Inkjet printing method and set

Abstract

To provide an inkjet printing method capable of making friction fastness and color development excellent when adhering a reaction liquid on a fabric by an inkjet method.SOLUTION: The inkjet printing method according to an embodiment of the present invention includes: a reaction liquid adhesion step of adhering a reaction liquid containing an aggregating agent for aggregating components in ink and water, to a fabric by an inkjet method; a transparent ink adhesion step of adhering a transparent ink composition containing anionic resin particles and water to the fabric by the inkjet method; and a colored ink adhesion step of adhering a colored ink composition containing pigments, resin particles, and water to an area where the transparent ink composition is adhered, by the inkjet method. The reaction liquid adhesion step and the transparent ink adhesion step include the following step 1, in which a range of the minimum value of the total adhered amount of the reaction liquid and the transparent ink composition per unit area / unit time is 34 mg / (s inch2) or more. Step 1: Coating of the reaction liquid and the transparent ink composition during one scan of the inkjet head in the same area of the fabric.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Conventionally, in textile printing using an inkjet ink composition containing a pigment as a coloring material (pigment textile printing), 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 abrasion fastness and color development.

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

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

[0005] However, when the reaction liquid is applied to a fabric by the ink-jet method, it has not been possible to obtain good resistance to rubbing and good color development. [Means for solving the problem]

[0006] One aspect of the inkjet printing method according to the present invention includes: a reaction liquid attachment step of attaching a reaction liquid containing a flocculant for flocculating 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 a fabric by an inkjet method; a color ink applying step of applying a color ink composition containing a pigment, resin particles, and water by an ink jet method onto the area to which the transparent ink composition has been applied; The reaction liquid applying step and the transparent ink applying step include the following step 1: In the step 1, the range of the minimum value of the total amount of the reaction liquid and the transparent ink composition attached per unit area and unit time is 34 mg / (s·inch 2 )That's all. Step 1: applying the reaction liquid and the transparent ink composition to the same area of ​​the fabric in one scan of an inkjet head.

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

[0008] [Figure 1] FIG. [Diagram 2] FIG. 2 is a schematic diagram showing an example of a nozzle row arrangement of an inkjet head. [Diagram 3] FIG. 1 is a schematic side view of a line printer. [Figure 4] 4 is a table showing example compositions of a reaction liquid, a clear ink composition, and a colored ink composition. [Diagram 5] 1 is a table showing recording conditions of the inkjet printing method according to each of the examples and comparative examples. [Figure 6] 1 is a table showing recording conditions of the inkjet printing method according to each of the examples and comparative examples. [Figure 7]1 is a table showing recording conditions of the inkjet printing method according to each of the examples and comparative examples. [Figure 8] 1 is a table showing the evaluation results of the inkjet printing methods according to the respective examples and comparative examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

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

[0011] 1. Inkjet printing method An inkjet textile printing method according to one embodiment of the present invention comprises a reaction liquid applying step of applying a reaction liquid containing water and an aggregating agent for aggregating components in an ink to a 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, and a colored ink applying step of applying a colored ink composition containing a pigment, resin particles, and water to an area to which the transparent ink composition has been applied by an inkjet method, the reaction liquid applying step and the transparent ink applying step comprising the following steps: step 1: applying the reaction liquid and the transparent ink composition to the same area on the fabric in one scan of an inkjet head, and in step 1, a range of a minimum value of the total amount of application of the reaction liquid and the transparent ink composition per unit area·unit time is 34 mg / (s·inch 2 )That's all.

[0012] Conventionally, in inkjet textile printing, a process is carried out in which a reaction liquid that aggregates ink components is applied to a fabric in order to improve the color development of a coloring material. This process is usually carried out using a device or equipment separate from the inkjet recording device, or is often carried out manually, requiring large equipment and complicated processes. Therefore, a mode has been studied in which not only the ink but also the reaction liquid is ejected by the inkjet method, and the reaction liquid and the ink are continuously applied within the same device. In such a mode, there is no need to use a separate device or equipment, and the process can be simplified.

[0013] However, in the above embodiment, as the total amount of the applied reaction liquid or ink increases, it becomes more difficult to achieve both friction fastness and color development. This is presumably because, when the total amount of the applied reaction liquid or ink is large, the moisture content increases, so that the coagulation action of the reaction liquid when the ink lands tends to be insufficient, and the ink penetrates into the fabric, causing a decrease in color development. It is also assumed that an increase in moisture content i) reduces drying properties and makes the ink layer more likely to adhere insufficiently, and further ii) reduces the ink's ability to penetrate the fabric as the moisture content of the woven fabric increases, causing gaps to form between the ink layer and the surface layer of the fabric and making it more likely that adhesion will be insufficient, thereby reducing adhesion between the ink layer and the fabric and reducing friction fastness. In particular, when printing on colored fabrics, a white ink layer may be provided as a base to improve color development. However, since the amount of white ink applied in such printing is relatively large, the total amount of the reaction liquid and ink to be applied tends to be larger, making it particularly difficult to achieve both friction fastness and color development. It is difficult.

[0014] In contrast, according to the inkjet printing method of this embodiment, the aggregating agent in the reaction liquid aggregates the transparent ink composition on the fabric, forming a transparent ink layer (resin layer, base) near the surface of the fabric. Here, the fabric absorbs the droplets that land on it, so if the amount of droplets attached per unit time is different, the adhesion pattern will be different even if the amount of attachment is the same. In other words, if the amount of droplets attached per unit time is small compared to the absorption speed of the droplets in the fabric, ink is unlikely to remain near the surface of the fabric. Therefore, by setting the total adhesion amount per unit time and unit area of ​​the reaction liquid and the transparent ink composition to a predetermined value or more, i.e., the total instantaneous adhesion amount to a predetermined value or more, it is possible to cause the ink to aggregate before it penetrates the fabric, and to satisfactorily form a resin layer near the surface of the fabric. With such a well-formed resin layer, even if a colored ink is further applied thereon and the total amount of reaction liquid and ink applied is large, the penetration of the colored ink into the fabric can be suppressed, and good color development can be obtained. In addition, the resin layer functions as a binding layer between the fabric and the colored ink layer, thereby obtaining good friction fastness.

[0015] In the inkjet printing method according to this embodiment, in the region on the fabric to which the reaction liquid, the transparent ink composition, and the colored ink composition are adhered, the total amount of the reaction liquid, the transparent ink composition, and the colored ink composition adhered is 100 mg / inch2 In this case, since the total amount of the reaction liquid and ink to be adhered is relatively large, it is difficult to achieve both friction fastness and color development, but the inkjet printing method according to this embodiment can provide good friction fastness and color development. The upper limit of the total amount of adhesion is not particularly limited, but is preferably 500 mg / inch 2 It is preferable that the concentration is less than 300 mg / inch. 2 More preferably, it is 200 mg / inch or less. 2 More preferably, it is 150 mg / inch or less. 2 It is particularly preferred that:

[0016] Hereinafter, each step of the inkjet textile printing method according to this embodiment will be described.

[0017] 1.1 Reaction solution attachment process The inkjet textile printing method according to this embodiment includes a reaction liquid attachment step of attaching a reaction liquid containing water and an aggregating agent that aggregates components in the ink to a fabric by an inkjet method.

[0018] 1.1.1 Process 1 In the inkjet printing method according to this embodiment, the reaction liquid application step and the transparent ink application step described below include step 1: applying the reaction liquid and the transparent ink composition to the same area of ​​the fabric in one scan of the inkjet head. In step 1, the range of the minimum value of the total amount of application of the reaction liquid and the transparent ink composition per unit area and unit time is 34 mg / (s·inch 2 )That's all. According to the coating method of step 1, the reaction liquid and the transparent ink composition can be applied to the fabric continuously in the same device.

[0019] <Scan> Here, "scanning" in step 1 refers to moving the inkjet head relative to the recording area on the fabric. In this case, the inkjet head may be moved relative to the fabric, or the fabric may be moved relative to the inkjet head. In addition, the relative positional relationship between the inkjet head and the fabric may change by moving both the inkjet head and the fabric.

[0020] Therefore, in the “scanning” in step 1, for example, in a serial type inkjet recording device 20 as shown in FIG. 1, recording is performed while a carriage 234 having an inkjet head 231 moves in a scanning direction SD that intersects with the transport direction TD of the recording medium F.

[0021] In the case of a serial printing method, in order to increase the printing resolution, the fabric may be transported between scans. The fabric is transported by moving the relative positions of the inkjet head and the fabric in a direction intersecting the direction of the scan. Note that while the fabric is being transported, ink or the like is not ejected from the inkjet head to deposit on the recording medium. That is, in the inkjet printing method according to this embodiment, step 1 may be performed multiple times, and the reaction liquid applying step and the transparent ink applying step may include step 2: transporting the fabric in a direction intersecting the scanning direction, and step 2 may be performed between multiple instances of step 1. This allows the reaction liquid and the transparent ink composition to be applied to the same region of the fabric in multiple batches.

[0022] More specifically, for example, in FIG. 1, 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 arranged in a direction intersecting the scanning direction SD of the inkjet head, then process 1 will be performed four times in the same part (same scanning 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.

[0023] The number of times step 1 is two or more, may be three or more, or may be four or more. The upper limit of step 1 is not particularly limited, but may be less than 20 times, may be less than 15 times, or may be less than 10 times. In addition, when step 1 is performed n times (n is an integer of 2 or more), step 2 is preferably performed n-1 times. Step 1 and step 2 are preferably performed alternately and repeatedly.

