Inkjet printing method

Abstract

To provide an ink-jet printing method which has good color development and suppresses penetration to the back side of a fabric. [Solution] The method comprises a reaction liquid application step of applying a reaction liquid containing water and an aggregating agent that aggregates the components in the ink to the fabric by an inkjet method; a clear ink application step of applying a transparent ink composition containing anionic resin particles and water to the fabric by an inkjet method; and a colored ink application step of applying a colored ink composition containing a colorant, resin particles, and water to the area of ​​the fabric to which the clear ink composition has been applied by an inkjet method, wherein the reaction liquid application step and the transparent ink application step are performed on the same area of ​​the fabric within the same scan; the reaction liquid and the transparent ink composition, when mixed in equal amounts, have a viscosity of 50 mPa·s or more at 20°C; the fabric has voids that penetrate through the thickness direction, and the shorter of the maximum length in the warp direction and the maximum length in the weft direction of the voids is 50 μm or more.

Description

[Technical Field]

[0001] The present invention relates to an ink-jet textile printing method. [Background technology]

[0002] BACKGROUND ART In textile printing using an inkjet ink composition, a technique has been known in which a fabric is treated with a reaction liquid containing an aggregating agent that aggregates components in the ink in order to improve the color development and other properties of the printed matter.

[0003] For example, Patent Document 1 describes an inkjet printing method for printing on a textile substrate, which includes the steps of applying a pretreatment composition, applying a clear ink, and applying a white 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, when the reaction liquid is applied to a fabric by the inkjet method, it has not been possible to obtain a printed matter that has good color development and is inhibited from permeating to the back side 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 a flocculant that aggregates components in the ink and water to the fabric by an inkjet method; a transparent ink applying step of applying a transparent ink composition containing anionic resin particles and water to the fabric by an inkjet method; a colored ink applying step of applying a colored ink composition containing a coloring material, resin particles, and water by an inkjet method onto the area of ​​the fabric to which the transparent ink composition has been applied; the reaction liquid applying step and the transparent ink applying step are performed on the same region of the fabric during the same scan; a viscosity of a mixture of equal amounts of the reaction liquid and the transparent ink composition is 50 mPa·s or more at 20°C; The fabric has voids penetrating in the thickness direction, When the fabric is viewed in a plane in the thickness direction, the shape of the voids has a maximum length in the warp direction of the fabric and a maximum length in the weft direction of the fabric, the shorter of which is 50 μm or more. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. [Figure 2] 4A and 4B are diagrams showing examples of the shape of voids in a fabric. [Figure 3] FIG. 1 is a perspective view of a serial printer. [Figure 4] FIG. 1 is a schematic side view of a line printer. [Figure 5] FIG. 2 is a schematic diagram showing an example of the arrangement of nozzle rows of an inkjet head. [Figure 6] Table 1 shows examples of the composition of the reaction liquid and the transparent ink composition. [Figure 7] Table 2 shows examples of colored ink compositions. [Figure 8] Table 3 shows the recording conditions of the inkjet printing method according to each example. [Figure 9] Table 4 shows the recording conditions of the inkjet printing method according to each comparative example. DETAILED DESCRIPTION OF THE INVENTION

[0008] 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.

[0009] 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 method in which droplets of inkjet ink are ejected from the nozzles of an inkjet head and adhered to a recording medium. In this specification, "(meth)acrylic" refers to acrylic or methacrylic, and "(meth)acrylate" refers to acrylate or methacrylate.

[0010] 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 by an inkjet method; a clear ink applying step of applying a transparent ink composition containing anionic resin particles and water to the fabric by an inkjet method; and a colored ink applying step of applying a colored ink composition containing a colorant, resin particles, and water to the fabric in an area to which the clear ink composition has been applied by an inkjet method, wherein the reaction liquid applying step and the transparent ink applying step are performed on the same area of ​​the fabric within the same scan; a mixture of equal amounts of the reaction liquid and the transparent ink composition has a viscosity of 50 mPa·s or more at 20°C; the fabric has voids that penetrate the fabric in the thickness direction; and the shape of the voids when viewed in a plane in the thickness direction is such that the shorter of the maximum length of the shape in the warp direction of the fabric and the maximum length of the shape in the weft direction of the fabric is 50 μm or more.

[0011] Conventionally, in inkjet textile printing, a process of depositing a reaction liquid that aggregates ink components onto fabric has been performed to improve the color development of colorants. This process has typically involved the use of separate equipment or facilities from the inkjet recording device, or has often been performed manually, requiring large-scale equipment and complicated processes. Therefore, studies have been conducted on a method in which not only the ink but also the reaction liquid is ejected by the inkjet method, and the reaction liquid and ink are deposited continuously within the same device. This method eliminates the need for separate equipment or facilities and simplifies the process.

[0012] However, in the above embodiment, as the total amount of the applied reaction liquid or ink increases, it becomes more difficult to achieve both color development and suppression of penetration to the back side of the fabric. In other words, when the total amount of the applied reaction liquid or ink increases, the amount of water increases, which makes it more likely that the aggregation action of the reaction liquid when the ink lands becomes insufficient, and the ink penetrates into the fabric more easily, resulting in a decrease in color development. Furthermore, if the amount of applied ink is increased to compensate for the decrease in color development, while color development improves, penetration to the back side of the fabric becomes even worse.

[0013] This is particularly noticeable in fabrics having voids of a certain size or larger.

[0014] In contrast, according to the inkjet textile printing method of this embodiment, a reaction liquid having a viscosity of 50 mPa·s or more when mixed and a transparent ink composition (hereinafter also referred to as "transparent ink") are simultaneously applied by an inkjet method. This causes the resin particles in the transparent ink to aggregate near the surface of the fabric, forming a resin layer that exhibits a sealing effect. This prevents ink from striking through to the back of the fabric when applied to the fabric, even on fabrics with voids of a predetermined size or larger, and also provides good color development.

