Inkjet recording method

Abstract

To provide an inkjet recording method that can suppress both image cracking and ink bleeding. [Solution] An inkjet recording method according to one embodiment of the present invention comprises: an acidic reaction solution application step of applying an acidic reaction solution containing an acid and water to a fabric by an inkjet method; an anionic transparent ink application step of applying an anionic transparent ink composition containing first anionic resin particles and water to the fabric by an inkjet method; an anionic colored ink application step of applying an anionic colored ink composition containing a pigment, second anionic resin particles and water to the area to which the transparent ink composition has been applied by an inkjet method; and an anionic solution coating step of applying an anionic alkaline aqueous solution with a pH of 8.0 or higher to the area to which the colored ink composition has been applied.

Description

[Technical Field]

[0001] The present invention relates to an inkjet recording method. [Background technology]

[0002] Conventionally, in textile printing using inkjet ink compositions, a technique is known in which a reaction solution containing a coagulant that aggregates components in the ink is used to treat the fabric in order to improve the color development of the recorded material.

[0003] For example, Patent Document 1 describes an inkjet printing method for printing on a textile product substrate, which includes the steps of applying a pretreatment composition, applying a transparent ink, and applying a white ink. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Special Publication No. 2022-548985 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, there is a challenge in achieving both the suppression of image cracking and the suppression of ink bleeding. [Means for solving the problem]

[0006] One aspect of the inkjet recording method according to the present invention is: An acidic reaction solution application step in which an acidic reaction solution containing acid and water is applied to the fabric by an inkjet method, An anionic transparent ink application step in which an anionic transparent ink composition containing primary anionic resin particles and water is applied to the fabric by an inkjet method, An anionic colored ink application step involves applying an anionic colored ink composition containing a pigment, secondary anionic resin particles, and water to an area on which the transparent ink composition is attached by an inkjet method. The method includes an anionic solution coating step of applying an anionic alkaline aqueous solution with a pH greater than 8.0 to the area to which the colored ink composition is attached. [Brief explanation of the drawing]

[0007] [Figure 1] A perspective view of a serial printer. [Figure 2] A schematic diagram showing an example of the nozzle row arrangement of an inkjet head. [Figure 3] Schematic side view of a line printer. [Figure 4] Table 1 shows examples of the composition of each composition. [Figure 5] Table 2 shows the conditions and evaluation results for each example. [Figure 6] Table 3 shows the conditions and evaluation results for each example and comparative example. [Modes for carrying out the invention]

[0008] Embodiments of the present invention will be described below. The embodiments described below are examples of the present invention. The present invention is not limited in any way to the embodiments described below, and includes various modifications that can be implemented without changing the gist of the present invention. Not all of the configurations described below are necessarily essential to the present invention.

[0009] In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this specification, "inkjet method" refers to a method of ejecting droplets of an inkjet composition from the nozzles of an inkjet head and adhering them to a recording medium. In this specification, "(meth)acrylic" means acrylic or methacrylic, and "(meth)acrylate" means acrylate or methacrylate.

[0010] 1. Inkjet recording method An inkjet recording method according to one embodiment of the present invention comprises: an acidic reaction solution application step of applying an acidic reaction solution containing an acid and water to a fabric by an inkjet method; an anionic transparent ink application step of applying an anionic transparent ink composition containing first anionic resin particles and water to the fabric by an inkjet method; an anionic colored ink application step of applying an anionic colored ink composition containing a pigment, second anionic resin particles and water to the area to which the transparent ink composition has been applied by an inkjet method; and an anionic solution coating step of applying an anionic alkaline aqueous solution with a pH of over 8.0 to the area to which the colored ink composition has been applied.

[0011] When colored ink applied to a fabric penetrates into the fabric, its color development deteriorates. Therefore, it is conceivable to use an acidic reaction solution to aggregate the components of anionic transparent ink (e.g., anionic resin particles) and form a layer of transparent ink near the surface of the fabric. This layer of transparent ink near the surface of the fabric acts as a base for the resin layer, suppressing the penetration of colored ink applied on top of the transparent ink layer into the fabric, thus enabling the production of a recording with good color development.

[0012] In this case, the acidic reaction solution has relatively high volatility (compared to cases where polyvalent metal salts, etc., are used as flocculants), so it is less likely to remain on the fabric and less likely to cause discoloration of the fabric when drying. On the other hand, using an acidic reaction solution can cause cracking of the coating on the recorded material after drying. This is thought to be because the acid, which was not neutralized by the anionic components in the ink, promotes excessive aggregation. In particular, if there are multiple types of ink to be aggregated and a large amount of acidic reaction solution needs to be applied, coating cracking is more likely to occur. In addition, when a sufficient amount of the reaction solution is not adhered, excessive aggregation is less likely to proceed and film cracking is less likely to occur. On the other hand, a sufficient ink aggregation effect cannot be obtained, and there is a risk of ink bleeding.

[0013] On the contrary, according to the inkjet recording method according to this embodiment, an anionic alkaline aqueous solution with a pH exceeding 8.0 can be adhered to the region where the colored ink is adhered, thereby neutralizing the excess acid. As a result, excessive aggregation during drying can be suppressed, and film cracking can be suppressed. In addition, with such a method, a sufficient amount of the reaction solution can be adhered, so that ink bleeding can also be suppressed.

[0014] Hereinafter, each step included in the inkjet recording method according to this embodiment will be described.

[0015] 1.1 Acidic reaction solution adhesion step The inkjet recording method according to this embodiment includes an acid reaction solution adhesion step of adhering an acid reaction solution containing an acid and water to a fabric by an inkjet method.

[0016] 1.1.1 Adhesion mode 1.1.1.1 Coating amount In the acid reaction solution adhesion step, the coating amount (X) per unit area of the reaction solution on the fabric is not particularly limited, but is preferably 0.010 g / inch 2 or more, more preferably 0.020 g / in ch 2 or more, even more preferably 0.030 g / inch 2 or more, still more preferably 0.040 g / inch 2 or more, even still more preferably 0.045 g / inch 2 or more, particularly preferably 0.050 g / inch 2 or more, even more particularly preferably. Also, the coating amount (X) per unit area of the reaction solution on the fabric is preferably 0.100 g / inch 2 or less, more preferably 0.080 g / inch 2 or less, even more preferably 0.070 g / inch 2The following is even more preferable: 0.060 g / inch 2 The following is particularly preferred: 0.055 g / inch 2 The following are particularly preferable. The amount of reaction solution applied is 0.010 g / inch. 2 The above values ​​tend to further suppress ink bleeding. Also, the amount of reaction solution applied is 0.100 g / inch. 2 The following conditions tend to better suppress image cracking.

[0017] In the acidic reaction solution application step, it is preferable that the amount of reaction solution applied per unit area (X) to the fabric, the neutralization power equivalent value (Y) of the transparent ink composition applied to the fabric to the reaction solution in the anionic transparent ink application step, and the neutralization power equivalent value (Z) of the colored ink composition applied to the fabric to the reaction solution in the anionic colored ink application step satisfy the following relationship. X - (Y + Z) ≥ 0 ... Equation (1)

[0018] The "neutralizing power equivalent value (Y)" is calculated using the following procedure. The reaction solution is added dropwise to 50 g of transparent ink composition, and the amount of reaction solution added when the pH of the mixture of transparent ink composition and reaction solution becomes 7.0 is calculated (NW C ) Measure and NW C The value obtained by dividing this by the weight of the transparent ink composition (50 [g]) is the neutralization weight ratio (NR) of the transparent ink composition. c [-]) And the amount of transparent ink composition applied per unit area (V c [g / inch 2 ]) to NR c The value obtained by multiplying by this factor is defined as the neutralization power (Y) of the transparent ink composition relative to the reaction solution. NR c =NW C ÷50 Y=V c ×NR c

[0019] The "neutralizing power equivalent value (Z)" is calculated using the following procedure. The reaction solution is added dropwise to 50 g of the colored ink composition, and the amount of reaction solution added when the pH of the mixture of the colored ink composition and the reaction solution becomes 7.0 is calculated (NW w ) Measure and NW w The value obtained by dividing this by the weight of the colored ink composition (50 [g]) is the neutralization weight ratio (NR) of the colored ink composition. w [-]) And the amount of colored ink composition applied per unit area (V w [g / inch 2 ]) to NR w The value obtained by multiplying by is defined as the neutralization power (Z) of the colored ink composition in relation to the reaction solution. NR w =NW w ÷50 Z=V w ×NR w

[0020] When the above equation (1) is satisfied, it can be said that a sufficient amount of the reaction solution is applied during the acidic reaction solution application process, which tends to further suppress ink bleeding and improve color development.