[0024] On the other hand, in the "scanning" in step 1, in a line-type inkjet recording apparatus 1 as shown in Fig. 3, recording is performed while the recording medium F moves in position relative to a line head 300 having a length equivalent to the width of the recording medium F in a direction intersecting the width direction. In line-type recording, the inkjet head (line head) is fixed and does not move during recording, and recording is performed in one scan.

[0025] "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 equal, 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 the ink is to be ejected (on which the image is to be recorded).

[0026] <Amount of adhesion per unit area / unit time> In step 1, the minimum range of the total amount of reaction liquid and transparent ink composition attached per unit area and unit time is 34 mg / (s·inch 2 ) or more, but 40 mg / (s·inch 2 ) or more is preferable, and 45 mg / (s·inch 2 ) or more is preferable, and 50 mg / (s·inch 2 ) or more is more preferable, and 55 mg / (s·inch 2 ) or more is particularly preferable, and 60 mg / (s·inch 2 ) or more are more particularly preferred. The minimum range is 34 mg / (s·inch 2) or more, the total amount of ink instantly attached is large, and the ink can be coagulated before it penetrates into the fabric, thereby allowing a resin layer to be satisfactorily formed near the surface of the fabric.

[0027] The maximum range of the total amount of reaction liquid and transparent ink composition attached per unit area and unit time is , but is not limited to 250 mg / (s·inch 2 ) or less is preferable, and 225 mg / (s·inch 2 ) or less is more preferable, and 200 mg / (s·inch 2 ) or less is more preferable, and 150 mg / (s·inch 2 ) or less is even more preferable, and 100 mg / (s·inch 2 ) or less is particularly preferable, and 80 mg / (s·inch 2 ) The following are more particularly preferred: When the maximum value is within the above range, the feel of the fabric tends to be better.

[0028] The total amount of reaction liquid and transparent ink composition deposited per unit area and unit time can be adjusted as appropriate by changing the printing area in one scan, the amount of ink applied, the carriage movement speed, the head drive frequency, etc. The printing area in one scan is, for example, 3 to 30 inches. 2 is preferable, and 5 to 20 inches 2 More preferably, 7 to 15 inches 2 is more preferred. The application amount of the reaction liquid and the transparent ink composition in one scan is, for example, preferably from 100 to 1000 mg, more preferably from 200 to 800 mg, and even more preferably from 400 to 600 mg. The carriage movement speed in the serial method is, for example, preferably 6 to 40 inch / s, more preferably 6 to 30 inch / s, further preferably 6 to 20 inch / s, particularly preferably 8 to 17 inch / s, and more particularly preferably 10 to 15 inch / s.

[0029] In step 1, the ratio (A / B) of the amount of reaction liquid adhered per unit area and unit time (A) to the amount of transparent ink composition adhered per unit area and unit time (B) is preferably 0.5 to 2.0, more preferably 0.6 to 1.7, even more preferably 0.7 to 1.5, particularly preferably 0.8 to 1.3, and more particularly preferably 0.9 to 1.1. When the ratio (A / B) is within the above range, a resin layer tends to be better formed in the vicinity of the surface of the fabric, and better color development and rubbing fastness may be obtained.

[0030] 1.1.2 Fabric Examples of the form of the fabric used in the inkjet printing method according to this embodiment include fabric, clothing, and other accessories. Fabrics include woven fabrics, knitted fabrics, and nonwoven fabrics. Clothing and other accessories include furniture such as sewn T-shirts, handkerchiefs, scarves, towels, carrier bags, cloth bags, curtains, sheets, bed covers, and wallpaper, as well as fabrics before and after cutting as parts before sewing. Examples of the form of these include long ones wound in a roll, ones cut to a specified size, and ones in the shape of a product.

[0031] Examples of materials constituting the fabric include natural fibers such as cotton, hemp, 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 fibers. Among these materials, the fabric is preferably made of cotton, polyester, or a blend of cotton and polyester, as these materials are easily available.

[0032] In addition, the fabric is L * It is preferable that the value is 75 or less. *The value may be 60 or less, or may be 50 or less. In printing on such fabrics, a relatively large amount of colored ink composition (especially white ink) may be applied in order to obtain excellent color development. Therefore, it is particularly difficult to achieve both friction fastness and color development. In contrast, according to the inkjet printing method of this embodiment, even when such fabrics are used, excellent friction fastness and color development can be obtained.

[0033] In addition, L * By L * a * b * Represents the lightness in the color space. * The value can be measured using a known colorimeter, for example, Spectrolino (Gretag). It can be determined.

[0034] In addition, L * Examples of fabrics having a value of 75 or less include colored fabrics that have been pre-colored with dyes, etc. 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 dispersants (surfactants), reactive dyes, etc. Methods for coloring fabrics with dyes can be known methods depending on the material and shape of the fabric.

[0035] From the viewpoint of availability and of enjoying the effects of the present invention, the fabric is L * 75 or less, and is preferably made of cotton, polyester, or a blend of cotton and polyester.

[0036] 1.1.3 Reaction solution The reaction liquid used in the reaction liquid application step contains water and an aggregating agent that aggregates the components in the ink.

[0037] Each component contained in the reaction solution will be described below.

[0038] <Flocculant> 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 transparent ink composition and pigments and resin particles contained in the colored ink composition, thereby aggregating at least one of these components. The degree of aggregation of the dispersion by the aggregating agent varies depending on the type of aggregating agent and the target, and can be adjusted. This aggregating action can, for example, improve the color development and fixability of the image.

[0039] The reaction liquid preferably contains, as an aggregating agent, one or more selected from, for example, organic acids, polyvalent metal salts, and cationic polymers. Such aggregating agent may have better resistance to friction and color development.

[0040] 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, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, derivatives of these compounds, and salts thereof. The organic acids may be used alone or in combination of two or more. Note that metal salts of organic acids are included in the metal salts described below.

[0041] A polyvalent metal salt is a compound composed of a divalent or higher metal ion and an anion. 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 the ink components.

[0042] The anions constituting the polyvalent metal salt are inorganic ions or organic ions. Examples of such inorganic ions include chloride ions, bromide ions, iodide ions, formate ions, nitrate ions, sulfate ions, hydroxide ions, etc. Examples of organic ions include organic acid ions, such as carboxylate ions.

[0043] 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, and aluminum lactate. These polyvalent metal salts may be used alone or in combination of two or more. Among these, at least one of magnesium sulfate, calcium formate, calcium nitrate, aluminum lactate, and calcium propionate is preferred in terms of sufficient solubility in water. These metal salts may have water of hydration in the raw material form, such as magnesium sulfate heptahydrate and magnesium sulfate tetrahydrate.

[0044] The cationic polymer refers to a polymer compound having a cationic group. 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. The allylamine resin includes those having a structure derived from an allyl group in the main skeleton of the resin. The polyamine resin includes those having an amino group in the main skeleton of the resin. The quaternary ammonium salt polymer includes a resin 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.

[0045] The flocculants may be used alone or in combination of two or more.

[0046] From the viewpoint of achieving better color development and friction fastness, the lower limit of the content of the coagulant is, for example, preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, particularly preferably 3% by mass or more, and more particularly preferably 4% by mass or more, relative to the total mass of the reaction liquid. In addition, the upper limit of the content of the flocculant is not particularly limited, but for example, it is preferably 20 mass% or less, more preferably 15 mass% or less, even more preferably 10 mass% or less, particularly preferably 8 mass% or less, and more particularly preferably 7 mass% or less, relative to the total mass of the reaction liquid.

[0047] <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, and water with reduced ionic impurities such as ultrapure water. In addition, if water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, the growth of bacteria and fungi can be suppressed when the reaction solution is stored for a long period of time.

[0048] The water content is preferably 40% by mass or more, more preferably 45% by mass or more, more preferably 50% by mass or more, and particularly preferably 60% by mass or more, based on the total mass of the reaction liquid. 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, based on the total mass of the reaction liquid.

[0049] <Organic solvent> The reaction liquid may contain an organic solvent, such as esters, alkylene glycol ethers, cyclic esters, amides, alcohols, and polyhydric alcohols.

[0050] Examples of esters include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, Examples of the glycol diesters include glycol monoacetates such as propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and methoxybutyl acetate; and glycol diesters such as ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, ethylene glycol 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.

[0051] 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 propylene glycol monomethyl ether. and alkylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol methyl butyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and tripropylene glycol dimethyl ether.

[0052] Examples of the cyclic esters include cyclic esters (lactones) such as β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, β-butyrolactone, β-valerolactone, γ-valerolactone, β-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 of the methylene group adjacent to the carbonyl group is substituted with an alkyl group having 1 to 4 carbon atoms.

[0053] Examples of the amides include cyclic amides and non-cyclic amides. Examples of the non-cyclic amides include alkoxyalkyl amides.

[0054] Examples of the 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.

[0055] Examples of the alkoxyalkylamides include 3-methoxy-N,N-dimethylpropionamide, 3-methoxy-N,N-diethylpropionamide, 3-methoxy-N,N-methylethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-diethylpropionamide, 3-ethoxy-N,N-methylethylpropionamide, 3-n-butoxy-N,N-dimethylpropionamide, 3-n-butoxy-N,N-diethylpropionamide, 3-n-butoxy-N,N-methylethylpropionamide, 3-n-propoxy-N,N-dimethylpropionamide, Examples of the propionamide include 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.

