[0149] The viscosity of the colored ink composition at 20°C is preferably 1.0 to 10 mPa·s, more preferably 2.0 to 10 mPa·s, even more preferably 3.0 to 8.0 mPa·s, and particularly preferably 4.0 to 6.0 mPa·s. In particular, a viscosity of 4.0 mPa·s or higher tends to provide better color development. A viscosity of 6.0 mPa·s or lower tends to provide better ejection stability.

[0150] 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, even more preferably 20 to 30 mN / m, and particularly preferably 20 to 27 mN / m.

[0151] 1.4 Pressure application process The inkjet printing method according to this embodiment includes a pressure applying step of applying pressure to the area of ​​the fabric to which the reaction liquid and the clear ink composition have been applied, after the reaction liquid applying step and the clear ink applying step.

[0152] The pressure applying means is not particularly limited as long as it can apply pressure to the fluff in the area of ​​the fabric to which the reaction liquid and the transparent ink composition are attached. Examples of the pressure applying means include a method that is performed without contacting the fabric and a method that is performed in direct contact with the fabric.

[0153] Pressure can be applied without contact with the fabric by blowing air from a blower or the like. Examples include:

[0154] Examples of pressure applying means that come into direct contact with the fabric include pressure applying means that come into surface contact and pressure applying means that come into line contact. An example of applying pressure by surface contact is applying pressure by the surface of a plate or the like. Examples of applying pressure by line contact include applying pressure with a roller, a squeegee, or the like.

[0155] The pressure applying step is preferably performed by direct contact between the fabric and the pressure applying means, and more preferably by line contact between the fabric and the pressure applying means, in which case each step including the pressure applying step can be easily performed in the same device, and the steps can be further simplified.

[0156] The pressure applied in the pressure application step is not particularly limited as long as it is capable of flattening the fuzz of the fabric, but for example, it is preferably 1000 Pa or less, more preferably 100 Pa or less, even more preferably 10 Pa or less, particularly preferably 1 Pa or less, even more particularly preferably 0.1 Pa or less, even more particularly preferably 0.01 Pa or less, and even more particularly preferably 0.001 Pa or less.

[0157] The pressure application step is preferably carried out before the colored ink application step, as this tends to further improve the fluff fixing effect and further reduce image quality disturbances caused by fluffing of the fabric.

[0158] Furthermore, the pressure application step is preferably carried out within 30 minutes, more preferably within 20 minutes, even more preferably within 10 minutes, particularly preferably within 5 minutes, and even particularly preferably within 1 minute after the above-mentioned clear ink application step. In this case, pressure is applied to the clear ink when it is not completely dry and is in the form of a gel-like aggregate, which makes it easier for the fluff to be fixed in a flattened state due to viscosity, further improving the fluff fixing effect and tending to further reduce image quality disturbances caused by fluffing of the fabric.

[0159] 1.5 Fabric position between processes The fabric is placed on a mounting table, and the reaction liquid application step, the clear ink application step, the pressure application step, and the colored ink application step are performed without changing the relative positional relationship between the fabric and the mounting table between each step, which allows each step to be performed consecutively and simplifies the process.

[0160] Examples of the form of fabric used in the inkjet printing method according to this embodiment include fabrics, clothing, and other accessories. Fabrics include woven fabrics, knitted fabrics, and nonwoven fabrics. Clothing and other accessories include sewn T-shirts, handkerchiefs, scarves, towels, carrier bags, cloth bags, curtains, sheets, bedspreads, wallpaper, and other furniture, as well as fabrics before and after cutting as parts before sewing. These may be in the form of long rolls, cut to a specified size, or in the shape of a finished product.

[0161] Examples of materials constituting the fabric include 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, and blends of these may also be used. Among these materials, fabrics made of cotton, polyester, or a blend of cotton and polyester are easily available and are therefore preferred.

[0162] The fabric is preferably a fabric having fluff. In particular, from the viewpoint of obtaining the effects of the present invention more effectively, it is preferable that the fabric has fluff, which is fibers protruding from the fiber bundles constituting the fabric, and the length of the fluff in the perpendicular direction from the surface of the fiber bundle to the peak of the fluff is preferably 50 μm or more, more preferably 100 μm or more. Such fabrics are more likely to suffer from image quality disturbance due to fluffing. In contrast, the inkjet printing method according to this embodiment makes it possible to form an image while reducing the influence of fluffing on the printing surface, even when such fabrics are used.