[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 a reaction liquid applying step of applying a reaction liquid containing a flocculant that aggregates components in the ink and water to fabric by an inkjet method.

[0017] 1.1.1 Fabric The fabric used in the inkjet printing method according to this embodiment has voids that penetrate through the fabric in the thickness direction, and when the fabric is viewed in a plane in the thickness direction, the shape of the voids has a maximum length in the warp direction of the fabric and a maximum length in the weft direction of the fabric, whichever is shorter, of 50 μm or more. In the case of such fabrics, it is particularly difficult to achieve both color development and suppression of penetration to the back side of the fabric, but the inkjet printing method according to this embodiment makes it possible to achieve both.

[0018] As an example of a fabric, a plan view of the fabric is shown in Figure 1. As shown in Figure 1, the fabric 400 is weft-knitted, in which the fibers 4 advance in the X-axis direction (the weft direction of the fabric 400) to form loops (courses), and the knitted fabric is formed from a plurality of such loops connected in the Y-axis direction (the warp direction of the fabric 400) to form wales.

[0019] The form of the fabric 400 is not limited to weft knitting, but may also be warp knitting. Furthermore, fabrics other than knitted fabrics, such as woven fabrics and nonwoven fabrics, may also be used. Furthermore, the form of the fabric 400 may also be clothing or other accessories. Examples of 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 forms include long rolls, cut to a specified size, and finished products.

[0020] Examples of the fiber 4 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 may be blends of these. Among these materials, cotton, polyester, or a blend of cotton and polyester is preferred for the fabric because it is easily available. The fabric is preferably polyester. Since polyester tends to have poor water absorbency, it is particularly difficult to achieve both color development and suppression of penetration to the back side of the fabric. However, the inkjet printing method according to this embodiment can achieve both.

[0021] The fabric is preferably a dark-colored fabric. When printing on such fabric, a relatively large amount of colored ink composition (especially white ink) may be applied to obtain excellent color development. Therefore, it is particularly difficult to achieve both color development and suppression of penetration to the back side of the fabric. In contrast, the inkjet printing method according to this embodiment can achieve both of these goals even when using such fabric. The dark color is more preferably black.

[0022] Dark fabric L * The value is preferably 75 or less, more preferably 60 or less, even more preferably 50 or less, and particularly preferably 30 or less. * That is, L * a * b * Represents lightness in color space. * The value can be measured using a known colorimeter, for example, Spectrolino (Gretag).

[0023] An example of a dark-colored fabric is a fabric that has 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), and reactive dyes. Known methods can be used to color fabrics with dyes, depending on the material and shape of the fabric.

[0024] The fabric 400 has a plurality of voids 41 that penetrate in the thickness direction (Z-axis direction) of the fabric 400. The voids 41 penetrate in the thickness direction (Z-axis direction) of one layer of the fabric 400 to which ink is to be applied. For example, when ink is applied to multiple layers of the fabric 400 that are stacked, the voids 41 penetrate in the thickness direction (Z-axis direction) of one layer to which ink is to be applied.

[0025] The number of voids 41 per unit area of ​​the fabric 400 is not particularly limited, but is, for example, 1 to 15 voids / mm 2 is preferable, and 3 to 12 pieces / mm 2 More preferably, 5 to 8 pieces / mm 2 is more preferable.

[0026] 2 shows an example of the shape of the voids 41 when the fabric 400 is viewed in a plane in the thickness direction (Z-axis direction). In the shape of the voids 41, the maximum length of the shape in the warp direction (Y-axis direction; wale direction) of the fabric 400 is defined as La. Furthermore, the maximum length of the shape in the weft direction (X-axis direction; course direction) of the fabric 400 is defined as Lb. In the fabric 400, the shorter of La and Lb is 50 μm or more. In the case of such a fabric, it is particularly difficult to achieve both color development and suppression of penetration to the back side of the fabric, but the inkjet printing method according to this embodiment makes it possible to achieve both.

[0027] The shorter of La and Lb is 50 μm or more, but from the viewpoint of being able to enjoy the effects of the inkjet printing method according to this embodiment, it is preferably 80 μm or more, more preferably 120 μm or more, more preferably 150 μm or more, even more preferably 180 μm or more, and particularly preferably 200 μm or more. The upper limit of the shorter of La and Lb is not particularly limited, but is preferably 500 μm or less, more preferably 400 μm or less, even more preferably 300 μm or less, particularly preferably 250 μm or less, and more particularly preferably 220 μm or less.

[0028] The longer length of La and Lb is not particularly limited, but is preferably 150 μm or more, more preferably 170 μm or more, further preferably 200 μm or more, and particularly preferably 230 μm or more. The upper limit of the longer length of La and Lb is not particularly limited, but is preferably 600 μm or less, more preferably 500 μm or less, even more preferably 400 μm or less, particularly preferably 300 μm or less, and more particularly preferably 270 μm or less.

[0029] Note that La and Lb are the thicknesses of any region of the fabric 400 (for example, 10 mm 2 ) may be calculated as an average value of a plurality of voids 41 present in the fabric 400. Furthermore, it is preferable to measure La and Lb while leaving the fabric 400 at rest.

[0030] In the shape of voids 41 when fabric 400 is viewed in a plan view in the thickness direction (Z-axis direction), void shape 41 may be polygonal, with the shortest diagonal of the polygon having a length of 50 μm or more. In the case of such fabrics, it is particularly difficult to achieve both color development and suppression of penetration to the back side of the fabric, but the inkjet printing method according to this embodiment makes it possible to achieve both.

[0031] The polygon is not particularly limited, but is preferably a quadrangle or a pentagon. The length of the shortest diagonal of the polygon is 50 μm or more, but it is also preferable to set it to the same as the shorter of La and Lb.