[0056] Examples of alcohols include compounds in which one hydrogen atom of an alkane is replaced by a hydroxyl group. The alkane preferably has 10 or less carbon atoms, more preferably 6 or less carbon atoms, and even more preferably 3 or less 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, iso-propyl alcohol, n-butanol, 2-butanol, tert-butanol, iso-butanol, n-pentanol, 2-pentanol, 3-pentanol, and tert-pentanol, 2-phenoxyethanol, benzyl alcohol, and phenoxypropanol.

[0057] Polyhydric alcohols have two or more hydroxyl groups in the molecule. Polyhydric alcohols can be divided into, for example, alkanediols and polyols.

[0058] Examples of alkanediols include compounds in which an alkane is substituted with two hydroxyl groups. Examples of alkanediols include 1,2-alkanediol, which is a general term for compounds in which hydroxyl groups are substituted at the 1- and 2-positions of an alkane, and alkanediols other than 1,2-alkanediol.

[0059] 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, 3,4-dimethyl-1,2-pentanediol, 3-ethyl-1,2-pentanediol, 4-ethyl-1,2-pentanediol, 3-methyl-1,2-hexanediol, 4-methyl-1,2-hexanediol, 5-methyl-1,2-hexanediol, and 3,4-dimethyl-1,2-hexanediol. , 3,5-dimethyl-1,2-hexanediol, 4,5-dimethyl-1,2-hexanediol, 3-ethyl-1,2-hexanediol, 4-ethyl-1,2-hexanediol, 3-ethyl-4-methyl-1,2-hexanediol, and the like.

[0060] 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.

[0061] Examples of polyols include condensates in which two or more molecules of alkanediols are intermolecularly condensed via the hydroxyl groups, and compounds having three or more hydroxyl groups.

[0062] Examples of the condensation products 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.

[0063] The compound having three or more hydroxyl groups is a compound having three or more hydroxyl groups and having an alkane or polyether structure as a backbone. Examples of the compound having three or more hydroxyl groups include glycerin, trimethylolethane, trimethylolpropane, 1,2,5-hexanetriol, 1,2,6-hexanetriol, pentaerythritol, and polyoxypropylenetriol.

[0064] The organic solvents may be used alone or in combination of two or more kinds.

[0065] Among these, the organic solvent preferably contains alkanediols, more preferably contains 1,2-alkanediol, and particularly preferably contains propylene glycol. When the organic solvent contains these solvents, it may be excellent in color developability and rubbing fastness.

[0066] The content of the organic solvent is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, still more preferably 15 to 35% by mass, and particularly preferably 20 to 30% by mass based on the total amount of the reaction solution. When the content of the organic solvent is within the above range, it may be excellent in color developability and rubbing fastness.

[0067] <pH adjuster> The reaction solution may contain a pH adjuster for the purpose of adjusting the pH. The pH adjuster is not particularly limited, and examples include appropriate combinations of acids, bases, weak acids, and weak bases. Examples of the acids and bases used in such combinations include, as inorganic acids, sulfuric acid, hydrochloric acid, nitric acid, etc.; as inorganic bases, lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium dihydrogen phosphate, disodium hydrogen phosphate, potassium carbonate, sodium carbonate, sodium bicarbonate, ammonia, etc.; as organic bases, triethanolamine, diethanolamine, monoethanolamine, tripropanolamine, triisopropanolamine, diisopropanolamine, tris(hydroxymethyl)aminomethane (THAM), etc.; as organic acids, adipic acid, citric acid, succinic acid, lactic acid, N,N-bis(2-hi hydroxyethyl)-2-aminoethanesulfonic acid (BES), 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES), morpholinoethanesulfonic acid (MES), carbamoylmethyliminobisacetic acid (ADA), piperazine-1,4-bis(2-ethanesulfonic acid) (PIPES), N-(2-acetamido)-2-aminoethanesulfonic acid (ACES), cholamine hydrochloride, N-tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid (TES), acetamidoglycine, tricine, glycineamide, Good's buffer such as bicine, phosphate buffer, citrate buffer, Tris buffer, etc. may also be used. Among these, inorganic bases are preferred, and potassium hydroxide is more preferred.

[0068] The reaction solution may contain one or more pH adjusters. When the pH adjusters are used, the total content of the pH adjusters relative to the total mass of the reaction solution is, for example, 0.05% by mass to 3.0% by mass, and more preferably 0.1% by mass to 1.0% by mass.

[0069] <Surfactant> The reaction liquid may contain a surfactant. The surfactant can be used to reduce the surface tension of the reaction liquid and adjust and improve, for example, the permeability into the fabric. As the surfactant, any of nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used, and these may be used in combination. Among the surfactants, acetylene-based surfactants (acetylene glycol-based surfactants), silicon-based surfactants, and fluorine-based surfactants can be more preferably used, and silicon-based surfactants and acetylene-based surfactants can be more preferably used.

[0070] 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 such products include Olfin 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.).

[0071] The silicone surfactant is not particularly limited, but a polysiloxane compound is preferred. The polysiloxane compound is not particularly limited, but an example thereof is polyether-modified organosiloxane. Examples of commercially available polyether-modified organosiloxanes include BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-348 (trade names, manufactured by BYK Co.), 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.).

[0072] As the fluorine-based surfactant, it is preferable to use a fluorine-modified polymer, and a specific example thereof is BYK-340 (product name, manufactured by BYK-Chemie Japan KK).

[0073] The surfactant may be used alone or in combination of two or more kinds.

[0074] The reaction liquid preferably contains a surfactant having an HLB value of 10 or more. When the surfactant has an HLB value of 10 or more, the permeability of the reaction liquid into the fabric can be adjusted favorably, and the reaction liquid tends to be more easily retained near the fabric surface. This tends to result in better color development.

[0075] As used herein, the term "HLB value" refers to the hydrophilic and The HLB value is a numerical representation of the hydrophilic-hydrophobic balance of a compound. Here, the HLB value is a value calculated by the Griffin method and can be calculated using the following formula (1). HLB value = 20 × sum of formula weights of hydrophilic parts / molecular weight (1)

[0076] Specific examples of surfactants having an HLB value of 10 or more according to the Griffin method are given below.

[0077] Examples of acetylene-based surfactants (acetylene glycol-based surfactants) having an HLB value of 10 or more include Olfine E1010 (HLB value 12), E1020 (HLB value 15-16), EXP.4200 (HLB value 10-13), EXP.4123 (HLB value 10-13) [product name, manufactured by Nissin Chemical Industry Co., Ltd.], and the like.

[0078] Examples of silicone surfactants having an HLB value of 10 or more include BYK-348 (HLB value 11) [product name, manufactured by BYK], KF-6011 (HLB value 14.5), KF-6013 (HLB value 10), KF-6043 (HLB value 14.5), KF-643 (HLB value 14), KF-640 (HLB value 14), KF-351A (HLB value 12), KF-354L (HLB value 16) [product name, manufactured by Shin-Etsu Silicone Co., Ltd.], FZ-2105 (HLB value 11), L-7604 (HLB value 13), FZ-2104 (HLB value 14) [product name, manufactured by Dow Corning Toray Co., Ltd.], SILWET L-7604 (HLB value 13), SILWET Examples of the polyester resin include L-7607N (HLB value 17), SILWET FZ-2104 (HLB value 14), and SILWET FZ-2161 (HLB value 20) [product name, manufactured by Nippon Unicar Co., Ltd.].

[0079] The lower limit of the surfactant content is preferably 0.1 mass % or more, more preferably 0.3 mass % or more, even more preferably 0.5 mass % or more, and particularly preferably 0.7 mass % or more, based on the total mass of the reaction liquid. The upper limit of the surfactant content is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, and particularly preferably 1.5% by mass or less, based on the total mass of the reaction liquid. When the surfactant content is within the above range, it tends to be easier to adjust the permeability of the reaction liquid into the fabric.

[0080] <Other ingredients> The reaction liquid may contain additives such as preservatives, antifungals, rust inhibitors, chelating agents, viscosity adjusters, dissolution aids, antioxidants, etc., as necessary. The content of such additives, when contained, is preferably 0.1 to 5 mass%, more preferably 0.1 to 3 mass%, and even more preferably 0.1 to 1 mass%, based on the total amount of the reaction liquid.

[0081] The reaction liquid may 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, with the lower limit being 0% by mass, relative to the total mass of the reaction liquid. It is preferable that the reaction liquid does not contain a coloring material.

[0082] <Physical Properties> From the viewpoint of reducing skin irritation, the pH of the reaction solution is preferably 2.0 or more, and more preferably 3.0 or more. From the same viewpoint, the upper limit of the pH is preferably 11.5 or less, more preferably 10 or less, even more preferably 7.0 or less, and particularly preferably 5.0 or less.

[0083] The viscosity of the reaction liquid is preferably 1.0 to 10 mPa·s, more preferably 1.5 to 5.0 mPa·s, even more preferably 2.0 to 4.0 mPa·s, and particularly preferably 2.5 to 3.5 mPa·s. In particular, when the viscosity is 3.0 mPa·s or more, better color development tends to be obtained. When the viscosity is 5.0 mPa·s or less, better ejection stability tends to be obtained. The viscosity can be measured using, for example, a viscoelasticity tester MCR-300 (product name) manufactured by Pysica.