[0021] The value of "X-(Y+Z)" in formula (1) above is 0 or greater, but is more preferably 0.001 or greater, even more preferably 0.002 or greater, even more preferably 0.003 or greater, and particularly preferably 0.004 or greater. Furthermore, the value of "X-(Y+Z)" in formula (1) above is preferably 0.010 or less, more preferably 0.008 or less, and even more preferably 0.006 or less. When the value of "X-(Y+Z)" in equation (1) above is 0.010 or less, image cracking tends to be suppressed.

[0022] Furthermore, X, Y and Z mentioned above, and in the anionic solution coating process, colored ink It is preferable that the neutralization power (W) of the alkaline aqueous solution attached to the region to which the composition is attached satisfies the following relationship. W≧X-(Y+Z) ...Equation (2)

[0023] The "neutralizing power equivalent value (W)" is calculated using the following procedure. When the reaction solution is added dropwise to 50 g of alkaline aqueous solution, the amount of reaction solution added when the pH of the mixture of alkaline aqueous solution and reaction solution becomes 7.0 is calculated (NW). n ) Measure and NW n The value obtained by dividing by the weight of the alkaline aqueous solution (50 [g]) is the neutralization weight ratio (NR) of the alkaline aqueous solution. n [-]) And the amount of alkaline aqueous solution applied per unit area (V n [g / inch 2 ]) to NW n The value obtained by multiplying by is taken as the neutralizing power (W) of the alkaline aqueous solution in relation to the reaction solution. NR n =NW n ÷50 W=V n ×NR n

[0024] When equation (2) above is satisfied, it can be said that the excess acid deposited in the acidic reaction solution deposition process has been sufficiently neutralized, and there is a tendency for image cracking to be further suppressed.

[0025] In formula (2) above, the value of "W-(X-(Y+Z))" is 0 or greater, but is more preferably 0.001 or greater, even more preferably 0.003 or greater, even more preferably 0.005 or greater, and particularly preferably 0.007 or greater. Furthermore, the value of "W-(X-(Y+Z))" in formula (2) above is preferably 0.015 or less, more preferably 0.012 or less, and even more preferably 0.010 or less.

[0026] 1.1.1.2 Attachment Order In the inkjet recording method according to this embodiment, the order in which the acid reaction solution application step is performed is not particularly limited. For example, it may be performed before, simultaneously with, or after the ink application step, i.e., the anionic transparent ink application step or the anionic colored ink application step. Furthermore, the acid reaction solution application step may be performed multiple times.

[0027] In the inkjet recording method according to this embodiment, it is preferable that the acidic reaction solution application step and the anionic transparent ink application step are performed within the same scanning area and on the same region of the fabric by applying the reaction solution and the transparent ink composition. This allows the reaction solution and the transparent ink composition to be simultaneously attached by the inkjet method, forming a resin layer closer to the fabric surface and tending to improve color development.

[0028] Furthermore, in the inkjet recording method according to this embodiment, it is also preferable that the acidic reaction solution application step and the anionic colored ink application step be performed within the same scan and on the same area of ​​the fabric by applying the reaction solution and the colored ink composition. This allows the reaction solution and the colored ink composition to be simultaneously attached using an inkjet method, making it easier to mix the two solutions and effectively promoting the aggregation reaction of the colored ink components, which tends to improve color development.

[0029] Here, "scanning" refers to moving the inkjet head relative to the recording area on the fabric. In this case, the inkjet head may move relative to the fabric, or the fabric may move relative to the inkjet head. Furthermore, the relative positional relationship between the inkjet head and the fabric may change as both move. The inkjet head can be mounted on a carriage, for example. The inkjet head may be moved as the carriage moves; in this case as well, it is the movement of the inkjet head.

[0030] Therefore, in the serial inkjet recording device 20 shown in Figure 1, for example, "scanning" is performed while the carriage 234 having the inkjet head 231 moves in a scanning direction SD that intersects the transport direction TD of the recording medium F.

[0031] Furthermore, "scanning" in a line-type inkjet recording device 1, as shown in Figure 3, involves recording being performed while the recording medium F moves relative to a line head 300 having a length corresponding to the width of the recording medium F in a direction intersecting the width direction. In line-type recording, the inkjet head (line head) remains fixed and does not move during recording, and recording is performed in a single scan.

[0032] "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 exactly the same; it may also mean that the length is greater than or equal to the width of the recording medium, or that the length is equivalent to the width of the recording medium (recorded width) on which the ink should be ejected (on which the image should be recorded).

[0033] The time difference between the adhesion of the reaction solution and the transparent ink composition in the same area of ​​the fabric is preferably 30 seconds or less, more preferably 15 seconds or less, even more preferably 5 seconds or less, even more preferably 1 second or less, particularly preferably 0.5 seconds or less, and most particularly preferably 0.1 seconds or less. When the time difference is within the above range, the resin layer tends to form closer to the surface of the fabric, and the color development tends to be further improved. Regarding the time difference between the adhesion of the reaction solution and the colored ink composition in the same area of ​​the fabric, it is preferable to keep it the same as described above, from the viewpoint that color development tends to be further improved.

[0034] 1.1.2 Reaction solution The reaction solution used in the acidic reaction solution deposition step of the inkjet recording method according to this embodiment is an acidic reaction solution containing an acid and water. The components contained in the reaction solution will be described below.

[0035] 1.1.2.1 Acids The reaction solution contains acid and is acidic. A reaction solution is considered "acidic" if its pH is less than 7.

[0036] Examples of acids include inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, as well as organic acids.

[0037] Suitable organic acids include, for example, 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, pyruvate, pyrrolidone carboxylic acid, pyrrone carboxylic acid, pyrrole carboxylic acid, furanic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, or derivatives of these compounds, or salts thereof.

[0038] As the acid, an organic acid is preferred, and a compound having 1 to 3 carboxyl groups is more preferred. In particular, when the acid is a compound having 1 to 3 carboxyl groups, the aggregation ability of the ink components is appropriate, and it tends to be possible to effectively suppress both image cracking and ink bleeding.

[0039] Examples of compounds having one carboxyl group include poly(meth)acrylic acid, formic acid, acetic acid, propionic acid, glycolic acid, lactic acid, pyruvate, pyrrolidone carboxylic acid, pyrrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, and nicotinic acid, with lactic acid being more preferred. Examples of compounds having two carboxyl groups include oxalic acid, malonic acid, malic acid, maleic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, and tartaric acid, with succinic acid being more preferred. Examples of compounds having three carboxyl groups include citric acid and isocitric acid, with citric acid being more preferred.

[0040] Among these, the compound having 1 to 3 carboxyl groups is preferably one or more selected from lactic acid, succinic acid, and citric acid.