[0163] The length can be measured by known means, for example, using a digital microscope (KEYENCE, VHX-5000), and the average value (arithmetic mean) of multiple fluffs (for example, 10 points) may be determined as the length.

[0164] The term "fiber bundle" refers to a bundle of multiple fibers and has a substantially circular cross section. The term "fluff" refers to the ends of short fibers that have been raised from the surface of the fiber bundle, and the ends of short fibers present inside the fiber bundle are not called fluff.

[0165] Also, the fabric is L * a * b * Lightness L in the color system * It is preferable that the value of L is 70 or less. * The value may be 60 or less, or may be 50 or less. In printing on such fabrics, a white ink (base) and a color ink may be used as the colored ink composition to obtain excellent color development. If the white ink appears on the surface of the fabric due to fuzzing, the image quality is likely to be significantly disrupted. In contrast, according to the inkjet printing method of this embodiment, even when such fabrics are used, it is possible to form an image while reducing the influence of fuzzing on the printing surface.

[0166] In addition, L * The value can be measured using a known colorimeter, for example, Spectrolino (Gretag).

[0167] In addition, L * Examples of fabrics having a value of 70 or less include colored fabrics that have been pre-colored with a dye or the like. Examples of dyes with which fabrics are pre-colored include water-soluble dyes such as acid dyes and basic dyes, disperse dyes that are used in combination with a dispersant (surfactant), reactive dyes, etc. Known methods can be used to color fabrics with dyes, depending on the material and shape of the fabric.

[0168] 1.6 Heat drying process The inkjet printing method according to this embodiment may include a step of heating and drying the ink or the like that has been applied to the fabric (heat drying step) after the colored ink application step described above.

[0169] The heat drying method is not particularly limited, but examples thereof include a belt conveyor oven, a normal pressure steam method, a high pressure steam method, a Thermofix method, etc. The heat source for heat drying is not particularly limited, but for example, an infrared lamp or the like can be used.

[0170] The heat drying temperature is preferably a temperature at which resin particles that may be contained in the ink are fused and media such as water are volatilized. The heat drying temperature is, for example, preferably 100°C or higher and 250°C or lower, more preferably 120°C or higher and 230°C or lower, even more preferably 140°C or higher and 200°C or lower, and particularly preferably 150°C or higher and 180°C or lower. Here, the heat drying temperature in the heat drying step refers to the surface temperature of an image or the like formed on the fabric. The heat drying time is not particularly limited, but is, for example, preferably 30 seconds to 20 minutes, more preferably 2 minutes to 5 minutes.

[0171] 1.7 Other processes The inkjet printing method according to this embodiment may include a step of washing the recorded fabric with water, a step of heating and drying the fabric again, etc. In the washing step, if necessary, components of the ink and the like that have not been fixed to the fabric may be washed away using a hot soapy solution or the like as a soaping treatment.

[0172] 1.8 Inkjet printing equipment An inkjet printing apparatus that can be preferably used in the inkjet printing method according to this embodiment will be described.

[0173] FIG. 1 is an external perspective view of the inkjet printing apparatus 1, FIG. 2 is a schematic diagram of the print material transport path of the inkjet printing apparatus 1, and FIG. 3 is a diagram showing the print material P and the state of the print material P placed on the placement table 7.

[0174] As shown in Figure 1, the inkjet printing device 1 has a guide table 8 at the bottom of the device main body 2, and a guide portion 8a formed on this guide table 8 guides the loading table 7 in the movement direction TD of the printing material P (the direction of arrow A in Figure 2).

[0175] The mounting table 7 is a flat table on which the material to be printed P is placed, and the material to be printed P is placed on the mounting surface 7a as shown in Fig. 3 (the material to be printed P in Fig. 3 is a T-shirt as an example), and the mounting table 7 on which the material to be printed P is placed moves in the transport direction A, so that the material to be printed P can pass through the printing execution unit 5. Note that illustration and description of the drive mechanism that drives the mounting table 7 are omitted in this specification. As described above, the mounting table 7 and the drive mechanism that drives it constitute a moving means that moves the material to be printed P.