[0084] The viscosity of the mixture obtained by mixing equal amounts of the reaction liquid and the transparent ink composition described below is preferably 50 mPa·s or more, more preferably 100 mPa·s or more, even more preferably 200 mPa·s or more, particularly preferably 300 mPa·s or more, and even more particularly preferably 320 mPa·s or more. When the viscosity of the mixture is within the above range, the water absorption rate into the fabric is slowed down, and it is possible to more satisfactorily form a transparent ink layer (resin layer) near the surface of the fabric. This makes it possible to more effectively suppress the penetration of the colored ink into the fabric, and there is a tendency for better color development to be obtained. In addition, the resin layer functions better as a binding layer between the fabric and the colored ink layer, and there is a tendency for better friction fastness to be obtained. Furthermore, there is no particular upper limit to the viscosity of the mixed liquid obtained by mixing equal amounts of the reaction liquid and a transparent ink composition described below, but it is preferably 10,000 mPa·s or less, more preferably 5,000 mPa·s or less, particularly preferably 2,500 mPa·s or less, and more particularly preferably 1,000 mPa·s or less.

[0085] The surface tension of the reaction liquid is preferably 25 to 40 mN / m, more preferably 25 to 35 mN / m, further preferably 27 to 35 mN / m, and particularly preferably 30 to 33 mN / m. The surface tension can be measured by the Wilhelmy method using, for example, a surface tensiometer (DY-300, manufactured by Kyowa Interface Science Co., Ltd.). The surface tension is preferably a value measured at 20°C.

[0086] 1.2 Transparent ink application process The inkjet textile printing method according to this embodiment includes a transparent ink applying step of applying a transparent ink composition containing anionic resin particles and water to a fabric by an inkjet method. The transparent ink application step and the above-mentioned reaction liquid application step include step 1: applying the reaction liquid and the transparent ink composition to the same area of ​​the fabric in one scan of the inkjet head. In step 1, the range of the minimum value of the total amount of the reaction liquid and the transparent ink composition applied per unit area and unit time is 34 mg / (s·inch 2 The embodiment of step 1 is as described above, so a detailed description thereof will be omitted.

[0087] 1.2.1 Transparent ink composition The transparent ink composition used in the transparent ink application step contains anionic resin particles and water.

[0088] Each component contained in the transparent ink composition will be described below.

[0089] <Anionic resin particles> The transparent ink composition contains anionic resin particles. In the same manner as the function of resin particles, the anionic resin particles have a function of improving the adhesion of the ink applied to the fabric, that is, a so-called fixing function. The anionic resin particles have a function as a resin. Although the anionic resin particles are often handled in an emulsion form, they may also be in a powder form.

[0090] The term "anionic resin particles" refers to resin particles having a negative charge as a whole, and preferably has one or more anionic groups selected from a carboxyl group, a sulfonic acid group, a phosphoric acid group, and the like.

[0091] Examples of the 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 them, urethane resin, acrylic resin, olefin resin, and ester resin are preferred. The resin particles may be used alone or in combination of two or more kinds.

[0092] Urethane resin is a general term for resins having urethane bonds. In addition to urethane bonds, polyether-type urethane resins containing ether bonds in the main chain, ester-type urethane resins containing ester bonds in the main chain, carbonate-type urethane resins containing carbonate bonds in the main chain, etc. may be used as urethane resins. In addition, commercially available products may be used as urethane resins, such as Superflex 460, 460s, 840, E-4000 (trade names, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Rezamin D-1060, D-2020, D-4080, D-4200, D-6300, D-6455 (trade names, manufactured by Dainichi Seiyaku Chemicals Co., Ltd.), Takelac WS-5100, WS-6021, W-512-A-6 (trade names, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.), Sancure 2710 (trade name, manufactured by LUBRIZOL), and Parmarin UA-150 (trade name, manufactured by Sanyo Chemical Industries, Ltd.).

[0093] Acrylic resin is a general term for polymers obtained by polymerizing at least acrylic monomers such as (meth)acrylic acid and (meth)acrylic acid esters as one component, and examples thereof include resins obtained from acrylic monomers and copolymers of acrylic monomers and other monomers. Examples thereof include acrylic-vinyl resins, which are copolymers of acrylic monomers and vinyl monomers. Examples of vinyl monomers include styrene. As the acrylic monomer, acrylamide, acrylonitrile, etc. can also be used. For the resin emulsion using acrylic resin as a raw material, a commercially available product may be used, and may be selected from, for example, FK-854 (trade name, manufactured by Chuo Rika Kogyo Co., Ltd.), Mowinyl 952B, 718A (trade names, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), Nipol LX852, LX874 (trade names, manufactured by Nippon Zeon Co., Ltd.), etc.

[0094] 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 Vinybran 2586 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0095] The olefin resin is a polymer having an olefin such as ethylene, propylene, or butylene in the structural skeleton, and any known olefin resin can be appropriately selected and used. For example, Arrowbase CB-1200, CD-1200 (product name, manufactured by Unitika Ltd.) and the like may be used.

[0096] The anionic resin particles are more preferably a urethane resin or an acrylic resin, and even more preferably a urethane resin, which tends to provide better resistance to rubbing.

[0097] The glass transition temperature (Tg) of the resin particles is preferably -60°C or more and 50°C or less, more preferably -60°C or more and 40°C or less, and even more preferably -30°C or more and 10°C or less. When the glass transition temperature (Tg) of the resin particles is within the above range, the fabric conformability (texture) tends to be more excellent. 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 of measuring transition temperature of plastics).

[0098] The content (solid content) 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 abrasion fastness tend to be obtained.

[0099] <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.

[0100] 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 mass of the transparent ink composition. The upper limit of the water content is not particularly limited, but is, for example, preferably 90% by mass or less, further 70% by mass or less, and more preferably 60% by mass or less, relative to the total mass of the transparent ink composition.

[0101] <Organic solvent> 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.

[0102] In the transparent ink composition, the organic solvent preferably contains an alkanediol, an alkylene glycol ether, and a trialkylene glycol, more preferably contains a 1,2-alkanediol, an alkylene glycol ether, and a trialkylene glycol, and further preferably contains propylene glycol, triethylene glycol monobutyl ether, and triethylene glycol. When the organic solvent contains these solvents, the color development and the friction fastness may be more excellent.

[0103] The content of the organic solvent is preferably 10 to 55 mass %, more preferably 15 to 45 mass %, further preferably 20 to 40 mass %, and particularly preferably 25 to 35 mass %, based on the total amount of the transparent ink composition. When the content of the organic solvent is within the above range, the color development and friction fastness may be more excellent.

[0104] <Surfactant> The transparent ink composition may contain a surfactant. The type of the surfactant may be the same as that of the reaction liquid described above.

[0105] 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 mass of the transparent ink composition. The upper limit of the surfactant content is preferably 3% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.8% by mass or less, relative to the total mass of the transparent ink composition. If the surfactant content is within the above range, it tends to be easier to adjust the permeability of the transparent ink composition into fabrics.

[0106] <Other ingredients> The transparent ink composition may contain additives, as necessary, such as a pH adjuster, a preservative / fungal inhibitor, an antirust agent, a chelating agent, a viscosity adjuster, a dissolution aid, an antioxidant, etc. The content of such additives, when contained, is preferably 0.1 to 5 mass % relative to the total amount of the transparent ink composition, more preferably 0.1 to 3 mass %, and even more preferably 0.1 to 1 mass %.

[0107] The transparent ink composition may 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, with the lower limit being 0% by mass, relative to the total mass of the transparent ink composition. It is preferable that the transparent ink composition does not contain a coloring material.

[0108] <Physical Properties> From the viewpoint of reducing skin irritation, the pH of the transparent ink composition is preferably 2.0 or more, more preferably 5.0 or more, and even more preferably 7.0 or more. From the same viewpoint, the upper limit of the pH is preferably 11.5 or less, more preferably 10 or less, even more preferably 9.0 or less, and particularly preferably 8.0 or less.

[0109] The viscosity of the transparent ink composition is preferably 1.0 to 10 mPa·s, more preferably 1.5 to 5.0 mPa·s, even more preferably 2.0 to 4.0 mPa·s, and particularly preferably 3.0 to 4.0 mPa·s. In particular, when the viscosity is 3.0 mPa·s or more, better color development tends to be obtained. When the viscosity is 5.0 mPa·s or less, better ejection stability tends to be obtained.

[0110] The surface tension of the transparent ink composition is preferably from 10 to 40 mN / m, more preferably from 15 to 35 mN / m, even more preferably from 20 to 30 mN / m, and particularly preferably from 20 to 27 mN / m.

[0111] 1.4 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 pigment, resin particles, and water onto the region to which the clear ink composition has been applied. The transparent ink composition applied in the above-mentioned manner forms a resin layer well formed near the surface of the fabric, which can suppress the penetration of the colored ink into the fabric and provide good color development. In addition, the resin layer functions as a binding layer between the fabric and the colored ink layer, providing good friction fastness.

[0112] 1.4.1 Simultaneous reaction solution attachment process From the viewpoint of obtaining superior color development, resistance to rubbing, texture, and the like, it is preferable that the reaction liquid applying step is carried out simultaneously with the colored ink applying step.

[0113] Here, the reaction liquid application step and the color ink application step are performed “simultaneously” with respect to the time from when the reaction liquid is last landed on the same area of ​​the fabric to when the color ink composition is first landed on the same area of ​​the fabric. It is meant that the difference is within 10 seconds, more preferably within 5 seconds, even more preferably within 3 seconds, and particularly preferably within 1 second.