[0032] 1.1.2 Adhesion pattern In the inkjet printing method according to this embodiment, the reaction liquid application step and the transparent ink application step described below are performed on the same region of the fabric within the same scan. This allows the reaction liquid and the transparent ink composition to be simultaneously applied by the inkjet method, forming a resin layer near the surface of the fabric, which contributes to the achievement of a sealing effect.

[0033] Here, "scanning" 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. Alternatively, the relative positional relationship between the inkjet head and the fabric may change as both the inkjet head and the fabric move. The inkjet head may be mounted on a carriage, for example. The inkjet head may be moved by the movement of the carriage, and in this case, too, the inkjet head is moved.

[0034] Therefore, in a serial inkjet recording device 20 such as that shown in FIG. 3, for example, "scanning" is performed while a carriage 234 carrying an inkjet head 231 moves in a scanning direction SD that intersects with the transport direction TD of the recording medium F.

[0035] On the other hand, in a line-type inkjet recording apparatus 1 as shown in Fig. 4, for example, "scanning" refers to recording performed while the recording medium F moves relative to a line head 300 having a length corresponding to the width of the recording medium F in a direction intersecting the width direction. In line-type recording, the inkjet head (line head) does not move during recording but is fixed, and recording is performed in one scan.

[0036] The "length equivalent to the width of the recording medium" does not necessarily mean that the width of the recording medium 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 recording medium, or a length equivalent to the width of the recording medium (recorded width) onto which ink is to be ejected (on which an image is to be recorded).

[0037] The number of times that the same area on the fabric is scanned in the reaction liquid application step and the transparent ink application step described below may be one or more times. When the same scan is performed multiple times on the same region of the fabric, the inkjet head that ejects the reaction liquid and the transparent ink passes over the same region of the fabric multiple times. The more scans there are, the more the reaction liquid and the transparent ink can be applied to the desired region in multiple separate passes (multiple passes), which tends to further improve the image quality of the resulting recorded matter.

[0038] More specifically, for example, in Figure 3, if the length of one transport of the recording medium F in the transport direction TD is one-fourth the length in the transport direction TD of the nozzle row of the inkjet head that is aligned in a direction intersecting the scanning direction SD, four scans will be performed on the same part (same area) of a rectangular scanning area that is the length of one transport in the transport direction TD and extends in the scanning direction SD.

[0039] When the same scan is performed multiple times, from the viewpoint of better image quality, the number is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and particularly preferably 6 or more. There is no upper limit, but from the viewpoint of better productivity, the number is preferably 24 or less, more preferably 12 or less, and even more preferably 8 or less.

[0040] 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, a resin layer is more satisfactorily formed near the fabric surface, which tends to contribute to the exertion of a sealing effect.

[0041] The total coating amount of the reaction liquid and the transparent ink composition described below was 50 mg / inch 2 It is preferable that the concentration is 70 mg / inch or more. 2 More preferably, it is 100 mg / inch or more. 2 More preferably, it is 110 mg / inch or more. 2When the total coating amount is within the above range, the resin layer is more satisfactorily formed in the vicinity of the fabric surface, which tends to contribute more to the exertion of the sealing effect. The upper limit of the total coating amount is not particularly limited, but is preferably 250 mg / inch. 2 Less than 200 mg / inch is preferred 2 Less than 150 mg / inch is more preferable. 2 Less than 130 mg / inch is more preferable. 2 The following are particularly preferred:

[0042] 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, a resin layer is more satisfactorily formed near the fabric surface, which tends to contribute more to the exertion of a sealing effect.

[0043] 1.1.3 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.

[0044] 1.1.3.1 Flocculants The reaction liquid contains an aggregating agent that aggregates the 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 colorants 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] Specific examples of the polyvalent metal salt include calcium carbonate such as 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, aluminum lactate, etc. These polyvalent metal salts may be used alone or in combination of two or more. Among these, magnesium sulfate, calcium formate, calcium nitrate, aluminum lactate, and calcium propionate are preferred because they have 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.

[0050] 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.

[0051] The flocculants may be used alone or in combination of two or more.

[0052] From the viewpoint of achieving better color development and suppression of penetration into the back side of the fabric, 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, and particularly preferably 3% 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.

[0053] 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, which tends to more effectively aggregate the clear ink composition and provide better color development and suppression of penetration to the back side of the fabric.

[0054] 1.1.3.2 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.

[0055] 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.

[0056] 1.1.3.3 Organic solvents The reaction liquid may contain an organic solvent, such as esters, alkylene glycol ethers, cyclic esters, amides, alcohols, and polyhydric alcohols.

[0057] Examples of esters include glycol monoacetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and methoxybutyl acetate; Examples of glycol diesters include ethylene 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.

[0058] 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.

[0059] Examples of cyclic esters include cyclic esters (lactones) such as β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, β-butyrolactone, β-valerolactone, γ-valerolactone, β-hexanolactone, γ-hexanolactone, δ-hexanolactone, β-heptanolactone, 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.

[0060] Examples of the amides include cyclic amides and non-cyclic amides. Examples of the non-cyclic amides include alkoxyalkyl amides.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] Polyhydric alcohols have two or more hydroxyl groups in the molecule and can be divided into, for example, alkanediols and polyols.

[0065] 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.

[0066] 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, 1,2-decanediol, 3-methyl-1,2-butanediol, 3-methyl-1,2-pentanediol, 4-methyl-1,2-pentanediol, and 3,4-dimethyl-1,2-pentanediol. hexanediol, 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] The organic solvents may be used alone or in combination of two or more.

[0072] Among these, the organic solvent preferably contains an alkanediol, more preferably a 1,2-alkanediol, and particularly preferably propylene glycol. When the organic solvent contains these solvents, the color development and the ability to suppress penetration to the back side of the fabric may be more excellent.

[0073] 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 the ability to suppress penetration to the back side of the fabric may be superior.