[0041] From the viewpoint of superior color development and suppression of ink bleeding, the acid content is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, even more preferably 2.0% by mass or more, and particularly preferably 3.0% by mass or more, relative to the total amount of the reaction solution. From the viewpoint of superior image crack suppression, the acid content is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 8% by mass or less, relative to the total amount of the reaction solution.

[0042] 1.1.2.2 Water The reaction solution contains water. Examples of water include pure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water, as well as ultrapure water, which has reduced ionic impurities. Furthermore, using water sterilized by ultraviolet irradiation or the addition of hydrogen peroxide can suppress the growth of bacteria and fungi when the reaction solution is stored for a long period of time.

[0043] The water content is preferably 40% by mass or more, more preferably 45% by mass or more, even more preferably 50% by mass or more, and particularly preferably 60% by mass or more, relative to the total amount of the reaction solution. There is no particular upper limit to the water content, but for example, it is preferably 90% by mass or less, more preferably 85% by mass or less, and more preferably 80% by mass or less, relative to the total amount of the reaction solution.

[0044] 1.1.2.3 Organic Solvents The reaction solution may contain an organic solvent. Examples of organic solvents include esters, glycol ethers, cyclic esters, amides, alcohols, and polyhydric alcohols.

[0045] Esters include glycol monoacetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, methoxybutyl acetate, ethylene glycol diacetate, and diethylene glycol. Examples of glycol diesters include propyl 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.

[0046] Examples of glycol ethers include monoethers or diethers of alkylene glycols. Examples of alkylene glycol monoethers include ethylene glycol monomethyl Examples include alkylene glycol monoalkyl ethers such as 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 monomethyl ether, tripropylene glycol monobutyl ether, 3-methoxy-3-methylbutanol, and 3-methoxy-butanol. Examples of alkylene glycol diethers include 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.

[0047] Examples of cyclic esters include cyclic esters (lactones) such as β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, β-butyrolactone, β-valerolactone, γ-valerolactone, β-hexanolactone, γ-hexanolactone, δ-hexanolactone, β-heptanolactone, γ-heptanolactone, δ-heptanolactone, ε-heptanolactone, γ-octanolactone, δ-octanolactone, ε-octanolactone, δ-nonalactone, ε-nonalactone, and ε-decanolactone, as well as compounds in which the hydrogen atoms of the methylene group adjacent to the carbonyl group are substituted with alkyl groups having 1 to 4 carbon atoms.

[0048] Examples of amides include cyclic amides and acyclic amides. Examples of acyclic amides include alkoxyalkyl amides. Examples of cyclic amides include lactams. Examples of lactams include pyrrolidones such as 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, and 1-(2-hydroxyethyl)pyrrolidine-2-one. Examples of alkoxyalkylamides include 3-methoxy-N,N-dimethylpropionamide, 3-methoxy-N,N-diethylpropionamide, 3-methoxy-N,N-methylethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-diethylpropionamide, 3-ethoxy-N,N-methylethylpropionamide, 3-n-butoxy-N,N-dimethylpropionamide, 3-n-butoxy-N,N-diethylpropionamide, 3-n-butoxy-N,N-methylethylpropionamide, 3-n-propoxy-N,N-dimethylpropionamide, 3-n-propoxy-N,N-diethylpropionamide, and 3-n-propoxy-N,N-methylethylpropionamide. Examples include ethylpropionamide, 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-dimethylisobutyrate amide.

[0049] 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 fewer carbon atoms, more preferably 6 or fewer, and even more preferably 3 or fewer. The alkane has 1 or more carbon atoms, preferably 2 or more. 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.

[0050] Polyhydric alcohols are molecules that contain two or more hydroxyl groups. Examples of polyhydric alcohols include alkanediols and polyols. Polyhydric alcohols may have a carbon-hydrogen skeleton and two or more hydroxyl groups in their molecule, and may also have an ether-bonded oxygen atom. It is preferable that they do not have any structures other than these.

[0051] Alkanediols include, for example, compounds in which an alkane is substituted with two hydroxyl groups. Examples of alkanediols include 1,2-alkanediols, which are a general term for compounds in which hydroxyl groups are substituted at the 1st and 2nd positions of an alkane, and other alkanediols other than 1,2-alkanediols. 1,2-alkanediols are preferred. The number of carbon atoms in alkanediols is preferably 2 or more, more preferably 3 to 10. Furthermore, 5 or more is preferred, and 5 to 8 is more preferred. On the other hand, 4 or fewer carbon atoms is also preferred.

[0052] Examples of 1,2-alkanediols include ethylene glycol, 1,2-propanediol (propylene glycol), 1,2-butanediol, 1,2-pentanediol (1,2PD), 1,2-hexanediol, 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, and 3 Examples include -ethyl-1,2-pentanediol, 4-ethyl-1,2-pentanediol, 3-methyl-1,2-hexanediol, 4-methyl-1,2-hexanediol, 5-methyl-1,2-hexanediol, 3,4-dimethyl-1,2-hexanediol, 3,5-dimethyl-1,2-hexanediol, 4,5-dimethyl-1,2-hexanediol, 3-ethyl-1,2-hexanediol, 4-ethyl-1,2-hexanediol, and 3-ethyl-4-methyl-1,2-hexanediol.

[0053] Other examples of alkanediols include 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. ru.

[0054] Examples of polyols include condensates formed by the intermolecular condensation of two or more alkanediol molecules via hydroxyl groups, and compounds having three or more hydroxyl groups.

[0055] Examples of condensates formed by the intermolecular condensation of two or more alkanediol molecules at their hydroxyl groups include dialkylene glycols such as diethylene glycol and dipropylene glycol, and trialkylene glycols such as triethylene glycol and tripropylene glycol.

[0056] Compounds having three or more hydroxyl groups are compounds with an alkane or polyether structure as their backbone and containing three or more hydroxyl groups. Examples of compounds having three or more hydroxyl groups include glycerin, trimethylolethane, trimethylolpropane, 1,2,5-hexanetriol, 1,2,6-hexanetriol, pentaerythritol, and polyoxypropylenetriol.

[0057] Organic solvents may be used individually or in combination of two or more types.

[0058] Among these, the organic solvent preferably contains alkanediols, more preferably 1,2-alkanediols, and particularly preferably propylene glycol. When the organic solvent contains these solvents, it may be even better at suppressing cracking and ink bleeding in images.

[0059] The content of the organic solvent is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, even more preferably 15 to 35% by mass, and particularly preferably 20 to 30% by mass, relative to the total amount of the reaction solution. When the content of the organic solvent is within the above range, it may be superior in suppressing cracking and ink bleeding in the image.

[0060] 1.1.2.4 Surfactants The reaction solution may contain a surfactant. The surfactant can be used to lower the surface tension of the reaction solution, for example, to adjust or improve its permeability to fabrics. Any of the following surfactants can be used: nonionic surfactants, anionic surfactants, cationic surfactants, or amphoteric surfactants, and these may be used in combination. Among surfactants, acetylene-based surfactants (acetylene glycol-based surfactants), silicone-based surfactants, and fluorine-based surfactants are more preferably used, and acetylene-based surfactants are even more preferably used.