[0114] More specifically, the reaction liquid applying step and the colored ink applying step being "simultaneous" may mean that the reaction liquid applying step and the colored ink applying step include the following step 3. Step 3: Applying the reaction liquid and the colored ink composition to the same area of ​​the fabric in one pass of the inkjet head.

[0115] The term "scanning" in step 3 refers to moving the inkjet head relatively to the recording area on the fabric, and is the same as the aspect of "scanning" in step 1 described above.

[0116] In the case of a serial recording method, step 3 is performed multiple times, and the reaction liquid applying step and the colored ink applying step include step 4: transporting the fabric in a direction intersecting the scanning direction, and step 4 may be performed between multiple instances of step 3. This allows the reaction liquid and the colored ink composition to be applied to the same region of the fabric in multiple batches.

[0117] The number of times step 3 is 2 or more, may be 3 or more, or may be 4 or more. The upper limit of step 3 is not particularly limited, but may be less than 20, may be less than 15, or may be less than 10. In addition, when step 3 is performed n (n is an integer of 2 or more) times, step 4 is preferably performed n-1 times. Steps 3 and 4 are preferably performed alternately and repeatedly.

[0118] The colored ink application step may be performed in the same scan as the clear ink application step described above, but is preferably performed in a different scan.

[0119] When the colored ink application step and the transparent ink application step are performed in the same scan, the "scan" in step 1 and the "scan" in step 3 described above are the same scan, and therefore the reaction liquid application steps accompanying step 1 and step 3 are the same step. In other words, the reaction liquid, the transparent ink composition, and the colored ink composition are applied to the same area of ​​the fabric in one scan of the inkjet head. This makes it possible to increase the recording speed. Note that, when the fabric is transported between scans, the above-mentioned steps 2 and 4 are the same step.

[0120] On the other hand, when the colored ink application step and the transparent ink application step are performed in different scans, the "scan" in step 1 and the "scan" in step 3 described above are different scans, and therefore the reaction liquid application steps accompanying step 1 and step 3 are different steps. In this case, since the colored ink layer can be formed on a better formed transparent ink layer (resin layer), it is possible to further suppress the penetration of the colored ink into the fabric, and there is a tendency for better color development to be obtained.

[0121] In step 3, the minimum range of the total amount of the reaction liquid and the colored ink composition attached per unit area and unit time is 50 mg / (s·inch 2 ) or more is preferable, and 60 mg / (s·inch 2 ) or more is preferable, and 70 mg / (s·inch 2 ) or more is more preferable, and 80 mg / (s·inch 2 ) or more is particularly preferable, and 90 mg / (s·inch 2 ) or more are more particularly preferred. According to the inkjet printing method of this embodiment, even when the total amount of deposited reaction liquid or ink is large as described above, penetration of the colored ink into the fabric can be suppressed, and good color development tends to be obtained.

[0122] The maximum range of the total amount of the reaction liquid and the colored ink composition attached per unit area and unit time is not particularly limited, but is preferably 500 mg / (s·inch 2 ) or less is preferable, and 400 mg / (s·inch 2 ) or less is more preferable, and 300 mg / (s·inch 2 ) or less is more preferable, and 200 mg / (s·inch 2 ) or less is even more preferable, and 150 mg / (s·inch 2 ) The following are particularly preferred: When the maximum value is within the above range, color development and rubbing fastness tend to be better.

[0123] The total amount of reaction liquid and colored ink composition deposited per unit area and unit time can be appropriately adjusted by changing the printing area in one scan, the amount of ink applied, the carriage movement speed, the head drive frequency, etc. The printing area in one scan is, for example, 3 to 30 inches. 2 is preferable, and 5 to 20 inches 2 More preferably, 7 to 15 inches 2 is more preferred. The application amount of the reaction liquid and the colored ink composition in one scan is, for example, preferably from 200 to 2000 mg, more preferably from 400 to 1500 mg, and even more preferably from 800 to 1000 mg. The carriage movement speed in the serial method is, for example, preferably 6 to 40 inch / s, more preferably 6 to 30 inch / s, further preferably 6 to 20 inch / s, particularly preferably 8 to 17 inch / s, and more particularly preferably 10 to 15 inch / s.

[0124] In step 3, the ratio (A / C) of the amount of reaction liquid adhered per unit area and unit time (A) to the amount of colored ink composition adhered per unit area and unit time (C) is preferably 0.1 to 1.5, more preferably 0.2 to 1.0, even more preferably 0.3 to 0.7, and particularly preferably 0.4 to 0.6. When the ratio (A / C) is within the above range, a resin layer tends to be better formed in the vicinity of the surface of the fabric, penetration of the colored ink into the fabric can be further suppressed, and better color development tends to be obtained.

[0125] 1.4.2 Colored ink composition The color ink composition used in the color ink application step contains a pigment, resin particles, and water.

[0126] Each component contained in the colored ink composition will be described below.

[0127] <Pigments> The colored ink composition contains a pigment. For example, an inorganic pigment or an organic pigment can be used as the pigment. The pigment is a type of color material. For example, the color material can be a pigment or a dye.

[0128] Examples of inorganic pigments include, but are not limited to, carbon blacks such as furnace black, lamp black, acetylene black, and channel black; and white pigments such as iron oxide, titanium oxide, zinc oxide, and silica.

[0129] Examples of carbon blacks include CI (Colour Index Generic Name) Pigment Black 1, 7 and 11. Commercially available carbon blacks may be used, such as No. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100 and No. 2200B from Mitsubishi Chemical Corporation, Raven (registered trademark) 5750, 5250, 5000, 3500, 1255 and 700 from Columbia Carbon Corporation, Rega1 (registered trademark) 400R, 330R, 660R, Mogul (registered trademark) L, Monarch (registered trademark) 700, 800, 880, 900, 1000, 1100, 1300 and 1400 from CABOT, and Color Black from Degussa. FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Printex(R) 35, U, V, 140U , SpecialBlack 6,5,4A,4 etc.

[0130] 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, it is preferable to use CI Pigment White 6, which has excellent color development and hiding properties.

[0131] The average particle size of the white pigment is preferably 100 nm or more and 500 nm or less, more preferably 50 nm or more and 450 nm or less, and even more preferably 200 nm or more and 400 nm or less. By setting the average particle size of the white pigment within this range, ejection stability from the inkjet head tends to be ensured. In addition, the hiding power tends to be improved. In this specification, the "average particle size" refers to the volume-based particle size distribution, which is the particle size at a cumulative distribution of 50 vol%, unless otherwise specified. The average particle size is measured by the dynamic light scattering method or the laser diffraction method described in JIS Z8825. Specifically, a particle size distribution meter using the dynamic light scattering method as the measurement principle (for example, "Microtrack UPA" manufactured by Nikkiso Co., Ltd.) can be used.

[0132] 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.

[0133] Specific examples of organic pigments include the following:

[0134] Examples of cyan pigments include CI Pigment Blue 1, 2, 3, 15:3, 15:4, 15:34, 16, 22, 60, etc.; CI Bat 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.

[0135] 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.

[0136] 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. Of these, preferred examples include one or a mixture of two or more selected from the group consisting of CI Pigment Yellow 74, 109, 110, 128, 138, 150, and 180. Cut.

[0137] Pigments of other colors may also be used, for example orange pigments, green pigments, etc.

[0138] The pigments may be used alone or in combination of two or more kinds.

[0139] The pigment contained in the colored ink composition is preferably a white pigment. A colored ink composition (white ink) containing a white pigment is suitable for forming a white ink layer as a base layer, but since a relatively large amount of the white ink needs to be adhered, the total amount of the reaction liquid and ink to be adhered tends to be large, making it particularly difficult to achieve both friction fastness and color development. In contrast, according to the inkjet printing method of this embodiment, even a colored ink composition containing a white pigment can obtain excellent friction fastness and color development.

[0140] The content of the pigment (particularly, the white pigment) 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 pigment is within the above range, it tends to be possible to improve the friction fastness and obtain better color development (whiteness).

[0141] The pigment may be used after being dispersed using a pigment dispersant, or may be used after being made into a self-dispersing pigment by oxidizing or sulfonating the pigment surface with ozone, hypochlorous acid, fuming sulfuric acid, or the like.

[0142] The pigment dispersant has the function of dispersing the pigment in the ink. The pigment dispersant may be water-soluble, but is preferably not completely water-soluble, and is considered to disperse the pigment by bonding or adsorbing in part or in whole to the pigment and increasing the hydrophilicity of the pigment surface.

[0143] 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.

[0144] Examples of the pigment dispersant include maleic acid-based resins and salts thereof, such as styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinyl naphthalene-maleic acid copolymer, and vinyl acetate-maleic acid ester copolymer; 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.

[0145] In addition to the above-mentioned polymers of acrylic monomers, the acrylic resin may be a copolymer of an acrylic monomer and another monomer. For example, an acrylic vinyl resin, which is a copolymer of a vinyl monomer as another monomer, is also called an acrylic resin. For example, among the above-mentioned styrene resins, a copolymer of a styrene monomer and an acrylic monomer is also included in the acrylic resin. Furthermore, when the acrylic resin is called an acrylic resin, its salts and esters are also included.

[0146] Examples of commercially available pigment dispersants include 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 Daiichi Kogyo Seiyaku Co., Ltd.).

[0147] 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.).