[0074] 1.1.3.4 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. Furthermore, among 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.

[0075] 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.).

[0076] 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.).

[0077] 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).

[0078] The surfactants may be used alone or in combination of two or more.

[0079] 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 transparent ink are mixed tends to increase, which leads to better formation of a resin layer near the surface of the fabric, contributing to the exertion of a sealing effect, and tends to result in better color development and suppression of penetration to the back side of the fabric. 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, based on the total amount of the reaction liquid.

[0080] 1.1.3.5 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.

[0081] The reaction liquid may contain a coloring material such as a pigment, but the amount is preferably 0.2% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.05% by mass or less, with the lower limit being 0% by mass, relative to the total amount of the reaction liquid. Preferably, the reaction liquid does not contain a coloring material.

[0082] 1.1.3.6 Physical Properties The viscosity of a mixture (equal 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) is 50 mPa·s or more at 20°C. When the viscosity of the equal mixture is 50 mPa·s or more at 20°C, the penetration rate into the fabric is slowed, allowing a transparent ink layer (resin layer) to be formed well near the surface of the fabric, which contributes to the achievement of a sealing effect.

[0083] The viscosity of the equal-volume mixture at 20°C is 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 more particularly preferably 750 mPa·s or more. The upper limit of the viscosity of the equal-volume mixture 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 more particularly preferably 1,500 mPa·s or less.

[0084] The viscosity can be measured using, for example, a viscoelasticity tester MCR-300 (product name) manufactured by Pysica.

[0085] 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 provide better color development. A viscosity of 8.0 mPa·s or lower tends to provide better ejection stability.

[0086] 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.

[0087] 1.2 Transparent ink application process The inkjet printing method according to this embodiment includes a clear ink applying step of applying a clear ink composition containing anionic resin particles and water to a fabric by an inkjet method.

[0088] 1.2.1 Adhesion pattern The manner of application in the transparent ink application step is the same as that explained in the reaction liquid application step, and therefore, explanation thereof will be omitted.

[0089] 1.2.2 Transparent ink composition The transparent ink composition used in the transparent ink application step contains anionic resin particles and water. Each component contained in the transparent ink composition will be described below.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.).

[0094] 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.).

[0095] Styrene-acrylic resins are copolymers obtained from styrene monomers and (meth)acrylic monomers, and examples thereof include styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylate copolymers, styrene-α-methylstyrene-acrylic acid copolymers, and styrene-α-methylstyrene-acrylic acid-acrylate copolymers. As the styrene-acrylic resin, commercially available products may be used, 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.).

[0096] 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.).

[0097] 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.

[0098] 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).

[0099] 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 more particularly preferably 8 to 12 mass %. When the content of the anionic resin particles is within the above range, better color development and suppression of penetration into the back side of the fabric tend to be obtained.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] In the transparent 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 better.

[0104] 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 the ability to suppress penetration to the back side of the fabric may be superior.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] 1.2.2.6 Physical Properties 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.

[0110] 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.

[0111] 1.3 Colored ink application process The inkjet textile printing method according to this embodiment includes a colored ink applying step of applying, by an inkjet method, a colored ink composition containing a coloring material, 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 manner described above exhibits a sealing effect by forming a resin layer due to aggregation of resin particles in the transparent ink near the surface of the fabric, and by suppressing penetration of the colored ink composition (hereinafter also referred to as "colored ink") into the fabric, good color development is achieved.

[0112] 1.3.1 Adhesion pattern The amount of colored ink composition applied is 50 to 300 mg / inch 2 It is preferable that the density is 60 to 270 mg / inch. 2 More preferably, it is 70 to 250 mg / inch. 2 More preferably, it is 100 to 250 mg / inch. 2 It is particularly preferable that the density is 100 to 200 mg / inch. 2 It is more particularly preferable that the concentration is 100 to 150 mg / inch. 2It is particularly preferred that: In the past, when the amount of deposited colored ink was increased to compensate for the decrease in color development, the color development improved but the penetration to the back side of the fabric worsened, making it difficult to achieve both color development and suppression of penetration to the back side of the fabric. In contrast, the inkjet printing method according to this embodiment tends to be able to obtain good color development and good suppression of penetration to the back side of the fabric, even with the above-mentioned amount of deposited colored ink composition.

[0113] The colored ink application step may be performed by the same scanning as that in the above-mentioned transparent ink application step, but is preferably performed by a scanning different from that in the above-mentioned transparent ink application step. In this case, the sealing effect of the resin layer formed near the surface of the fabric is more pronounced, which tends to result in better color development and suppression of penetration to the back side of the fabric.

[0114] The number of scans for the colored ink application step may be one or more for the same region of the fabric. When multiple scans are performed, from the viewpoint of better image quality, the number is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and particularly preferably 6 or more. There is no upper limit, but from the viewpoint of better productivity, the number is preferably 24 or less, more preferably 12 or less, and even more preferably 8 or less.

[0115] 1.3.2 Colored ink composition The color ink composition used in the color ink application step contains a coloring material, resin particles, and water. Each component contained in the color ink composition will be described below.

[0116] 1.3.2.1 Colorants The colored ink composition contains a coloring material. Examples of the coloring material include pigments and dyes. Examples of the pigment that can be used include inorganic pigments and organic pigments.

[0117] 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.

[0118] 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, Pretex 35, U, V, and 140U, and Special Black 6, 5, 4A, 4, and 250 manufactured by Degussa. Examples of carbon black include Conductex SC, Raven 1255, 5750, 5250, 5000, 3500, 1255, and 700 manufactured by Columbia Carbon Corporation. Examples include Cabot Corporation's Regal 400R, 330R, 660R, Mogul L, Monarch 700, 800, 880, 900, 1000, 1100, 1300, 1400, and Elftex 12.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] Specific examples of organic pigments include the following:

[0123] 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.

[0124] 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.