[0176] Furthermore, the mounting table 7 may be detachable from the apparatus main body 2. This allows the mounting table 7 to be removed from the apparatus main body 2 and transported while the material to be printed P remains placed 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 material to be printed P.

[0177] The inkjet head 14 constituting the printing execution unit 5 is an inkjet head of known structure having a plurality of nozzle rows in which a plurality of nozzles are arranged, each having a nozzle for ejecting a reaction liquid, a nozzle for ejecting a transparent ink composition, and a nozzle for ejecting a colored ink composition, and this inkjet head 14 is mounted on a carriage 13 that is driven to reciprocate in a direction intersecting the movement direction A of the material to be printed P (scanning direction SD in Figure 1: toward the back of the paper surface in Figure 2).

[0178] Fig. 4 shows an example of each nozzle row on the nozzle surface of the inkjet head 14. In Fig. 4, the inkjet head 14 has a plurality of nozzle rows, rows A to H, along the scanning direction SD, each row consisting of a plurality of nozzles arranged in a direction (movement direction TD of the print target material P) intersecting the direction in which the inkjet head 14 is moved (scanning direction SD). In this case, by arranging the nozzle row that ejects the reaction liquid so that it at least partially overlaps with the nozzle row that ejects the transparent ink composition in the movement direction TD of the material to be printed P when projected along the scanning direction SD, the above-mentioned step 1 (application of the reaction liquid and the transparent ink composition to the same area on the fabric in one and the same scan of the inkjet head) can be performed. The inks to be ejected from each nozzle row are selected as appropriate, but it is preferable to select rows A and B as nozzle rows that eject reaction liquid, rows C and D as nozzle rows that eject transparent ink compositions, and rows E to H as nozzle rows that eject colored ink compositions, for example.

[0179] In the case of a serial printer, the inkjet head 14 is provided with a head having a length smaller than the width of the material to be printed P, and the inkjet head 14 is arranged in the direction of movement TD of the material to be printed P. Printing is performed while moving in the intersecting scanning direction SD. In a serial printer, an inkjet head 14 is mounted on a carriage 13 that moves in a predetermined direction, and the inkjet head 14 moves in conjunction with the movement of the carriage 13, thereby ejecting ink and reaction liquid onto the material to be printed P. The material to be printed P may be moved between scans.

[0180] Furthermore, the inkjet textile printing apparatus is not limited to the serial printer described above, but may also be a line printer. Figure 5 shows a schematic side view of a line printer as another example of an inkjet textile printing apparatus. The line printer can have the same configuration as a serial printer except for the printing execution unit 5.

[0181] The line printer has a line head 300 having a length corresponding to the width of the printing material P. The line head 300 may be composed of multiple line heads. The line head 300 has cavities that contain reaction liquid, a clear ink composition, and a colored ink composition (such as ink), an ejection drive unit provided for each cavity, and nozzles that eject the ink, etc. A single head may have multiple cavities, ejection drive units provided for each cavity, and nozzles that are independent of each other. The ejection drive unit may be formed using an electromechanical conversion element such as a piezoelectric element that changes the volume of the cavity by mechanical deformation, or an electrothermal conversion element that generates heat to generate bubbles in the ink and eject it.

[0182] In a line printer, the head is fixed (almost) without moving, and printing is performed with a single scan of the inkjet head. Line printers have the advantage over serial printers in that they have a faster printing speed.

[0183] As shown in Fig. 2, the inkjet printing apparatus 1 includes a pressure applying means 10. The pressure applying means 10 applies pressure to an area of ​​the material to be printed P to which the reaction liquid and the transparent ink composition have been applied by the inkjet head 14. The pressure applying means 10 shown in Fig. 2 is configured to apply pressure by making line contact with the material to be printed P (for example, a roller or squeegee), but it may also be configured to apply pressure by the surface of a plate or the like, or by blowing air using a blower or the like.

[0184] The control unit 16 is a control means that controls a drive mechanism (not shown) that drives the mounting table 7, a drive mechanism (not shown) that drives the carriage 13, and a drive mechanism (not shown) that drives the inkjet head 14.