[0148] Commercially available urethane pigment dispersants include BYK-182, BYK-183, BYK-184, BYK-185 (manufactured by BYK-Chemie Co., Ltd.), TEGO Disperse710 (manufactured by Evonic Tego Chemi), and Borchi (registered trademark) Gen1350 (manufactured by OMG Borschers).

[0149] 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 phosphoric acid group, and the like.

[0150] It is preferable that at least one of the pigment and the resin particles described below in the colored ink composition is anionic. In this case, the aggregating action of the aggregating agent is superior, and therefore better color development and better friction fastness tend to be obtained. The pigment being anionic means that the pigment as a whole has a negative charge, and preferably has one or more anionic groups selected from a carboxyl group, a sulfonic acid group, a phosphate group, etc. The anionic group may be directly present on the pigment surface, or may be present via an anionic resin dispersant adsorbed or bonded to the pigment.

[0151] The pigment dispersant may be used alone or in combination of two or more. The total content of the pigment dispersant is preferably 0.1% by mass or more and 30% by mass or less, 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. By having the pigment dispersant content of 0.1% by mass or more, it is likely that the dispersion stability of the pigment can be ensured. In addition, if the pigment dispersant content is 30% by mass or less, it is likely that the viscosity of the colored ink composition can be kept low.

[0152] The weight average molecular weight of the pigment dispersant is more preferably equal to or greater than 500. By using such a pigment dispersant, there is a tendency for the pigment to have less odor and to have better dispersion stability.

[0153] When the pigment (particularly, a white pigment) is dispersed by a pigment dispersant, the ratio of the pigment to the pigment dispersant is preferably 10:1 to 1:10, and more preferably 4:1 to 1:3.

[0154] <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.

[0155] The resin particles in the colored ink composition are preferably anionic, since the aggregating action of the aggregating agent is superior, and therefore better color development and better abrasion resistance tend to be obtained.

[0156] 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 resistance to rubbing.

[0157] The glass transition temperature (Tg) of the resin particles in the colored ink composition is preferably −60° C. or more and 50° C. or less, more preferably −60° C. or more and 40° C. or less, and even more preferably −30° C. or more and 10° C. or less. When the glass transition temperature (Tg) of the resin particles is within the above range, the fabric conformability (handle) tends to be better.

[0158] 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 abrasion fastness tend to be obtained.

[0159] <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.

[0160] 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, based on the total mass of the colored ink composition. The upper limit of the water content is not particularly limited, but is, for example, preferably 90% by mass or less, and even more preferably 70% by mass or less, based on the total mass of the colored ink composition.

[0161] <Organic solvent> The color 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.

[0162] In the color ink composition, the organic solvent preferably contains alkanediols, alkylene glycol ethers, and trialkylene glycol, more preferably contains 1,2-alkanediols, alkylene glycol ethers, and trialkylene glycol, and even more preferably contains propylene glycol, triethylene glycol monobutyl ether, and triethylene glycol. When the organic solvent contains these solvents, the color development and friction fastness may be more excellent.

[0163] The colored ink composition further contains preferably 3.0% by mass or more, more preferably 4.0% by mass or more, and even more preferably 5.0% by mass or more of an organic solvent having a normal boiling point of 250° C. or more. 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 more is contained within the above range, the nozzle of the inkjet head is kept moist, and ejection reliability (continuous printing stability) tends to be improved. Such an embodiment is particularly useful in the case where the reaction liquid and the colored ink composition are applied to the same region of the fabric in the same scan, where aggregates are likely to form in the nozzle.

[0164] Examples of organic solvents having a normal boiling point of 250° C. or more include glycerin and polyethylene glycol monomethyl ether. Organic solvents having a normal boiling point of 250° C. or more are also called moisturizers. Organic solvents having a normal boiling point of 250° C. or more are preferably those having a normal boiling point of 270° C. or more. C. or higher, and more preferably the normal boiling point is 280.degree. C. or higher.

[0165] 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 %, based on the total amount of the color ink composition. When the content of the organic solvent is within the above range, the color development and friction fastness may be more excellent.

[0166] <Surfactant> The color ink composition may contain a surfactant. The type of the surfactant may be the same as that of the reaction liquid described above.

[0167] 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 mass of the colored ink composition. The upper limit of the surfactant content is preferably 3% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.8% by mass or less, relative to the total mass of the colored ink composition. If the surfactant content is within the above range, it tends to be easier to adjust the permeability of the colored ink composition into fabrics.

[0168] <Other ingredients> The color ink composition may contain additives, such as a pH adjuster, a preservative / fungal inhibitor, an antirust agent, a chelating agent, a viscosity adjuster, a dissolution aid, an antioxidant, etc. When such additives are contained, the content 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.

[0169] <Physical Properties> From the viewpoint of reducing skin irritation, the pH of the colored ink composition is preferably 2.0 or more, more preferably 5.0 or more, and even more preferably 7.0 or more. From the same viewpoint, the upper limit of the pH is preferably 11.5 or less, more preferably 10 or less, even more preferably 9.0 or less, and particularly preferably 8.0 or less.

[0170] The viscosity of the colored ink composition 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, when the viscosity is 4.0 mPa·s or more, better color development tends to be obtained. When the viscosity is 6.0 mPa·s or less, better ejection stability tends to be obtained.

[0171] The surface tension of the transparent ink composition is preferably from 10 to 40 mN / m, more preferably from 15 to 35 mN / m, even more preferably from 20 to 30 mN / m, and particularly preferably from 20 to 27 mN / m.

[0172] 1.5 Second transparent ink application process The inkjet textile printing method according to this embodiment may further include a second transparent ink applying step of applying, by an inkjet method, a second transparent ink composition containing anionic resin particles and water onto the region of the fabric to which the colored ink composition is applied. This allows the colored ink layer to be overcoated with the second transparent ink, further improving the resistance to rubbing, and in particular, effectively suppressing discoloration due to dry rubbing.

[0173] The deposition of the second transparent ink composition in the second transparent ink deposition step can be performed by moving an inkjet head relatively to the recording area on the fabric.

[0174] The second transparent ink application step may include applying the reaction liquid and the second transparent ink composition to the same region of the fabric in a single scan of the inkjet head, similar to the transparent ink application step described above. In this case, the aspect may be the same as in step 1 described above, and the amount of application, etc. may also be the same.

[0175] The minimum range of the amount of the second transparent ink applied per unit area and unit time during one scan of the inkjet head is 15 mg / (s·inch 2 ) or more is preferable, and 20 mg / (s·inch 2 ) or more is preferable, and 25 mg / (s·inch 2 ) or more is more preferable, and 30 mg / (s·inch 2 ) or more is particularly preferred. The maximum amount of the second transparent ink applied per unit area and unit time during one scan of the inkjet head is not particularly limited, but is preferably 150 mg / (s·inch 2 ) or less is preferable, and 100 mg / (s·inch 2 ) or less is more preferable, and 75 mg / (s·inch 2 ) or less is more preferable, and 50 mg / (s·inch 2 ) The following are particularly preferred:

[0176] The total amount of the second ink composition deposited per unit area and unit time can be appropriately adjusted by changing the printing area in one scan, the amount of ink applied, the carriage movement speed, the head drive frequency, and the like. The printing area in one scan is, for example, 3 to 30 inches. 2 is preferable, and 5 to 20 inches 2 More preferably, 7 to 15 inches 2 is more preferred. The amount of the second ink composition applied in one scan is, for example, preferably from 50 to 500 mg, more preferably from 100 to 400 mg, and even more preferably from 200 to 350 mg. The carriage movement speed in the serial method is, for example, preferably 6 to 40 inch / s, more preferably 6 to 30 inch / s, further preferably 6 to 20 inch / s, particularly preferably 8 to 17 inch / s, and more particularly preferably 10 to 15 inch / s.

[0177] The second transparent ink composition is the same as the transparent ink composition described above, and therefore a description thereof will be omitted. The second transparent ink composition may be the same composition as the transparent ink composition described above. By using the same composition, it is not necessary to provide a separate nozzle row, which is preferable in that the recording device can be made smaller.

[0178] 1.6 Heat drying process The inkjet printing method according to this embodiment may include a step of heating and drying the ink and the like applied to the fabric (heat drying step) after the above-mentioned step of applying the reaction liquid and the ink.

[0179] The heat drying method is not particularly limited, but examples thereof include a belt conveyor oven, a normal pressure steam method, a high pressure steam method, a Thermofix method, etc. The heat source for heat drying is not particularly limited, but for example, an infrared lamp or the like can be used.

[0180] The heat drying temperature is preferably a temperature at which the resin particles that may be contained in the ink are fused and the medium such as water volatilizes. The heat drying temperature is, for example, preferably 100°C or more and 250°C or less, more preferably 120°C or more and 230°C or less, even more preferably 140°C or more and 200°C or less, and particularly preferably 150°C or more and 180°C or less. Here, the heat drying temperature in the heat drying process refers to the surface temperature of the image formed on the fabric. The time for carrying out the heat drying is not particularly limited, but is, for example, preferably 30 seconds or more and 20 minutes or less, more preferably 2 minutes or more and 5 minutes or less.

[0181] 1.7 Other processes The inkjet printing method according to the present embodiment includes a process of washing the printed fabric with water, The washing process may include a step of drying by heating, etc. In the washing process, if necessary, a soaping treatment may be performed to wash away components of the ink and the like that have not been fixed to the fabric using a hot soapy solution or the like.

[0182] 1.8 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.