[0061] The acetylene glycol-based surfactant is not particularly limited, but for example, one or more selected from 2,4,7,9-tetramethyl-5-decine-4,7-diol and alkylene oxide adducts of 2,4,7,9-tetramethyl-5-decine-4,7-diol, and 2,4-dimethyl-5-decine-4-ol and alkylene oxide adducts of 2,4-dimethyl-5-decine-4-ol are preferred. The commercially available acetylene glycol-based surfactant is not particularly limited, but for example, Surfinol 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, DF 110D (All of the above are product names, manufactured by Air Products Japan Co., Ltd.), Olfin B, Y, P, A, STG, SPC, E1004, E1010, PD-001, PD-002W, PD-003, PD-004, EXP.4001, EXP.4036, EXP.4051, AF-103, AF-104, AK-02, SK-14, AE-3 (All of the above are product names, manufactured by Nisshin Chemical Industry Co., Ltd.) Examples include Acetylene glycol E00, E00P, E40, and E100 (all brand names, manufactured by Kawaken Fine Chemical Co., Ltd.). Acetylene glycol surfactants may be used individually or in combination of two or more types.

[0062] Examples of silicone-based surfactants are not particularly limited, but include polysiloxane compounds and polyether-modified organosiloxanes. Examples of commercially available silicone-based surfactants are not particularly limited, but include BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-348, BYK-349 (all trade names, manufactured by BI-Chemie Japan Co., Ltd.), KF-351A, KF-352A, KF-353, KF-354L, and KF-355. Examples include A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017 (all product names, manufactured by Shin-Etsu Chemical Co., Ltd.), Silface SAG503A, Silface SAG014 (all product names, manufactured by Nisshin Chemical Industry Co., Ltd.). Silicone-based surfactants may be used individually or in combination of two or more types.

[0063] Examples of fluorinated surfactants include, but are not limited to, perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphate esters, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines, and perfluoroalkylamine oxide compounds. Examples of commercially available fluorinated surfactants include, but are not limited to, S-144, S-145 (trade names, manufactured by Asahi Glass Co., Ltd.); FC-170C, FC-430, Florard-FC4430 (trade names, manufactured by Sumitomo 3M Limited); FSO, FSO-100, FSN, FSN-100, FS-300 (trade names, manufactured by Dupont); FT-250, 251 (trade names, manufactured by Neos Co., Ltd.). Fluorinated surfactants may be used individually or in combination of two or more types.

[0064] Surfactants may be used individually or in combination of two or more types.

[0065] The surfactant content is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, even more preferably 2.0% by mass or less, particularly preferably 1.5% by mass or less, and most particularly preferably 1.0% by mass or less, relative to the total amount of the reaction solution. When the surfactant content is within the above range, and especially 2.0% by mass or less, the viscosity of the mixed solution tends to increase when the reaction solution and transparent ink are mixed, which contributes to the better formation of a resin layer near the surface of the fabric, resulting in a better sealing effect and a tendency to be superior in color development and suppression of ink bleeding. The lower limit of the surfactant content is not particularly limited, but it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, relative to the total amount of the reaction solution.

[0066] 1.1.2.5 Other ingredients The reaction solution may contain various additives as needed, such as pH adjusters, preservatives / fungicides, rust inhibitors, chelating agents, viscosity modifiers, solubilizers, and antioxidants. When such additives are included, the content is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, and even more preferably 0.1 to 1% by mass, relative to the total amount of the reaction solution.

[0067] Furthermore, the reaction solution may contain colorants such as pigments, but it is preferable that the amount is 0.2% by mass or less, more preferably 0.1% by mass or less, even more preferably 0.05% by mass or less, and the lower limit is 0% by mass. It is preferable that the reaction solution does not contain colorants.

[0068] 1.1.2.6 Physical Properties The pH of the reaction solution is not particularly limited as long as it is acidic, but is preferably 6 or less, more preferably 5 or less, even more preferably 4 or less, and particularly preferably 3 or less.

[0069] The viscosity of the reaction solution is preferably 1.0 to 10 mPa·s at 20°C, more preferably 3.5 to 8.0 mPa·s, and even more preferably 2.0 to 4.0 mPa·s. In particular, a viscosity of 3.0 mPa·s or higher tends to yield better color development. A viscosity of 8.0 mPa·s or lower tends to yield better discharge stability. The viscosity can be measured using, for example, a viscoelasticity tester such as the MCR-300 (product name) from Pysica.

[0070] The surface tension of the reaction solution is preferably 25 to 40 mN / m, more preferably 25 to 35 mN / m, even more preferably 27 to 35 mN / m, and particularly preferably 30 to 33 mN / m. The surface tension can be measured, for example, using a surface tensimeter (Kyowa Interface Science Co., Ltd., DY-300) by the Wilhelmy method. The surface tension is preferably measured at 20°C.

[0071] 1.1.3 Fabric Examples of fabric materials used in the inkjet recording method according to this embodiment include natural fibers such as cotton, linen, wool, and silk; synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, and polyurethane; and biodegradable fibers such as polylactic acid. Blends of these fibers are also acceptable. Among these materials, fabrics made of cotton, polyester, or a blend of cotton and polyester are readily available and therefore preferred.

[0072] Furthermore, examples of fabric forms include cloth, clothing, and other fashion accessories. Cloth includes woven fabrics, knitted fabrics, and nonwoven fabrics. Clothing and other fashion accessories include finished items such as T-shirts, handkerchiefs, scarves, towels, tote bags, cloth bags, curtains, sheets, bedspreads, wallpaper and other furniture, as well as fabrics before and after cutting as components before sewing. These can take the form of long rolls, cut to a predetermined size, or in the shape of finished products.

[0073] The fabric is L * a* b * Lightness L in a color system * It is preferable that the value of L is 70 or less. * The value may be 60 or less, or 50 or less. In recording on such fabrics, white ink (undercoat) may be used as the colored ink composition to obtain excellent color development. White ink contains a relatively large amount of colorant and is applied in a relatively large quantity, so it is necessary to apply a large amount of reaction solution, which tends to cause cracking of the image. In contrast, the inkjet recording method according to this embodiment tends to suppress image cracking well, even when using such fabrics.

[0074] Note L * The values ​​can be measured using a known colorimeter, for example, Spectrolino (Gretag).

[0075] Note L * Examples of fabrics with a value of 70 or less include colored fabrics that have been pre-colored with dyes, and black fabrics are preferred. Examples of dyes used to pre-color fabrics include water-soluble dyes such as acid dyes and basic dyes, disperse dyes used in combination with dispersants (surfactants), and reactive dyes. Known methods can be used to color fabrics with dyes, depending on the material and form of the fabric.

[0076] 1.2 Anionic transparent ink application process The inkjet recording method according to this embodiment contains primary anionic resin particles and water. The process includes an anionic transparent ink application step in which an anionic transparent ink composition is applied to a fabric by an inkjet method.

[0077] 1.2.1 Adhesion Pattern 1.2.1.1 Application amount In the anionic transparent ink application process, the amount of transparent ink composition applied per unit area to the fabric (V c) is not particularly limited, but 0.010 g / inch 2 The above is preferable, and 0.030 g / inch 2 The above is more preferable, 0.050 g / inch 2 The above is even more preferable, 0.070 g / inch 2 The above is even more preferable, 0.100 g / inch 2 The above is particularly preferable. Also, the amount of transparent ink composition applied per unit area to the fabric (V c ) is 0.200g / inch 2 The following is preferable: 0.150 g / inch 2 The following is more preferable: 0.120 g / inch 2 The following are even more preferable. The application amount of the transparent ink composition is 0.010 g / inch. 2 When the above is achieved, the color development tends to be better. Also, the application amount of the transparent ink composition is 0.200 g / inch. 2 The following conditions tend to better suppress image cracking.

[0078] 1.2.1.2 Attachment Order In the inkjet recording method according to this embodiment, the order in which the anionic transparent ink adhesion step is performed is not particularly limited, as long as the anionic colored ink adhesion step, described later, can adhere the colored ink composition onto the area to which the transparent ink composition has been adhered. For example, the anionic transparent ink adhesion step may be performed before or simultaneously with the anionic colored ink adhesion step. However, when the anionic transparent ink adhesion step is performed simultaneously with the anionic colored ink adhesion step, the transparent ink composition is first adhered to the fabric, and then the colored ink composition is adhered to the fabric.