[0185] An example of the order of the above-mentioned steps in the inkjet printing method according to this embodiment using the inkjet printing apparatus 1 will be described below. First, the mounting table 7 on which the material to be printed P is placed moves in the direction T1 from the installation position (left side in FIG. 2) to the initial position of the ink application step (right side of the inkjet head 14 in FIG. 2). Next, while moving in the direction T2, the mounting table 7 deposits the reaction liquid and the transparent ink composition using the inkjet head 14, thereby performing the reaction liquid depositing step and the transparent ink depositing step. Thereafter, while further moving in the direction T2, the mounting table 7 performs the pressure applying step in which the pressure applying means 10 applies pressure to the material to be printed P, and then returns to the installation position (left side in FIG. 2). Next, the mounting table 7 on which the material to be printed P is placed moves again in the direction T1 from the installation position (left side in FIG. 2) to the initial position of the ink application step (right side of the inkjet head 14 in FIG. 2). Then, while the mounting table 7 is moving in the T2 direction, the inkjet head 14 applies the colored ink composition to the material P to be printed, thereby carrying out the colored ink application process. During these processes, the material P to be printed is not removed from the mounting table 7, and a series of operations are carried out.

[0186] 2. Ink set An ink set according to one embodiment of the present invention is an ink set for use in the inkjet textile printing method described above, and includes the reaction liquid, the clear ink composition, and the colored ink compositions described above.

[0187]

[0043] The ink set according to this embodiment can form an image while reducing the effects of fuzzing on the printed surface. The reaction liquid, the clear ink composition, and the colored ink compositions contained in the ink set are as described above, and therefore will not be described here.

[0188] In the present invention, an "ink set" refers to a set of inks that combine a reaction liquid, a clear ink composition, and a colored ink composition. An ink set is a set of inks that are mixed together for use. The ink set may contain only one colored ink composition, or two or more colored ink compositions. The same applies to the reaction liquid and the clear ink composition that the ink set contains.

[0189] 3. Working Example The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" below is based on mass.

[0190] 3.1 Preparation of reaction liquid, clear ink composition, and colored ink composition The components were placed in a container to obtain the composition shown in Table 1, mixed and stirred, and then filtered through a 5 μm membrane filter to obtain a reaction liquid, a clear ink composition, and a colored ink composition for each example. The numerical values ​​for each component shown in each example in the table represent mass % unless otherwise specified. The mass % of the pigment and resin particles in Table 1 represent the solids concentration, and ion-exchanged water was added so that the total mass of the composition was 100 mass %.

[0191] The pigment used was a pigment dispersion prepared in advance using the following procedure. CI Pigment White 6 (specific gravity: 4.2 g / mL), a titanium oxide pigment, was used as the pigment, and an anionic resin dispersant was used as the pigment dispersant. Specifically, a styrene-acrylic resin synthesized using 55% by weight of styrene, 20% by weight of acrylic acid, and 30% by weight of methyl methacrylate was used. Three parts by weight of pigment was mixed with 1 part by weight of dispersant and 10 parts by weight of ion-exchanged water. The resulting mixture was premixed and then dispersed using a bead mill disperser (Kotobuki Industries Co., Ltd., UAM-015) with 0.03 mm diameter zirconia beads at a peripheral speed of 10 m / s and a liquid temperature of 30°C for 15 minutes. Coarse particles were then separated using a centrifuge (Kuboyama Shoji Co., Ltd., Model-3600) to obtain a titanium oxide dispersion.

[0192] The following provides additional explanations for the items listed in Table 1. Takelac WS-6021 (product name, manufactured by Mitsui Chemicals Polyurethanes, Inc.) BYK-348 (product name, manufactured by BYK) Olfine E1010 (product name, manufactured by Nissin Chemical Industry Co., Ltd.)

[0193] The viscosity was measured in an environment of 20°C using a viscoelasticity tester MCR-300 (trade name, manufactured by Pysica). The surface tension was measured by checking the surface tension when a platinum plate was wetted with the reaction liquid or ink in an environment of 20°C using an automatic surface tensiometer CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.).

[0194] 3.2 Recording conditions Using the reaction liquid, the transparent ink composition, and the colored ink composition prepared as described above, inkjet textile printing methods according to the examples and comparative examples were carried out under the conditions below and the conditions shown in Table 2.