[0183] As an example of an inkjet recording device, a perspective view of a serial printer is shown in Fig. 1. As shown in Fig. 1, the serial printer 20 includes a conveying section 220 and a recording section 230. The conveying section 220 conveys the recording medium F fed to the serial printer to the recording section 230, and ejects the recording medium after recording outside the serial printer. Specifically, the conveying section 220 has feed rollers and conveys the fed recording medium F in a conveying direction TD.

[0184] 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.

[0185] Fig. 2 shows an example of each nozzle row of 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, arranged along the scanning direction SD, each row being made up of a plurality of nozzles arranged along a direction (transport direction TD) intersecting the direction in which the inkjet head 231 is moved (scanning direction SD). At this time, by arranging the nozzle row ejecting the reaction liquid so that it at least partially overlaps with the nozzle row ejecting the clear ink composition in the transport direction TD when projected along the scanning direction SD, the above-mentioned step 1 (application of the reaction liquid and the clear ink composition to the same region on the fabric in one scan of the inkjet head) can be performed. Similarly, by arranging the nozzle row ejecting the reaction liquid so that it at least partially overlaps with the nozzle row ejecting the colored ink composition in the transport direction TD when projected along the scanning direction SD, the above-mentioned step 3 (application of the reaction liquid and the colored ink composition to the same region on the fabric in one scan of the inkjet head) can be performed. The ink etc. to be ejected from each nozzle row is selected as appropriate; for example, 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.

[0186] 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 intersecting with the transport direction TD of the recording medium F. Also, 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 to eject the ink composition and reaction liquid onto the recording medium. The recording medium may be transported between scans.

[0187] In addition, the inkjet device is not limited to the serial printer, but may be a line printer. Fig. 3 shows a schematic side view of a line printer as another example of an inkjet recording device. As shown in Fig. 3, 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, a control unit 500, and a discharge unit 700.

[0188] The conveying mechanism is a mechanism for conveying a recording medium in a conveying direction. In FIG. 3, a roll-shaped recording medium F is supplied from a feeding section 100 to a conveying mechanism 200. 00 to the 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 transported recording medium F to the line head 300 downstream in the transport direction. As a transport method for the transport mechanism 200, a conventionally known method can be appropriately used, and one or more rollers, or a belt transported by rollers, etc. may be used.

[0189] The line printer 1 has a line head 300 having a length equivalent to the width of the recording medium F. The line head 300 may be made up of a plurality of line jets, and in Fig. 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 also simply referred to as line heads 300.

[0190] The line head 300 has cavities for accommodating the reaction liquid, the clear ink composition, and the colored ink composition (ink, etc.), an ejection drive unit provided for each cavity, and a nozzle for ejecting the ink, etc. A plurality of cavities, ejection drive units provided for each cavity, and nozzles provided for each cavity may be provided in one head independently of each other. The ejection drive unit can be formed using an electromechanical conversion element such as a piezoelectric element that changes the volume of the cavity by mechanical deformation, or an electrothermal conversion element that generates heat to generate bubbles in the ink and eject it.

[0191] 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 above-mentioned step 1 can be carried out suitably. It is also preferable that the reaction liquid is ejected from the third line head 330 and the colored ink composition is ejected from the fourth line head 340. In this way, it is easy to carry out the reaction liquid application step and the colored ink application step simultaneously.

[0192] In a line printer, the head is fixed (almost) without moving, and printing is performed with one scan of the inkjet head. Line printers have the advantage over serial printers in that they have a faster printing speed.

[0193] 2. Set A set according to one embodiment of the present invention is a set for use in the inkjet printing method described above, and includes the reaction liquid described above, the clear ink composition described above, and the colored ink composition described above.

[0194] The set according to this embodiment can provide good color development and abrasion resistance. The reaction liquid, the clear ink composition, and the colored ink compositions contained in the set are as described above, and therefore will not be described here.

[0195] 3. Working Example The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following, "%" is based on mass unless otherwise specified.

[0196] 3.1 Preparation of reaction liquid, transparent ink composition, and colored ink composition Each component was placed in a container to obtain the composition shown in Table 1, mixed and stirred, and then filtered through a 5 μm membrane filter to obtain a reaction liquid, a transparent ink composition, and a colored ink composition for each example. The numerical values ​​for each component shown in each example in the table represent mass % unless otherwise specified. The mass % of the pigment and resin particles in Table 1 represents the solid content concentration, and the mass % of ion-exchanged water represents the solid content concentration. The components were added so that the total mass of the composition was 100% by mass.

[0197] The pigment used was a pigment dispersion liquid prepared in advance by the following procedure. CI Pigment White 6 (specific gravity: 4.2 g / mL) was used as the pigment, and an anionic resin dispersant was used as the pigment dispersant. Specifically, a styrene-acrylic resin synthesized using 55% by mass of styrene, 20% by mass of acrylic acid, and 30% by mass of methyl methacrylate was used. 3 parts by mass of pigment was mixed with 1 part by mass of dispersant and 10 parts by mass of ion-exchanged water, and the resulting mixture was premixed, and then dispersed with zirconia beads having a diameter of 0.03 mm at a peripheral speed of 10 m / s and a liquid temperature of 30° C. for 15 minutes using a bead mill disperser (manufactured by Kotobuki Kogyo Co., Ltd., UAM-015), and coarse particles were centrifuged with a centrifuge (manufactured by Kuboyama Shoji Co., Ltd., Model-3600) to obtain a dispersion of titanium oxide.

[0198] The following provides additional explanations for the items listed in Table 1. Takelac WS-6021 (product name, manufactured by Mitsui Chemicals Polyurethanes, Inc.) BYK-348 (product name, manufactured by BYK) Olfin E1010 (product name, manufactured by Nissin Chemical Industry Co., Ltd.)

[0199] The viscosity was measured in an environment of 20° C. using a viscoelasticity tester MCR-300 (trade name, manufactured by Pysica). The surface tension was measured by checking the surface tension when a platinum plate was wetted with the reaction liquid or ink in an environment of 25°C using an automatic surface tensiometer CBVP-Z (product name, manufactured by Kyowa Interface Science Co., Ltd.).

[0200] 3.2 Recording conditions Using the reaction liquid, transparent ink composition, and colored ink composition prepared as above, inkjet printing methods according to each Example and Comparative Example were performed under the following conditions and the conditions shown in Tables 2 to 4. Table 2 shows the resin layer formation step (step a), Table 3 shows the white ink layer formation step (step b), and Table 4 shows the overcoat treatment step (step c) and drying step (step d), and recording was performed successively in the order of steps a, b, c, and d according to the recording conditions.

[0201] Printing machine: Modified SC-F2200 (Seiko Epson) Drying: The fabric was dried in a belt conveyor oven (M&R, Fusion R 36-6-4) at 160°C for 3 minutes. Fabric: 100% cotton, black T-shirt (Printstar), colored part L * Value 12

[0202] [Coating conditions] Image resolution: 1200 x 600 dpi - Hitting Duty for each row: 100% - CR (carriage) movement speed: 6-40inch / s Head drive frequency: 3-60kHz Coating amount adjustment: Adjust by CR movement speed and drive frequency

[0203] The head nozzle configuration was as shown in FIG. 2, with rows A and B being nozzle rows for ejecting the reaction liquid, rows C and D being nozzle rows for ejecting the transparent ink composition, and rows E and H being nozzle rows for ejecting the colored ink compositions.

[0204] In Table 2, "simultaneous" in "printing time difference between reaction liquid and transparent ink" indicates that the reaction liquid and the transparent ink composition were applied to the same area on the fabric in one scan of the inkjet head. In Table 3, "Simultaneous" means that the reaction liquid deposition process and the colored ink deposition process are simultaneous. More specifically, it indicates that the reaction liquid and the colored ink composition are applied to the same area of ​​the fabric in a single scan of the inkjet head.

[0205] The "viscosity of equal amounts of reaction liquid and transparent ink mixture" in Table 5 is the viscosity of the mixture when equal amounts of reaction liquid and transparent ink composition are dropped onto the non-rotating plate so as to be symmetrical with respect to the center of the non-rotating plate in a measurement section of a rheometer (Anton Paar, MCR302e) consisting of a non-rotating disk plate and a rotating disk plate, and the viscosity is measured at a shear rate of 50 [s -1 ] is the viscosity obtained by measuring the liquid viscosity 10 seconds after the plate started rotating.