[0079] By applying a transparent ink composition and a colored ink composition to the same area of ​​the fabric within the same scan, the anionic transparent ink adhesion process and the anionic colored ink adhesion process can be performed simultaneously. However, the order in which the inks land on the fabric is such that the transparent ink composition is applied first, followed by the colored ink composition.

[0080] The time difference between the adhesion of the transparent ink composition and the colored ink composition in the same area of ​​the fabric can be the same as the time difference between the adhesion of the reaction solution and the transparent ink composition described above.

[0081] 1.2.2 Transparent Ink Composition The transparent ink composition used in the anionic transparent ink application step of the inkjet recording method according to this embodiment is an anionic transparent ink composition containing first anionic resin particles and water. The components contained in the transparent ink composition will be described below.

[0082] A transparent ink composition is considered "anionic" if it contains at least one anionic component.

[0083] 1.2.2.1 Primary anionic resin particles The transparent ink composition contains primary anionic resin particles. Similar to the function of resin particles, the primary anionic resin particles function as a so-called fixing resin, improving the adhesion of the ink to the fabric. Furthermore, the primary anionic resin particles react with the reaction solution described above and aggregate, thereby thickening the transparent ink composition. The primary anionic resin particles are often handled in emulsion form, but they may also be in powder form.

[0084] "Anionic resin particles" refer to resin particles that have a negative charge as a whole, and that possess one or more anionic groups selected from carboxyl groups, sulfonic acid groups, phosphate groups, etc. It is preferable to do so.

[0085] Examples of primary anionic resin particles include resin particles made from 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, and the like. Among these, urethane resin, acrylic resin, ofrefin resin, and ester resin are preferred. Furthermore, primary anionic resin particles may be used individually or in combination of two or more types.

[0086] Urethane resin is a general term for resins that have urethane bonds. In addition to urethane bonds, urethane resins may also be polyether-type urethane resins containing ether bonds in the main chain, ester-type urethane resins containing ester bonds in the main chain, or carbonate-type urethane resins containing carbonate bonds in the main chain. Commercially available urethane resins may also be used, such as Superflex 460, 460s, 840, E-4000 (product names, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Rezamin D-1060, D-2020, D-4080, D-4200, D-6300, D-6455 (product names, manufactured by Dainichi Seika Kogyo Co., Ltd.), Takelac WS-5100, WS-6021, W-512-A-6 (product names, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.), SanCure 2710 (product name, manufactured by LUBRIZOL), and Permarin UA-150 (product name, manufactured by Sanyo Chemical Industries, Ltd.).

[0087] Acrylic resin is a general term for polymers obtained by polymerizing at least one acrylic monomer, such as (meth)acrylic acid or (meth)acrylic acid ester. Examples include resins obtained from acrylic monomers and copolymers of acrylic monomers with other monomers. For example, acrylic-vinyl resin, which is a copolymer of acrylic monomers and vinyl monomers, is an example. For example, styrene can be used as a vinyl monomer. Acrylic monomers such as acrylamide and acrylonitrile can also be used. For resin emulsions made from acrylic resin, commercially available products may be used, for example, selected from FK-854 (trade name, manufactured by Chuo Rika Kogyo Co., Ltd.), Movinyl 952B, 718A (trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), Nipol LX852, LX874 (trade name, manufactured by Nippon Zeon Co., Ltd.).

[0088] Styrene-acrylic resins are copolymers obtained from styrene monomers and (meth)acrylic monomers, and examples include styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylic acid ester copolymers, styrene-α-methylstyrene-acrylic acid copolymers, and styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymers. For 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, 7610 (product names, manufactured by BASF), Movinyl 966A, 975N (product names, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), Vinibran 2586 (manufactured by Nisshin Chemical Industry Co., Ltd.), etc.

[0089] Olefin resins are polymers having olefins such as ethylene, propylene, and butylene as their structural backbone, and known olefin resins can be appropriately selected and used. Commercially available olefin resins can be used, for example, Arrowbase CB-1200, CD-1200 (trade names, manufactured by Unitika Ltd.), etc.

[0090] The primary anionic resin particles are more preferably urethane resin or acrylic resin, and even more preferably urethane resin. In this case, the frictional fastness tends to be superior. It is located there.

[0091] The glass transition temperature (Tg) of the primary anionic resin particles is preferably between -60°C and 50°C, more preferably between -60°C and 40°C, and even more preferably between -30°C and 10°C. Having the glass transition temperature (Tg) of the primary anionic resin particles within this range tends to result in superior fabric conformability (texture). The glass transition temperature is measured, for example, using a differential scanning calorimeter "DSC7000" manufactured by Hitachi High-Tech Science Corporation, in accordance with JIS K7121 (Method for measuring the transition temperature of plastics).

[0092] The content of primary anionic resin particles (solid content concentration) is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, even more preferably 4 to 20% by mass, particularly preferably 6 to 15% by mass, and most particularly preferably 8 to 12% by mass, relative to the total amount of the transparent ink composition. When the content of primary anionic resin particles is within the above range, there is a tendency to obtain better color development.

[0093] 1.2.2.2 Water The transparent ink composition contains water. The same type of water as described in the reaction solution can be used.

[0094] The water content is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more, relative to the total amount of the transparent ink composition. There is no particular upper limit to the water content, but for example, it is preferably 90% by mass or less, more preferably 70% by mass or less, and more preferably 60% by mass or less, relative to the total amount of the transparent ink composition.

[0095] 1.2.2.3 Organic Solvents The transparent ink composition may contain an organic solvent. The type and amount of the organic solvent can be determined in the same way as in the reaction solution described above.

[0096] In transparent ink compositions, the organic solvent preferably contains alkanediols, glycol ethers, and trialkylene glycol; more preferably contains 1,2-alkanediols, 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, it may be even better at suppressing image cracking and ink bleeding.

[0097] The content of the organic solvent is preferably 10 to 55% by mass, more preferably 15 to 45% by mass, even more preferably 20 to 40% by mass, and particularly preferably 25 to 35% by mass, based on the total amount of the transparent ink composition. When the organic solvent content is within the above range, it may be superior in suppressing image cracking and ink bleeding.

[0098] 1.2.2.4 Surfactants The transparent ink composition may contain a surfactant. The type of surfactant can be the same as that used in the reaction solution described above. Preferably, the transparent ink composition contains a silicone-based surfactant.

[0099] 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, based on the total amount of the transparent ink composition. Furthermore, the upper limit of the surfactant content is preferably 3% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.8% by mass or less, relative to the total amount of the transparent ink composition. When the surfactant content is within the above range, it tends to be easier to adjust the permeability of the transparent ink composition to the fabric.

[0100] 1.2.2.5 pH adjusters The transparent ink composition may contain a pH adjuster.

[0101] pH adjusters are not particularly limited, but include appropriate combinations of acids, bases, weak acids, and weak bases. Examples of acids and bases used in such combinations include: inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid; inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium dihydrogen phosphate, disodium hydrogen phosphate, potassium carbonate, sodium carbonate, sodium bicarbonate, and ammonia; organic bases such as triethanolamine, diethanolamine, monoethanolamine, trippropanolamine, triisopropanolamine, diisopropanolamine, and trishydroxymethylaminomethane (THAM); and organic acids such as adipic acid, citric acid, succinic acid, lactic acid, and N,N-bis(2-hydroxymethylaminomethane). Good's buffers such as thioethyl)-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-acetamide)-2-aminoethanesulfonic acid (ACES), cholamine hydrochloride, N-tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid (TES), acetamidoglycine, tricine, glycinamide, bicine, etc., as well as phosphate buffers, citrate buffers, Tris buffers, etc., may be used. Among these, inorganic bases are preferred, and potassium hydroxide is more preferred.