[0125] 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.

[0126] Pigments of other colors can also be used, such as orange pigments and green pigments.

[0127] The pigments may be used alone or in combination of two or more.

[0128] The colored ink composition is preferably a white ink composition (hereinafter also referred to as "white ink") containing a white pigment as a colorant. A colored ink composition 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 color development and suppression of penetration into the back side of the fabric. In contrast, the inkjet printing method according to this embodiment tends to achieve excellent color development and suppression of penetration into the back side of the fabric, even with a colored ink composition containing a white pigment.

[0129] In this specification, the term "white" when referring to a white ink composition, a white pigment, etc. does not refer only to a completely white color, but also includes chromatic or achromatic colors and glossy colors as long as they are visually recognizable as white. It also includes inks and coloring materials that are named and sold with names that suggest they are white inks or white coloring materials.

[0130] More quantitatively, "white" refers to the color of a recording that is, for example, in CIELAB, L * Not only the color where L is 100, * is between 60 and 100, and a * and b * Also included are colors where the difference is less than ±10. More specifically, for example, when a white ink composition is used to record a transparent film recording medium surface in an amount that sufficiently covers the surface, the brightness (L * ) and chromaticity (a * , b * When the color of the ink is measured using a spectrophotometer conforming to CIELAB, it is preferable that the color is in the above range. 2 More preferably, the amount of adhesion is 80≦L *≦100, -4.5≦a * ≦2, -10≦b * ≦2.5. An example of a recording medium made of transparent film is the LAG Jet E-1000ZC (manufactured by Lintec Corporation). An example of a spectrophotometer conforming to CIELAB is the Spectrolino (trade name, manufactured by GretagMacbeth), and measurement is performed under the following measurement conditions: D50 light source, observation field of view of 2°, density of DIN NB, white standard of Abs, filter of No, and measurement mode of Reflectance. Anything other than "white" is considered "non-white."

[0131] 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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] 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.).

[0137] 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.

[0138] 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).

[0139] 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.

[0140] It is preferable that at least one of the colorant 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 suppression of penetration into the back side of the fabric tend to be obtained. The colorant being anionic means that the colorant 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 group may be present directly on the surface of the colorant, or may be present via an anionic resin dispersant adsorbed or bonded to the colorant.

[0141] 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.

[0142] 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.

[0143] 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.

[0144] The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used. The dyes may be used alone or in combination of two or more.

[0145] The dye is not particularly limited, and examples thereof include CI Acid Yellow 17, 23, 42, 44, 79, 142, CI Acid Red 52, 80, 82, 249, 254, 289, CI Acid Blue 9, 45, 249, CI Acid Black 1, 2, 24, 94, CI Food Black 1, 2, CI Direct Yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 14 2, 144, 173, CI Direct Red 1, 4, 9, 80, 81, 225, 227, CI Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202, CI Direct Black 19, 38, 51, 71, 154, 168, 171, 195, CI Reactive Red 14, 32, 55, 79, 249, CI Reactive Black 3, 4, 35.

[0146] The content of the colorant (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 colorant is within the above range, better color development (whiteness) tends to be obtained.

[0147] 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. By including resin particles in the colored ink composition, the colored ink composition exhibits a sealing effect on the resin layer formed by aggregation of the resin particles in the transparent ink near the surface of the fabric, thereby improving color development and the ability to suppress penetration to the back side of the fabric.

[0148] The resin particles in the colored ink composition are preferably 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.

[0149] 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.

[0150] 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.

[0151] The content of the resin particles (solid content concentration) is preferably 1 to 30 mass % relative to the total amount of the colored ink composition, 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 suppression of penetration into the back side of the fabric tend to be obtained.

[0152] 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.

[0153] 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.

[0154] 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.

[0155] 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 the ability to suppress penetration into the back side of the fabric may be superior.

[0156] The colored ink composition preferably further contains 3.0% by mass or more, more preferably 5.0% by mass or more, and even more preferably 7.0% 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).

[0157] 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.

[0158] The content of the organic solvent is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, even more preferably 15 to 30% by mass, and particularly preferably 20 to 25% by mass, relative to the total amount of the color ink composition. When the content of the organic solvent is within the above range, the color development and the ability to suppress penetration to the back side of the fabric may be superior.

[0159] 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.

[0160] 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 0.5% 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 preferred manner.

[0161] 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.

[0162] 1.3.2.7 Physical Properties

[0163] 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.

[0164] 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.

[0165] 1.4 Second colored ink application process The inkjet textile printing method according to this embodiment may include a second colored ink applying step of applying a colored ink composition by an inkjet method onto the region of the fabric to which the above-described colored ink composition has been applied. In particular, when the colored ink composition in the colored ink applying step is a white ink composition, the color development of the color image in the second colored ink applying step can be further improved, which is preferable.

[0166] The amount of the color ink composition applied in the second color ink application step is 5 to 30 mg / inch 2 It is preferable that the density is 6 to 25 mg / inch. 2 More preferably, it is 8 to 20 mg / inch. 2 More preferably, it is 10 to 15 mg / inch. 2 It is particularly preferred that:

[0167] The second color ink application step is preferably performed by a scanning method different from that of the color ink application step described above, which tends to result in better color development.

[0168] The colored ink composition used in the second colored ink applying step is as described above, and therefore a description thereof will be omitted. Note that the colored ink composition used in this step can be prepared independently of the colored ink composition used in the above-described colored ink applying step.

[0169] When the colored ink composition used in the above-described colored ink applying step is a white ink composition, the colored ink composition used in the second colored ink applying step is preferably a non-white ink composition.

[0170] In the non-white ink composition, the content of the colorant is preferably 1 to 20 mass %, more preferably 2 to 15 mass %, even more preferably 3 to 10 mass %, and particularly preferably 3 to 8 mass %, relative to the total amount of the non-white ink composition.