[0206] 3.3 Evaluation method 3.3.1 Whiteness measurement (color development) For the printed matter obtained by the inkjet printing method according to each of the Examples and Comparative Examples, the L * The value (whiteness) of each image was measured, and the image quality (whiteness) was judged according to the following criteria. (Judgment criteria) Good: L * 85[-] or more Defective: L * Less than 85[-]

[0207] 3.3.2 Texture The printed material obtained by the inkjet printing method according to each of the Examples and Comparative Examples was cut to a size of 20 x 20 cm, and a tension-curvature curve was measured under the conditions of a shear tension of 10 gf / cm and a shear shear angle of ±8° using a tensile shear tester KE-S-FB1-A (product name of Kato Tech Co., Ltd.). The shear hardness [gf / (cm·deg)] was determined by linear regression between curvatures of 0.5° to 2.5° in the measured tension-curvature curve. Furthermore, the shear hardness was determined in the same manner as for the printed material described above for a cotton fabric (Printstar 00085-CVT, the same fabric used in each Example) to which the reaction liquid composition and the ink composition were not applied. The absolute value of the difference between the shear hardness of the printed material and the shear hardness of the cotton fabric was calculated, and the texture was evaluated according to the following evaluation criteria. (Judgment criteria) A: The absolute value of the difference in shear hardness is 3.5 or less. B: The absolute value of the difference in shear hardness is greater than 3.5 and less than -5.0. C: Over 5.0

[0208] 3.3.3 Rub fastness test The prints obtained by the inkjet printing method according to each of the Examples and Comparative Examples were evaluated for rubbing fastness according to the following dry rubbing standard or wet rubbing standard in accordance with the dry test or wet test stipulated in the "Test method for color fastness to rubbing" in JIS L 0849. The test was performed by the crockmeter method. The evaluation was performed by visually determining the staining grade according to JIS L 0801, Clause 10 (Determination of color fastness) cited in JIS L 0849. (Dry friction standard) AA: Abrasion fastness is between grade 3-4 (intermediate grade) and grade 4. A: The friction fastness is between grade 2-3 (intermediate grade) and grade 3. B: The friction fastness is between grade 1-2 (intermediate grade) and grade 2. C: Abrasion fastness is grade 1 or lower. (Wet friction standard) AA: Abrasion fastness is between grade 3-4 (intermediate grade) and grade 4. A: The friction fastness is between grade 2-3 (intermediate grade) and grade 3. B: The friction fastness is between grade 1-2 (intermediate grade) and grade 2. C: Abrasion fastness is grade 1 or lower.

[0209] 3.3.4 White ink continuous printing stability The colored ink composition (white ink) used in each example and each comparative example was filled into an ink cartridge of SC-F2200 (manufactured by Seiko Epson Corporation). Next, after confirming that ink was ejected from all nozzles, printing was performed continuously for 1 minute. The application conditions were the same as those described above. Until the ink application was completed, the evaluation was performed under an environment of a temperature of 25.0°C and a relative humidity of 40.0%. After printing, the number of nozzles where abnormal ejection occurred was confirmed. This test was performed three times, and the continuous printing stability was evaluated according to the following criteria using the average value of the three times. (Judgment criteria) AA: After continuous ejection, no print voids or irregularities were observed. A: After continuous ejection, there are print defects and irregularities in one or more but not more than two nozzles.

[0210] 3.4 Evaluation results The evaluation results are shown in Table 5. The method comprises 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 transparent 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 pigment, resin particles, and water to the area to which the transparent ink composition has been applied by an inkjet method, the reaction liquid applying step and the transparent ink applying step comprising the following steps 1: applying the reaction liquid and the transparent ink composition to the same area on the fabric in one scan of an inkjet head, and in step 1, the range of the minimum value of the total amount of application of the reaction liquid and the transparent ink composition per unit area·unit time is 34 mg / (s·inch 2 As described above, each of the examples relating to the ink-jet printing method was excellent in color development and rub fastness.

[0211] In contrast, the ink-jet printing methods according to the comparative examples not satisfying the above-mentioned features were inferior in at least one of color development and rub fastness.

[0212] Although not shown in the table, even when printing satisfying the above constitution was performed using a line printer, the obtained printed matter had excellent color development and rubbing fastness.

[0213] The following can be derived from the above-described embodiment.

[0214] One aspect of the inkjet printing method includes: a reaction liquid attachment step of attaching a reaction liquid containing a flocculant for flocculating 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 a fabric by an inkjet method; a color ink applying step of applying a color ink composition containing a pigment, resin particles, and water by an ink jet method onto the area to which the transparent ink composition has been applied; The reaction liquid applying step and the transparent ink applying step include the following step 1: In the step 1, the range of the minimum value of the total amount of the reaction liquid and the transparent ink composition attached per unit area and unit time is 34 mg / (s·inch 2 )That's all. Step 1: applying the reaction liquid and the transparent ink composition to the same area of ​​the fabric in one scan of an inkjet head.

[0215] In one embodiment of the inkjet printing method, The step 1 is carried out multiple times, The reaction liquid applying step and the transparent ink applying step include the following step 2: The step 2 may be carried out between the steps of the step 1 being carried out multiple times.

[0216] In any one of the above ink-jet printing methods, The pigment may be a white pigment.

[0217] In any one of the above ink-jet printing methods, A mixture of equal amounts of the reaction liquid and the transparent ink composition may have a viscosity of 50 mPa·s or more.

[0218] In any one of the above ink-jet printing methods, The reaction liquid applying step may be carried out simultaneously with the colored ink applying step.

[0219] In any one of the above ink-jet printing methods, The colored ink depositing step may be performed in a different scan than the clear ink depositing step.

[0220] In any one of the above ink-jet printing methods, The method may further include a second transparent ink applying step of applying, by an inkjet method, a second transparent ink composition containing anionic resin particles and water onto the area of ​​the fabric to which the colored ink composition is applied.

[0221] In any one of the above ink-jet printing methods, At least one of the pigment and the resin particles in the colored ink composition may be anionic.

[0222] In any one of the above ink-jet printing methods, The resin particles in the colored ink composition may be a urethane resin or an acrylic resin.

[0223] In any one of the above ink-jet printing methods, The colored ink composition may further contain 3.0% by mass or more of an organic solvent having a normal boiling point of 250° C. or higher.

[0224] In any one of the above ink-jet printing methods, The fabric is L * 75 or less and may be cotton, polyester, or a blend of cotton and polyester.

[0225] In any one of the above ink-jet printing methods, The pH of the reaction solution may be 2.0 or higher.

[0226] In any one of the above ink-jet printing methods, In the region of the fabric to which the reaction liquid, the transparent ink composition, and the colored ink composition are adhered, the total amount of the reaction liquid, the transparent ink composition, and the colored ink composition adhered is 100 mg / inch 2 It may be more than that.

[0227] One aspect of the set is A set for use in the ink-jet printing method according to any one of the above aspects, The ink jet recording medium comprises the reaction liquid, the transparent ink composition, and the colored ink composition.

[0228] The present invention is not limited to the above-described embodiment, and various modifications are possible. For example, the present invention includes configurations that are substantially the same as the configurations described in the embodiments, for example configurations with the same functions, methods, and results, or configurations with the same purpose and effect. 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 as the configurations described in the embodiments or that can achieve the same purpose. The present invention also includes configurations in which publicly known technology is added to the configurations described in the embodiments. [Explanation of symbols]

[0229] 20...serial printer, 220...transport section, 230...recording section, 231...inkjet head, 234...carriage, 235...carriage movement mechanism, 1...line printer, 100...feed section, 200...transport 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 section, Y...feed direction, F...recording medium, SD...scanning direction, TD...transport direction

Claims

1. a reaction liquid attachment step of attaching a reaction liquid containing a flocculant for flocculating 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 a fabric by an inkjet method; a color ink applying step of applying a color ink composition containing a pigment, resin particles, and water by an ink jet method onto the area to which the transparent ink composition has been applied; The reaction liquid applying step and the transparent ink applying step include the following step 1: In the step 1, the range of the minimum value of the total amount of the reaction liquid and the transparent ink composition attached per unit area and unit time is 34 mg / (s·inch ２ ) The ink-jet printing method. Step 1: applying the reaction liquid and the transparent ink composition to the same area of ​​the fabric by one scan of an inkjet head

2. The step 1 is carried out multiple times, The reaction liquid applying step and the transparent ink applying step include the following step 2: The ink-jet printing method according to claim 1 , wherein the step 2 is performed between the step 1 which is performed a plurality of times. Step 2: Transporting the fabric in a direction intersecting the scanning direction

3. The ink-jet printing method according to claim 1 or 2, wherein the pigment is a white pigment.

4. The ink-jet printing method according to claim 1 or 2, wherein a mixed liquid obtained by mixing equal amounts of the reaction liquid and the transparent ink composition has a viscosity of 50 mPa·s or more.

5. The ink-jet printing method according to claim 1 or 2, wherein the reaction liquid applying step is carried out simultaneously with the colored ink applying step.

6. The ink-jet printing method according to claim 1 or 2, wherein the colored ink applying step is performed in a different scan from the transparent ink applying step.

7. 3. The ink-jet textile printing method according to claim 1, further comprising a second transparent ink applying step of applying, by an ink-jet method, a second transparent ink composition containing anionic resin particles and water onto the region of the fabric to which the colored ink composition is applied.

8. The ink-jet printing method according to claim 1 or 2, wherein at least one of the pigment and the resin particles in the colored ink composition is anionic.

9. The ink-jet printing method according to claim 1 or 2, wherein the resin particles in the colored ink composition are a urethane resin or an acrylic resin.

10. The ink-jet printing method according to claim 1 or 2, wherein the colored ink composition further contains 3.0% by mass or more of an organic solvent having a normal boiling point of 250° C. or higher.

11. The fabric is L ＊ The ink-jet textile printing method according to claim 1 or 2, wherein the fiber has a viscosity of 75 or less and is made of cotton, polyester, or a blend of cotton and polyester.

12. The inkjet printer according to claim 1 or 2, wherein the reaction liquid has a pH of 2.0 or more. Printing method.

13. In an area of ​​the fabric to which the reaction liquid, the transparent ink composition, and the colored ink composition are adhered, the total amount of the reaction liquid, the transparent ink composition, and the colored ink composition adhered is 100 mg / inch ２ The ink-jet printing method according to claim 1 or 2, wherein

14. A set for use in the ink-jet printing method according to claim 1, A set comprising the reaction liquid, the clear ink composition, and the colored ink composition.

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