[0102] The above pH adjusting agents may be used individually or in combination of two or more.

[0103] The total content of pH adjusters is preferably 3.00% by mass or less, more preferably 1.00% by mass or less, even more preferably 0.50% by mass or less, particularly preferably 0.30% by mass or less, and most particularly preferably 0.20% by mass or less, relative to the total amount of the transparent ink composition. The lower limit of the total content of pH adjusters is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 0.10% by mass or more, and still more preferably 0.15% by mass or more, relative to the total amount of the transparent ink composition.

[0104] 1.2.2.6 Other Ingredients The transparent ink composition may optionally contain various additives such as preservatives, antifungal agents, rust inhibitors, chelating agents, viscosity modifiers, solubilizers, and antioxidants. When such additives are included, the content is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, and even more preferably 0.1 to 1% by mass, relative to the total amount of the transparent ink composition.

[0105] Furthermore, the transparent ink composition may contain colorants such as pigments, but it is preferable that the amount is 0.2% by mass or less, more preferably 0.1% by mass or less, even more preferably 0.05% by mass or less, and the lower limit is 0% by mass. It is preferable that the transparent ink composition does not contain any colorants.

[0106] 1.2.2.7 Physical Properties The pH of the transparent ink composition is not particularly limited, but is preferably greater than 7, more preferably greater than 7 and 10 or less, and even more preferably greater than 7 and 8 or less.

[0107] The viscosity of the transparent ink composition is preferably 1.0 to 10 mPa·s at 20°C, more preferably 1.5 to 8 mPa·s, even more preferably 3.0 to 8.0 mPa·s, even more preferably 3.0 to 5.0 mPa·s, and particularly preferably 3.0 to 4.0 mPa·s. In particular, a viscosity of 3.0 mPa·s or higher tends to yield better color development. A viscosity of 8.0 mPa·s or lower tends to yield better discharge stability.

[0108] The surface tension of the transparent ink composition is preferably 10 to 40 mN / m at 20°C, more preferably 15 to 35 mN / m, even more preferably 20 to 30 mN / m, and particularly preferably 20 to 27 mN / m.

[0109] 1.3 Anionic colored ink application process The inkjet recording method according to this embodiment includes an anionic colored ink deposition step in which an anionic colored ink composition containing a pigment, second anionic resin particles, and water is deposited onto an area on which a transparent ink composition is attached by an inkjet method.

[0110] 1.3.1 Adhesion Pattern 1.3.1.1 Application amount In the anionic colored ink application process, the amount of colored ink composition applied per unit area to the fabric (V w ) is not particularly limited, but 0.010 g / inch 2 The above is preferable, and 0.050 g / inch 2 The above is more preferable, 0.080 g / inch 2 The above is even more preferable, 0.120 g / inch 2 The above is even more preferable, 0.150 g / inch 2 The above is particularly preferable. Also, the amount of colored ink composition applied per unit area to the fabric (V w ) is 0.300g / inch 2 The following is preferable: 0.200 g / inch 2 The following is more preferable: 0.170 g / inch 2 The following are even more preferable. The application amount of the colored ink composition is 0.010 g / inch. 2 When the amount of the colored ink composition is above this level, the color development tends to be better. 2 The following conditions tend to better suppress image cracking.

[0111] 1.3.1.2 Attachment Order In the inkjet recording method according to this embodiment, the order in which the anionic colored ink adhesion process is performed is as described above in the order in which the anionic transparent ink adhesion process is performed.

[0112] Furthermore, the anionic colored ink application process and the anionic transparent ink application process may be performed as simultaneous application, where the colored ink composition and the transparent ink composition are applied to the same area of ​​the fabric within the same scan, or as layered application, where the colored ink composition and the transparent ink composition are applied to the same area of ​​the fabric in different scans.

[0113] 1.3.2 Colored ink compositions The colored ink composition used in the anionic colored ink application step of the inkjet recording method according to this embodiment is an anionic colored ink composition containing a pigment, secondary anionic resin particles, and water. The components contained in the colored ink composition will be described below.

[0114] A colored ink composition is considered "anionic" if it contains at least one anionic component.

[0115] 1.3.2.1 Pigments The colored ink composition contains a pigment. Examples of pigments include inorganic pigments and organic pigments. It can be used.

[0116] Inorganic pigments are not particularly limited, but examples include carbon blacks such as CI Pigment Black 6 (Lamp Black, Vegetable Black), CI Pigment Black 7 (Furnace Black, Channel Black, Thermal Black, Acetylene Black), CI Pigment Black 8 (Charcoal Black), and CI Pigment Black 10 (Graphite); and white pigments such as iron oxide, titanium oxide, zinc oxide, and silica.

[0117] Examples of carbon black include Mitsubishi Chemical Corporation's No. 2300, 900, MCF88, No. 20B, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, and No. 2200B. Examples of Degussa's Color Black FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Pritex 35, U, V, 140U, and Special Black 6, 5, 4A, 4, and 250. Examples of Columbia Carbon's Conductex SC, Raven 1255, 5750, 5250, 5000, 3500, 1255, and 700. Examples include Cabot's Regal 400R, 330R, 660R, Mogul L, Monarch 700, 800, 880, 900, 1000, 1100, 1300, 1400, and Elftex 12.

[0118] Examples of white pigments include CI Pigment White 1, which is basic lead carbonate; CI Pigment White 4, which is zinc oxide; CI Pigment White 5, which is a mixture of zinc sulfide and barium sulfate; CI Pigment White 6, which is titanium dioxide; CI Pigment White 6:1, which is titanium dioxide containing other metal oxides; CI Pigment White 7, which is zinc sulfide; CI Pigment White 18, which is calcium carbonate; CI Pigment White 19, which is clay; CI Pigment White 20, which is titanium mica; CI Pigment White 21, which is barium sulfate; CI Pigment White 22, which is gypsum; CI Pigment White 26, which is magnesium oxide and silicon dioxide; CI Pigment White 27, which is silicon dioxide; and CI Pigment White 28, which is anhydrous calcium silicate. Among these, it is preferable to use CI Pigment White 6, which has excellent color development and opacity.

[0119] The average particle size of the white pigment is preferably between 100 nm and 500 nm, more preferably between 50 nm and 450 nm, and even more preferably between 200 nm and 400 nm. Setting the average particle size of the white pigment within this range tends to ensure ejection stability from the inkjet head and improve opacity. In this specification, "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 using the dynamic light scattering method or the laser diffraction method described in JIS Z8825. Specifically, a particle size analyzer that uses the dynamic light scattering method as its measurement principle (e.g., "Microtrac UPA," manufactured by Nikkiso Co., Ltd.) can be used.

[0120] Examples of organic pigments include quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, ancenthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimimidazolone pigments, isoindolinone pigments, azomethine pigments, or azo pigments.

[0121] Specific examples of organic pigments include the following:

[0122] 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. Preferably, one or more mixtures selected from the group consisting of CI Pigment Blue 15:3, 15:4, and 60 can be exemplified.

[0123] 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. Preferably, one or more mixtures selected from the group consisting of CI Pigment Red 122, 202, and 209, and CI Pigment Violet 19 can be exemplified.

[0124] 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, 185, etc. Preferably, one or more mixtures selected from the group consisting of CI Pigment Yellow 74, 109, 110, 128, 138, 150, and 180 can be exemplified.