[0171] In the non-white ink composition, the content (solids concentration) of the resin particles is preferably 1 to 20 mass % relative to the total amount of the non-white ink composition, more preferably 2 to 15 mass %, even more preferably 3 to 10 mass %, and particularly preferably 3 to 8 mass %.

[0172] 1.5 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.

[0173] The heat drying method is not particularly limited, but examples thereof include a heat press, 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.

[0174] 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 130°C or higher and 200°C or lower, and particularly preferably 130°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 10 seconds or higher and 5 minutes or lower, more preferably 20 seconds or higher and 3 minutes or lower, and even more preferably 30 seconds or higher and 60 seconds or lower.

[0175] The heat drying step is preferably carried out while applying pressure using a heat press or the like. The pressure to be applied is not particularly limited, but is preferably 1 to 10 N / cm. 2 Preferably, the strength is 1 to 8 N / cm 2 More preferably, it is 1 to 5 N / cm 2 It is more preferable that:

[0176] 1.6 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.

[0177] 1.7 Inkjet recording device An inkjet recording apparatus that can be preferably used in the inkjet textile printing method according to this embodiment will be described.

[0178] As an example of an inkjet recording device, a perspective view of a serial printer is shown in Fig. 3. As shown in Fig. 3, the serial printer 20 includes a conveying unit 220 and a recording unit 230. The conveying unit 220 conveys the recording medium F fed to the serial printer to the recording unit 230, and ejects the recording medium after recording outside the serial printer. Specifically, the conveying unit 220 has feed rollers and conveys the fed recording medium F in the conveying direction TD.

[0179] The recording unit 230 also includes a carriage 234 carrying an inkjet head 231 having a nozzle for ejecting a reaction liquid onto the recording medium F sent from the transport unit 220, a nozzle for ejecting a transparent ink composition, and a nozzle for ejecting a colored ink composition, and a carriage moving mechanism 235 for moving the carriage 234 in the scanning direction SD of the recording medium F.

[0180] Fig. 5 shows an example of each nozzle row on the nozzle surface of the inkjet head 231. In Fig. 2, the inkjet head 231 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 (transport direction TD) that intersects with the direction in which the inkjet head 231 is moved (scanning direction SD). In this case, by arranging the nozzle row that ejects the reaction liquid so that when projected along the scanning direction SD, it at least partially overlaps with the nozzle row that ejects the transparent ink composition in the transport direction TD, the reaction liquid application step and the transparent ink application step can be performed on the same region of the fabric within the same scan. 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.

[0181] In the case of a serial printer, an inkjet head 231 having a length smaller than the width of the recording medium is provided, and recording is performed while the head moves in a scanning direction SD that intersects with the transport direction TD of the recording medium F. In addition, in a serial printer, the head 231 is mounted on a carriage 234 that moves in a predetermined direction, and the head moves in conjunction with the movement of the carriage, thereby ejecting the ink composition and reaction liquid onto the recording medium. The recording medium may be transported between scans.

[0182] Furthermore, the inkjet device is not limited to the serial printer described above, but may also be a line printer. Fig. 4 shows a schematic side view of a line printer as another example of an inkjet recording device. As shown in Fig. 4, the line printer 1 includes a feed unit 100, a transport mechanism 200 that transports the recording medium in the transport direction, a line head 300 that ejects ink onto the recording medium to adhere it, a control unit 500, and a discharge unit 700.

[0183] The transport mechanism is a mechanism that transports a recording medium in a transport direction. In FIG. 4, a roll-shaped recording medium F is supplied from a feeding unit 100 to a transport mechanism 200, and the transport mechanism 200 is configured to transport the recording medium F sent from the feeding unit 100 to a line head 300. Specifically, the transport mechanism 200 has a first feed roller 201 and a second feed roller 202, and is configured to transport the fed recording medium F to the line head 300 downstream in the transport direction. A conventionally known transport method can be used as appropriate for the transport mechanism 200, and one or more rollers, or a belt fed by rollers, may be used.

[0184] The line printer 1 has a line head 300 having a length corresponding to the width of the recording medium F. The line head 300 may be made up of multiple line jets, and in Figure 3, the line head 300 is made up of a first line head 310, a second line head 320, a third line head 330, and a fourth line head 340. When there is no need to distinguish between the first line head 310, the second line head 320, the third line head 330, and the fourth line head 340, they are simply referred to as line heads 300.

[0185] The line head 300 has cavities that contain reaction liquid, a clear ink composition, and colored ink compositions (such as inks), an ejection drive unit provided for each cavity, and nozzles that eject the inks, etc. A single head may have a plurality of cavities, ejection drive units, and nozzles that are independent of each other. The ejection drive units may be formed using electromechanical conversion elements such as piezoelectric elements that change the volume of the cavities through mechanical deformation, or electrothermal conversion elements that generate heat to generate bubbles in the ink and eject it.

[0186] The line head 300 is preferably configured, for example, so that the reaction liquid is ejected from the first line head 310 and the clear ink composition is ejected from the second line head 320. In this way, the reaction liquid application step and the clear ink application step can be performed on the same region of the fabric within the same scan. Also, it is preferable that the white ink composition as the colored ink composition is ejected from the third line head 330 and the non-white ink composition as the colored ink composition is ejected from the fourth line head 340.

[0187] 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.

[0188] 2. 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.

[0189] 2.1 Preparation of reaction liquid, transparent ink composition, and colored ink composition The components were placed in a container to obtain the compositions shown in Table 1 (Figure 6) and Table 2 (Figure 7), mixed and stirred, and then filtered through a 5 μm membrane filter to obtain the reaction liquid (Ink 1-1), clear ink composition (Ink 1-2), and colored ink composition (Wh ink, Ink 2) for each example. The numerical values ​​for each component shown in each example in the tables represent % by mass unless otherwise specified. The % by mass of the colorant and resin particles in the tables represent the solids concentration, and pure water was added so that the total mass of the composition was 100% by mass.