[0195] Printer: Modified SC-F2200 (Seiko Epson, serial type) Drying: The fabric was dried in a belt conveyor oven (M&R, Fusion R 36-6-4) at 160°C for 3 minutes. Fabric: 100% cotton, black T-shirt (Printstar), colored part L * Value 20, average fluff height over 50 μm Image resolution: 1200 x 600 dpi -Duty of each row: 100%

[0196] The head nozzle configuration was as shown in FIG. 4, with rows A and B being nozzle rows for ejecting the reaction liquid, rows C and D being nozzle rows for ejecting the clear ink composition, and rows E and H being nozzle rows for ejecting the colored ink composition. The fabric was placed on a platen, and printing was performed without removing it from the platen between the step of applying the reaction liquid and the transparent ink, the step of applying pressure with a squeegee, and the step of applying the white ink. In Examples 1 to 12, the step of applying the reaction liquid and the transparent ink and the step of applying pressure using a squeegee were performed, followed by the step of applying the white ink. In Comparative Example 1, the step of applying the reaction liquid and the transparent ink was performed, followed by the step of applying the white ink. In all Examples, after the step of applying the white ink was performed, drying was performed under the above-mentioned conditions to obtain a printed textile. In Table 2, with respect to whether or not a squeegee (wiping) was used, "Yes" indicates that a rubber wiper was used, except for Example 2, and "Yes" in Example 2 indicates that a rubber roller was used. The "mixture viscosity" shown in Table 2 is the viscosity of the mixture measured in a measuring section of a rheometer (Anton Paar, MCR302e) consisting of a disc-shaped non-rotating plate and a disc-shaped rotating plate. The reaction liquid and the transparent ink composition were dropped in equal amounts onto the non-rotating plate so as to be symmetrical about the center of the non-rotating plate, and the viscosity was measured at a shear rate of 50 [s -1 ] is the viscosity obtained by measuring the liquid viscosity 10 seconds after the start of plate rotation. The average fluff height was determined by measuring the height of fibers (fluff) protruding from the fabric surface using the 3D observation function of a digital microscope (KEYENCE, VHX-5000) and averaging the height of 10 fluff points. In Table 2, "difference in landing time (reaction liquid / clear ink)" is the time difference between the deposition of the reaction liquid and the deposition of the clear ink composition in the same area of ​​the fabric, and is expressed in seconds. In Examples 1 to 6, 9 to 12 and Comparative Example 1, the reaction liquid and the transparent ink composition were applied to the fabric in one identical scan, while in Examples 7 and 8, the reaction liquid was applied first and then the transparent ink composition was applied in a different scan. In Table 2, "time difference from application of the second liquid to squeegee (wiping)" indicates the time difference from application of the clear ink composition to squeegeeing.

[0197] 3.3 Evaluation method 3.3.1 Color development The printed products obtained by the inkjet printing method according to each of the Examples and Comparative Examples were measured for L using a fluorescence spectrodensitometer (FD-7, manufactured by Konica Minolta, Inc.). * The value (whiteness) was measured, and the color development was evaluated according to the following criteria. (Judgment criteria) A+:L * Over 90 A:L * Between 80 and 90 B:L * 75 or more and less than 80 C:L * Under 75

[0198] 3.3.2 Image quality distortion In the printed textiles 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 image quality disturbance was evaluated according to the following criteria. (Judgment criteria) A: The white ink layer (surface layer) does not have any fluffing, exposing the media surface (cotton). B: The white ink layer (surface layer) has fuzz, causing slight exposure of the media surface (cotton). C: The white ink layer (surface layer) is fuzzed, exposing the media surface (cotton). 3.3.3 Cracking in the Wh ink layer In the printed textiles 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 presence or absence of cracks was evaluated according to the following criteria. (Judgment criteria) A: No cracks B: Slight cracks C: There are cracks

[0199] 3.4 Evaluation results The evaluation results are shown in Table 2. In all of the examples relating to the inkjet textile printing method, which included a reaction liquid applying step of applying to the fabric a reaction liquid containing water and an aggregating agent that aggregates the components in the ink, a clear ink applying step of applying to the fabric a clear ink composition containing water and anionic resin particles that react with the aggregating agent to aggregate, and a colored ink applying step of applying by an inkjet method a colored ink composition containing a pigment, resin particles, and water onto the area of ​​the fabric to which the clear ink composition had been applied, and which included a pressure applying step of applying pressure to the area of ​​the fabric to which the reaction liquid and the clear ink composition had been applied, after the reaction liquid applying step and the clear ink applying step, wherein the fabric was placed on a mounting table, and the reaction liquid applying step, the clear ink applying step, the pressure applying step, and the colored ink applying step were performed without changing the relative positional relationship between the fabric and the mounting table between each step, the effects of fuzzing on the printed surface were successfully reduced, and images could be formed.