[0125] Other colored pigments can also be used. For example, orange pigment and green pigment can be used.

[0126] Pigments may be used individually or in combination of two or more types.

[0127] The colored ink composition is preferably a white ink composition containing a white pigment (hereinafter also referred to as "white ink"). A colored ink composition containing a white pigment is suitable for forming a white ink layer as a base layer, but since a relatively large amount of white ink needs to be applied, a large amount of acidic reaction solution needs to be applied, which makes the coating film cracking more pronounced. In contrast, the inkjet recording method according to this embodiment tends to suppress image cracking well even with a colored ink composition containing a white pigment.

[0128] In this specification, the term "white" in relation to white ink compositions, white pigments, etc., does not refer only to pure white, but also includes chromatic and achromatic colors, as well as glossy colors, as long as they are visible as white. Furthermore, it includes inks and colorants that are named and sold in a way that suggests they are white inks or white colorants.

[0129] More quantitatively, "white" refers to a recording that, for example, in CIELAB, L * Not only colors where L is 100, * is between 60 and 100, and a * and b * This also includes colors that are within ±10 of each other. More specifically, for example, when a white ink composition is recorded in an amount sufficient to adequately cover the surface of a transparent film recording medium with the ink, the brightness (L) of the recorded portion of the recording material is increased. * ) and chromaticity (a * , b * When the color of the material is measured using a spectrophotometer compliant with CIELAB, it is preferable that the result falls within the above range. A recording with a sufficient coating amount is, for example, 15 mg / inch 2 This is the amount of adhesion. More preferably, 80 ≤ L * ≤100, -4.5 ≤a * ≤ 2, -10 ≤ b * The value is ≤2.5. An example of a transparent film recording medium is the LAG Jet E-1000ZC (manufactured by Lintec Corporation). An example of a spectrophotometer compliant with CIELAB is the Spectrolino (product name, manufactured by GretagMacbeth Corporation), and measurements are taken with the following conditions: D50 light source, observation field of view 2°, density DIN NB, white reference Abs, filter No, and measurement mode Reflectance. Anything other than "white" will be referred to as "non-white."

[0130] The pigment may be dispersed using a pigment dispersant. Alternatively, the pigment surface may be oxidized or sulfonated with ozone, hypochlorous acid, fuming sulfuric acid, etc., to form a self-dispersing pigment which can then be dispersed for use.

[0131] Pigment dispersants have the function of dispersing pigments in ink. Pigment dispersants may be water-soluble, but those that are not completely water-soluble are preferred. It is thought that they disperse pigments by partially or completely binding to or adsorbing to the pigment, thereby increasing the hydrophilicity of the pigment surface.

[0132] Pigment dispersants are polymer compounds, and examples include acrylic resins and their salts 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.

[0133] Furthermore, examples of pigment dispersants include maleic acid-based resins and their salts, such as styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinylnaphthalene-maleic acid copolymer, and vinyl acetate-maleic acid ester copolymer; urethane-based resins and their salts, with or without crosslinking structures; polyvinyl alcohols; and resins such as vinyl acetate-crotonic acid copolymer and its salts.

[0134] Furthermore, acrylic resins may be copolymers of acrylic monomers (acrylic monomers) as described above, or copolymers of acrylic monomers with other monomers. For example, acrylic vinyl resin, which is a copolymer of vinyl monomers as the other monomer, is also called an acrylic resin. Also, among the styrene resins mentioned above, those which are copolymers of styrene monomers and acrylic monomers are included in acrylic resins. Moreover, when referring to acrylic resins, their salts and esterified products are also included.

[0135] Examples of commercially available pigment dispersants include X-200, X-1, X-205, X-220, X-228 (manufactured by Seikoh PMC), Nopcospers® 6100, 6110 (manufactured by Sunnopco Corporation), Joncryl 67, 586, 611, 678, 680, 682, 819 (manufactured by BASF), DISPERBYK-190 (manufactured by Bic Chemie Japan Co., Ltd.), N-EA137, N-EA157, N-EA167, N-EA177, N-EA197D, N-EA207D, and E-EN10 (manufactured by Daiichi Kogyo Seiyaku).

[0136] Examples of commercially available acrylic pigment dispersants include BYK-187, BYK-190, BYK-191, BYK-194N, BYK-199 (manufactured by Big Chemie Co., Ltd.), Aron A-210, A6114, AS-1100, AS-1800, A-30SL, A-7250, and CL-2 (manufactured by Toagosei Co., Ltd.).

[0137] Commercially available urethane-based pigment dispersants include BYK-182, BYK-183, BYK-184, BYK-185 (manufactured by Bic Chemi Co., Ltd.), TEGO Disperse710 (manufactured by Evonic Tego Chemi), and Borchi® Gen1350 (manufactured by OMG Borschers).

[0138] The pigment dispersant is preferably an anionic pigment dispersant. An "anionic pigment dispersant" refers to a pigment dispersant that has a negative charge as a whole, and it is preferable that it has one or more anionic groups selected from carboxyl groups, sulfonic acid groups, phosphate groups, etc.

[0139] The pigment in the colored ink composition is preferably anionic. In this case, the agglomeration effect by the reaction solution described above is superior, and therefore better color development tends to be obtained. A pigment is anionic if it has a negative charge as a whole, and it is preferable that it has one or more anionic groups selected from, for example, carboxyl groups, sulfonic acid groups, phosphate groups, etc. The anionic groups may be directly present on the pigment surface, or they may be present via an anionic resin dispersant adsorbed or bound to the pigment.

[0140] The pigment dispersant may be used alone or in combination of two or more types. The total content of the pigment dispersant is preferably 0.1% to 30% by mass, more preferably 0.5% to 25% by mass, even more preferably 1% to 20% by mass, and particularly preferably 1.5% to 15% by mass, based on 100% by mass of the colored ink composition. A pigment dispersant content of 0.1% by mass or more tends to ensure the dispersion stability of the pigment. Furthermore, a pigment dispersant content of 30% by mass or less tends to keep the viscosity of the colored ink composition low.

[0141] Furthermore, it is even more preferable that the weight-average molecular weight of the pigment dispersant be 500 or higher. Using such a pigment dispersant tends to result in less odor and improved dispersion stability of the pigment.

[0142] When dispersing a pigment (especially a white pigment) with a pigment dispersant, the ratio of pigment to pigment dispersant is preferably 10:1 to 1:10, and more preferably 4:1 to 1:3.

[0143] The pigment content (especially white pigment) is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, even more preferably 4 to 20% by mass, particularly preferably 6 to 15% by mass, and most preferably 8 to 12% by mass, relative to the total amount of the colored ink composition. When the pigment content is within the above range, better color development (whiteness) tends to be obtained.

[0144] 1.3.2.2 Second anionic resin particles The colored ink composition contains secondary anionic resin particles. The secondary anionic resin particles can be in the same form as the primary anionic resin particles contained in the transparent ink composition described above, so a detailed explanation is omitted. The secondary anionic resin particles and the primary anionic resin particles may be the same or different.

[0145] When a colored ink composition contains secondary anionic resin particles, the sealing effect of the colored ink composition is more pronounced on the resin layer formed by the aggregation of primary anionic resin particles in the transparent ink near the surface of the fabric, which tends to improve color development and other properties.

[0146] The secondary anionic resin particles in the colored ink composition are preferably urethane resin or acrylic resin, and more preferably urethane resin. In this case, the friction fastness tends to be superior.

[0147] The glass transition temperature (Tg) of the secondary anionic resin particles in the colored ink composition is preferably -60°C to 50°C, more preferably -60°C to 40°C, and even more preferably -30°C to 10°C. Having the glass transition temperature (Tg) of the secondary anionic resin particles within this range tends to result in superior fabric conformability (texture).