[0190] The white pigment used was titanium dioxide dispersion A, which had been prepared in advance using the following procedure. CI Pigment White 6 (specific gravity: 4.2 g / mL) was used as the colorant, 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 the 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. Large particles were then separated using a centrifuge (Kuboyama Shoji Co., Ltd., Model-3600) to obtain titanium dioxide dispersion A (with cation response).

[0191] As the black pigment, a self-dispersing carbon black pigment "CAB-O-JET300" (manufactured by Cabot Corporation, solid content 15%) was used.

[0192] The following provides additional explanations for the items listed in Tables 1 and 2. Takelac WS-6021 (product name, manufactured by Mitsui Chemicals Polyurethanes, Inc.; the urethane resin in Table 2 was also the same product) BYK-348 (product name, manufactured by BYK, silicone surfactant) Olfine E1010 (product name, manufactured by Nissin Chemical Industry Co., Ltd., acetylene glycol surfactant)

[0193] 2.2 Recording conditions Using the reaction liquid (Ink 1-1), the transparent ink composition (Ink 1-2), and the colored ink compositions (Wh ink, Ink 2) obtained above, inkjet textile printing methods according to the examples and comparative examples were carried out under the conditions described in Table 3 (FIG. 8) and Table 4 (FIG. 9). Specifically, an inkjet printer (product name PX-G930, manufactured by Seiko Epson Corporation) was filled with the reaction liquid (Ink 1-1), the clear ink composition (Ink 1-2), and the colored ink compositions (Wh ink, Ink 2) obtained above, and printing was performed on the recording media listed in Tables 3 and 4 under the conditions listed in Tables 3 and 4 using a fill pattern that could be recorded at a resolution of 720 dpi horizontally and 720 dpi vertically and with a duty of 100%. After printing, a heat press dryer was used to dry the paper at 30°C and 1.5N / cm 2 The resulting material was dried under the conditions of 100°C for 60 seconds, to obtain a printed product.

[0194] In Tables 3 and 4, the "knitting pitch width" refers to the shorter of the maximum length of the shape of the voids that penetrate the thickness direction of the fabric in the warp direction of the fabric and the maximum length of the shape of the shape in the weft direction of the fabric. Here, this refers to the length Lb in Figure 2. In addition, the "dark color (black)" fabric L * The value was 20.

[0195] In Tables 3 and 4, when "Pretreatment agent application (roller application)" is "Yes," a pretreatment agent composition containing 8.0 mass% calcium nitrate, 25.0 mass% propylene glycol, 0.5 mass% Olfine E1010, and 66.5 mass% water was used at a concentration of 114.6 mg / inch2 The coating was applied to the fabric with a roller in an amount of 1000 ml.

[0196] In Tables 3 and 4, "Resin layer application amount (Ink 1-1 + Ink 1-2)" indicates the total application amount of the reaction liquid (Ink 1-1) and the clear ink composition (Ink 1-2). The application amount ratio of the reaction liquid (Ink 1-1) to the clear ink composition (Ink 1-2) was 1:1.

[0197] In Tables 3 and 4, when "Ink 1-1 + 1-2 simultaneous deposition" is marked "Yes," this indicates that the reaction liquid (Ink 1-1) and the transparent ink composition (Ink 1-2) were deposited on the same area of ​​the fabric within the same scan. The inkjet head shown in Figure 5 was used, and recording was performed with rows A and B as nozzle rows ejecting the reaction liquid, rows C and D as nozzle rows ejecting the transparent ink composition, and rows E and H as nozzle rows ejecting the colored ink compositions. The application of the colored ink compositions (Wh ink, Ink 2) was performed by a scan different from the scan in which the reaction liquid (Ink 1-1) and the transparent ink composition (Ink 1-2) were applied. The Wh ink was applied onto the area of ​​the fabric to which the transparent ink composition or the pretreatment agent had been applied. When the Wh ink and Ink 2 were used, Ink 2 was applied onto the area of ​​the fabric to which the Wh ink had been applied.

[0198] In Tables 3 and 4, "Viscosity when Ink 1-1 and Ink 1-2 are mixed" refers to the viscosity (mPa·s) of a mixture of equal amounts of the reaction liquid (Ink 1-1) and the clear ink composition (Ink 1-2), measured 3 minutes after mixing using a viscoelasticity tester MCR-300 (trade name, manufactured by Pysica) at 20°C.

[0199] 2.3 Evaluation method 2.3.1 Color development The color development properties of the printed textiles according to the examples and comparative examples obtained under the above-mentioned recording conditions were evaluated. Specifically, the OD value of the recorded area of ​​each color of each of the printed textiles was determined by measurement using a spectrodensitometer FD-7 (Konica Minolta), and the ratio to the OD value of the recorded area of ​​the printed textile of Comparative Example 2 was determined for Examples 1 and 2 and Comparative Examples 1 and 3 to 5, and the ratio to the OD value of the recorded area of ​​the printed textile of Comparative Example 6 was determined for Examples 3 to 6 and Comparative Examples 7 to 11, and the evaluation was carried out according to the following criteria. The higher this ratio, the better the color development. A level of B or higher was determined to be good. (Evaluation criteria) A: The OD value is 120% or more of that of the comparative example. B: The OD value is 100% or more and less than 120% of that of the comparative example. C:OD values ​​are less than 100% of those of the comparative examples.

[0200] 2.3.2 Washing fastness The prints of each example and comparative example obtained under the above-mentioned printing conditions were evaluated for washing fastness. A washing fastness test (ISO 105 C10 (B2)) was conducted, and a score of B or higher was considered to be good. (Evaluation criteria) A: Washing fastness is grade 3 or higher. B: Washing fastness is between grade 2 and grade 3. C: Washing fastness is less than grade 2.