[0200] In contrast, in the inkjet printing method according to the comparative example, which does not satisfy the above-mentioned configuration, it was not possible to form an image with the influence of fuzzing on the printing surface reduced satisfactorily.

[0201] The following can be derived from the above-described embodiment.

[0202] One aspect of the inkjet printing method is a reaction liquid applying step of applying a reaction liquid containing water and an aggregating agent that aggregates components in the ink to the fabric; a transparent ink applying step of applying a transparent ink composition containing anionic resin particles that react with the aggregating agent and aggregate, and water, to the fabric; a colored ink applying step of applying a colored ink composition containing a pigment, resin particles, and water by an inkjet method onto the area of ​​the fabric to which the transparent ink composition has been applied; a pressure application step of applying pressure to an area of ​​the fabric to which the reaction liquid and the transparent ink composition have been applied, after the reaction liquid application step and the transparent ink application step; The fabric is placed on a mounting table, and the reaction liquid application process, the transparent ink application process, the pressure application process, and the colored ink application process are performed without changing the relative positional relationship between the fabric and the mounting table between each process.

[0203] In one embodiment of the inkjet printing method, The time difference between the deposition of the reaction liquid and the deposition of the transparent ink composition in the same region of the fabric may be within 30 seconds.

[0204] In any one of the above ink-jet printing methods, The reaction liquid applying step and the transparent ink applying step may include the following step 1. Step 1: applying the reaction liquid and the transparent ink composition to the same area of ​​the fabric in one and the same scan

[0205] In any one of the above ink-jet printing methods, the reaction liquid and the transparent ink composition have a viscosity of 3 to 8 mPa s at 20°C; A mixture of equal amounts of the reaction liquid and the transparent ink composition may have a viscosity of 50 mPa·s or more at 20°C.

[0206] In any one of the above ink-jet printing methods, The total coating amount of the reaction liquid and the transparent ink composition was 0.02 g / inch 2 It may be more than that.

[0207] In any one of the above ink-jet printing methods, The ratio of the application amount of the reaction liquid to the application amount of the transparent ink composition may be 1:10 to 10:1.

[0208] In any one of the above ink-jet printing methods, The fabric may be a fabric having fluff.

[0209] In any one of the above ink-jet printing methods, The L of the fabric * a * b * Lightness L in the color system * The value of may be 70 or less.

[0210] In any one of the above ink-jet printing methods, The pigment may be a white pigment.

[0211] In any one of the above ink-jet printing methods, The flocculant may contain an organic acid, and the organic acid may be contained in an amount of 1 to 6% by mass relative to the total amount of the reaction liquid.

[0212] In any one of the above ink-jet printing methods, The pressure applying step may be performed by direct contact between the fabric and a pressure applying means.

[0213] In any one of the above ink-jet printing methods, The reaction liquid may contain a surfactant, and the content of the surfactant may be 2.0 mass % or less relative to the total amount of the reaction liquid.

[0214] In any one of the above ink-jet printing methods, The pressure application step may be performed before the colored ink deposition step.

[0215] In any one of the above ink-jet printing methods, The pressure application step may be carried out within 30 minutes after the transparent ink application step.

[0216] In any one of the above ink-jet printing methods, The reaction liquid applying step and the transparent ink applying step may be performed by an inkjet method.

[0217] In any one of the above ink-jet printing methods, The pH of the reaction solution may be 2.0 or higher.

[0218] In any one of the above ink-jet printing methods, The total amount of the reaction liquid, the transparent ink composition, and the colored ink composition deposited is 100 mg / inch 2 It may be more than that.

[0219] One aspect of the ink set is An ink set for use in the inkjet printing method according to any one of the above aspects, comprising: The ink jet recording medium includes the reaction liquid, the transparent ink composition, and the colored ink composition.