[0201] 2.3.3 Texture The texture of the printed textiles according to each of the Examples and Comparative Examples obtained under the above-mentioned printing conditions was evaluated. For each printed item, a specific evaluator performed a sensory evaluation of the feel according to the following criteria to evaluate the texture. The evaluation results are ranked in order of C, B, and A, which indicate excellent texture. Evaluation results of A and B can be said to be good. (Evaluation criteria) A: It is soft and does not feel stiff. B: Slightly hard and slightly stiff to the touch. C: There is a noticeable stiffness to the touch.

[0202] 2.3.4 Strike-through (prevention of penetration to the back side of the fabric) The backside of each printed item according to each example and comparative example obtained under the above recording conditions was observed, and the ink strike-through (penetration) was visually confirmed. A grade of B or higher is a good level. (Evaluation criteria) A: No bleed-through. B: Slight bleed-through is observed. C: bleed-through is clearly observed.

[0203] 2.3.5 Workability When "pretreatment agent application (roller application)" was "present," the rating was C, and when "not present," the rating was A. A is a good level.

[0204] 2.4 Evaluation results The evaluation results are shown in Tables 3 and 4. The method includes a reaction liquid applying step of applying a reaction liquid containing water and an aggregating agent for aggregating components in the ink to the fabric by an inkjet method, a clear ink applying step of applying a clear ink composition containing anionic resin particles and water to the fabric by an inkjet method, and a colored ink applying step of applying a colored ink composition containing a coloring material, resin particles, and water to the area of ​​the fabric to which the clear ink composition has been applied by an inkjet method, and the reaction liquid applying step and the clear ink applying step are performed within the same scan. Each example relating to the inkjet printing method in which the reaction liquid and the transparent ink composition were mixed in equal amounts and the viscosity of the mixture was 50 mPa·s or more at 20°C, the fabric had voids that penetrated the fabric in the thickness direction, and the shape of the voids when the fabric was viewed in a plane in the thickness direction was such that the shorter of the maximum length of the shape in the warp direction of the fabric and the maximum length of the shape in the weft direction of the fabric was 50 μm or more, had good workability, color development, and suppression of penetration to the back side of the fabric.

[0205] In contrast, the inkjet printing methods according to the comparative examples that did not satisfy the above-mentioned requirements were inferior in at least one of workability, color development, and suppression of penetration to the back side of the fabric.

[0206] The following can be derived from the above-described embodiment.

[0207] One aspect of the inkjet printing method is a reaction liquid applying step of applying a reaction liquid containing a flocculant that aggregates components in the ink and water to the fabric by an inkjet method; a transparent ink applying step of applying a transparent ink composition containing anionic resin particles and water to the fabric by an inkjet method; a colored ink applying step of applying a colored ink composition containing a coloring material, resin particles, and water by an inkjet method onto the area of ​​the fabric to which the transparent ink composition has been applied; the reaction liquid applying step and the transparent ink applying step are performed on the same region of the fabric during the same scan; a viscosity of a mixture of equal amounts of the reaction liquid and the transparent ink composition is 50 mPa·s or more at 20°C; The fabric has voids penetrating in the thickness direction, When the fabric is viewed in a plane in the thickness direction, the shape of the voids has a maximum length in the warp direction of the fabric and a maximum length in the weft direction of the fabric, the shorter of which is 50 μm or more.

[0208] In one embodiment of the inkjet printing method, The colored ink composition may be a white ink composition.

[0209] In any one of the above ink-jet printing methods, The amount of the colored ink composition deposited is 100 to 250 mg / inch 2 may be.

[0210] In any one of the above ink-jet printing methods, The fabric may be polyester.

[0211] In any one of the above ink-jet printing methods, The fabric may be a dark colored fabric.

[0212] 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 with respect to the total amount of the reaction liquid.

[0213] 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]

[0214] 400...fabric, 4...fiber, 41...gap, La...maximum length of the shape in the warp direction of the fabric, Lb...maximum length of the shape in the weft direction of the fabric, 20...serial printer, 220...conveying unit, 230...recording unit, 231...inkjet head, 234...carriage, 235...carriage moving mechanism, 1...line printer, 100...feeding unit, 200...conveying mechanism, 201...first feed roller, 202...second feed roller, 300...line head, 310...first line head, 320...second line head, 330...third line head, 340...fourth line head, 500...control unit, Y...feed direction, F...recording medium, SD...scanning direction, TD...conveying direction.

Claims

1. A reaction solution application step in which a reaction solution containing a coagulant that aggregates components in the ink and water is applied to a fabric by an inkjet method, A transparent ink application step in which a transparent ink composition containing anionic resin particles and water is applied to the fabric by an inkjet method, a colored ink applying step of applying a colored ink composition containing a coloring material, resin particles, and water by an inkjet method onto the area of ​​the fabric to which the transparent ink composition has been applied; The reaction solution application step and the transparent ink application step are performed within the same scan and on the same area of ​​the fabric. The reaction solution and the transparent ink composition have a viscosity of 50 mPa·s or more at 20°C when mixed in equal volumes. The aforementioned fabric has voids that penetrate in the thickness direction, an inkjet printing method, wherein, in the shape of the void when the fabric is viewed in a plane in the thickness direction, the shorter of the maximum length of the shape in the warp direction of the fabric and the maximum length of the shape in the weft direction of the fabric is 50 μm or more.

2. The inkjet printing method according to claim 1, wherein the colored ink composition is a white ink composition.

3. The amount of the colored ink composition applied is 100 to 250 mg / inch. ２ The inkjet printing method according to claim 1 or claim 2.

4. The inkjet printing method according to claim 1 or claim 2, wherein the fabric is polyester.

5. The inkjet printing method according to claim 1 or claim 2, wherein the fabric is a dark-colored fabric.

6. The inkjet printing method according to claim 1 or 2, 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.

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