[0220] The present invention is not limited to the above-described embodiments, and various modifications are possible. For example, the present invention includes configurations that are substantially the same as the configurations described in the embodiments, such as configurations with the same functions, methods, and results, or configurations with the same purpose and effects. The present invention also includes configurations in which non-essential parts of the configurations described in the embodiments are replaced. The present invention also includes configurations that achieve the same effects or purposes as the configurations described in the embodiments. The present invention also includes configurations in which publicly known technology is added to the configurations described in the embodiments. [Explanation of symbols]

[0221] REFERENCE SIGNS LIST 1... inkjet printing device, 2... device main body, 5... printing execution unit, 7... placement table, 7a... placement surface, 8... guide table, 8a... guide unit, 10... pressure application means, 13... carriage, 14... inkjet head, 16... control unit, 300... line head, P... material to be printed

Claims

1. a reaction liquid applying step of applying a reaction liquid containing water and an aggregating agent that aggregates components in the ink to the fabric; a transparent ink applying step of applying a transparent ink composition containing anionic resin particles that react with the aggregating agent and aggregate, and water, to the fabric; a colored ink applying step of applying a colored ink composition containing a pigment, resin particles, and water by an inkjet method onto the area of ​​the fabric to which the transparent ink composition has been applied; a pressure application step of applying pressure to an area of ​​the fabric to which the reaction liquid and the transparent ink composition have been applied, after the reaction liquid application step and the transparent ink application step; the fabric is placed on a placement table, and the reaction liquid applying step, the transparent ink applying step, the pressure applying step, and the colored ink applying step are performed without changing the relative positional relationship between the fabric and the placement table between each step.

2. The ink-jet printing method according to claim 1 , wherein the time difference between the deposition of the reaction liquid and the deposition of the transparent ink composition on the same region of the fabric is within 30 seconds.

3. The ink-jet printing method according to claim 1 , wherein the reaction liquid applying step and the transparent ink applying step include the following step 1: Step 1: Applying the reaction liquid and the transparent ink composition to the same area of ​​the fabric in one identical scan

4. the reaction liquid and the transparent ink composition have a viscosity of 3 to 8 mPa·s at 20°C; The ink-jet printing method according to claim 1, wherein the viscosity of the mixture of equal amounts of the reaction liquid and the transparent ink composition is 50 mPa·s or more at 20°C.

5. The total coating amount of the reaction liquid and the transparent ink composition is 0.02 g / inch ２ The ink-jet printing method according to claim 1 , wherein

6. 2. The ink-jet printing method according to claim 1, wherein the ratio of the amount of the reaction liquid to the amount of the transparent ink composition applied is 1:10 to 10:

1.

7. The ink-jet printing method according to claim 1 , wherein the fabric is a fabric having fluff.

8. The L of the fabric ＊ a ＊ b ＊ Lightness L in the color system ＊ The ink-jet printing method according to claim 1, wherein the value of

9. The ink-jet printing method according to claim 1 , wherein the pigment is a white pigment.

10. 2. The ink-jet printing method according to claim 1, wherein the aggregating agent contains an organic acid, and the organic acid is contained in an amount of 1 to 6% by mass relative to the total amount of the reaction liquid.

11. The ink-jet printing method according to claim 1, wherein the pressure applying step is carried out by bringing the fabric into direct contact with a pressure applying means.

12. The inkjet printing method according to claim 1, wherein the reaction liquid contains a surfactant, and the content of the surfactant is 2.0% by mass or less with respect to the total amount of the reaction liquid.

13. The ink-jet printing method according to claim 1 , wherein the pressure application step is performed before the colored ink deposition step.

14. The ink-jet printing method according to claim 1 , wherein the pressure applying step is carried out within 30 minutes after the transparent ink applying step.

15. The ink-jet printing method according to claim 1 , wherein the reaction liquid applying step and the transparent ink applying step are performed by an ink-jet method.

16. The ink-jet printing method according to claim 1, wherein the reaction liquid has a pH of 2.0 or higher.

17. The total amount of the reaction liquid, the transparent ink composition, and the colored ink composition deposited is 100 mg / inch ２ The ink-jet printing method according to claim 1 , wherein

18. An ink set for use in the inkjet textile printing method according to claim 1, An ink set comprising the reaction liquid, the clear ink composition, and the colored ink composition.

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