[0148] The content (solid content) of secondary anionic resin particles is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, even more preferably 4 to 20% by mass, particularly preferably 6 to 15% by mass, and most particularly preferably 8 to 12% by mass, relative to the total amount of the colored ink composition. When the content of secondary anionic resin particles is within the above range, it tends to be superior in suppressing cracking and ink bleeding in images.

[0149] 1.3.2.3 Water The colored ink composition contains water. The same type of water as described in the reaction solution can be used.

[0150] The water content is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more, relative to the total amount of the colored ink composition. There is no particular upper limit to the water content, but for example, it is preferably 90% by mass or less, and more preferably 70% by mass or less, relative to the total amount of the colored ink composition.

[0151] 1.3.2.4 Organic Solvents The colored ink composition may contain an organic solvent. The type and amount of the organic solvent can be determined in the same way as in the reaction solution described above.

[0152] In a colored ink composition, the organic solvent preferably contains alkanediols, glycol ethers, and trialkylene glycol; more preferably contains 1,2-alkanediols, 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, it may be even better at suppressing image cracking and ink bleeding.

[0153] Furthermore, the colored ink composition preferably contains 3.0% by mass or more of an organic solvent with a standard boiling point of 250°C or higher, more preferably 5.0% by mass or more, and even more preferably 7.0% by mass or more. The upper limit of the content is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. When organic solvents with a standard boiling point of 250°C or higher are included within the above range, the nozzles of the inkjet head tend to be moistened, which can improve ejection reliability (continuous printing stability).

[0154] Examples of organic solvents with a standard boiling point of 250°C or higher include glycerin and polyethylene glycol monomethyl ether. Organic solvents with a standard boiling point of 250°C or higher are also called humectants. More preferably, the organic solvent has a standard boiling point of 270°C or higher, and even more preferably 280°C or higher.

[0155] The content of the organic solvent is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, even more preferably 15 to 30% by mass, and particularly preferably 20 to 25% by mass, based on the total amount of the colored ink composition. When the organic solvent content is within the above range, it may be superior in suppressing cracking and ink bleeding in the image.

[0156] 1.3.2.5 Surfactants The colored ink composition may contain a surfactant. The type of surfactant can be the same as that used in the reaction solution described above. Preferably, the colored ink composition contains a silicone-based surfactant.

[0157] The lower limit of the surfactant content is 0.05% by mass or more relative to the total amount of the colored ink composition. Preferably, 0.1% by mass or more is more preferable, 0.2% by mass or more is even more preferable, and 0.3% by mass or more is particularly preferable. Furthermore, the upper limit of the surfactant content is preferably 3% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less, relative to the total amount of the colored ink composition. When the surfactant content is within the above range, it tends to be easier to adjust the permeability of the colored ink composition to the fabric.

[0158] 1.3.2.6 pH adjusters The colored ink composition may contain a pH adjuster. The type and amount of the pH adjuster can be the same as that of the transparent ink composition described above.

[0159] 1.3.2.7 Other Ingredients The colored ink composition may optionally contain additives such as preservatives, antifungal agents, rust inhibitors, chelating agents, viscosity modifiers, solubilizers, and antioxidants. When such additives are included, the content is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, and even more preferably 0.1 to 1% by mass, relative to the total amount of the colored ink composition.

[0160] 1.3.2.8 Physical Properties The pH of the colored ink composition is not particularly limited, but is preferably greater than 7, more preferably greater than 7 and 10 or less, and even more preferably greater than 7 and 8 or less.

[0161] The viscosity of the colored ink composition is preferably 1.0 to 10 mPa·s at 20°C, more preferably 2.0 to 10 mPa·s, even more preferably 3.0 to 8.0 mPa·s, and particularly preferably 4.0 to 6.0 mPa·s. In particular, a viscosity of 4.0 mPa·s or higher tends to yield better color development. A viscosity of 6.0 mPa·s or lower tends to yield better discharge stability.

[0162] The surface tension of the colored ink composition is preferably 10 to 40 mN / m at 20°C, more preferably 15 to 35 mN / m, even more preferably 20 to 30 mN / m, and particularly preferably 20 to 27 mN / m.

[0163] 1.4 Anionic Solution Coating Process The inkjet recording method according to this embodiment includes an anionic solution coating step in which an anionic alkaline aqueous solution with a pH greater than 8.0 is applied to an area to which a colored ink composition is attached.

[0164] 1.4.1 Adhesion Pattern 1.4.1.1 Application Method As the method for applying the aqueous alkali solution in the anionic solution application step, it is not particularly limited. For example, there are a dipping application method in which the fabric is dipped in the aqueous alkali solution, a roller application method in which the aqueous alkali solution is applied using a mangle roller, a roll coater, etc., a spray application method in which the aqueous alkali solution is sprayed by a spray device, etc., and an inkjet application method in which the aqueous alkali solution is sprayed by an inkjet method. These application methods may be used alone to attach the aqueous alkali solution to the fabric, or two or more methods may be combined to attach the aqueous alkali solution to the fabric.

[0165] The anionic solution application step is preferably a method in which the aqueous alkali solution can be attached only to the region where the colored ink composition is attached, and it is particularly preferably performed by an inkjet method. When performing the anionic solution application step by the inkjet method, since the application area and the application amount can be precisely controlled, the aqueous alkali solution can be attached evenly and in a necessary and sufficient amount to the region where the colored ink is attached, and thus it tends to be excellent in suppressing image cracking and ink bleeding. amount can be attached, and as a result, it tends to be excellent in suppressing image cracking and ink bleeding.

[0166] 1.4.1.2 Application amount In the anionic solution application step, the application amount (V n ) of the aqueous alkali solution per unit area of the fabric is not particularly limited, but it is preferably 0.010 g / inch 2 or more, more preferably 0.050 g / inch 2 or more, even more preferably 0.080 g / inch 2 or more, still more preferably 0.120 g / inch 2 or more, and particularly preferably 0.150 g / inch 2 or more. Also, the application amount (V n ) of the aqueous alkali solution per unit area of the fabric is preferably 0.300 g / inch 2 or less, more preferably 0.200 g / inch 2 or less, and even more preferably 0.170 g / inch 2 or less. The application rate of the alkaline aqueous solution is 0.010 g / inch. 2 The above conditions tend to result in better suppression of image cracking.

[0167] 1.4.1.3 Order of attachment In the inkjet recording method according to this embodiment, the order in which the anionic solution coating step is performed is not particularly limited, as long as it allows the alkaline aqueous solution to be applied to the area to which the colored ink composition is attached. For example, the anionic solution coating step may be performed after or simultaneously with the anionic colored ink application step. However, when the anionic solution coating step is performed simultaneously with the anionic colored ink application step, the colored ink composition is applied to the fabric first, and then the alkaline aqueous solution is applied to the fabric.

[0168] The anionic solution coating step and the anionic colored ink adhesion step may be performed as simultaneous adhesion, where the alkaline aqueous solution and the colored ink composition are applied to the same area on the fabric within the same scan, or as layered adhesion, where the alkaline aqueous solution and the colored ink composition are applied to the same area on the fabric in different scans. When applying the two materials simultaneously, the order in which they should be applied to the fabric is as follows: first, the colored ink composition should be applied, followed by the alkaline aqueous solution.

[0169] The time difference between the adhesion of the alkaline aqueous solution and the colored ink composition in the same area of ​​the fabric can be the same as the time difference between the adhesion of the reaction solution and the transparent ink composition described above.

[0170] 1.4.2 Alkaline aqueous solution The alkaline aqueous solution used in the anionic solution coating step of the inkjet recording method according to this embodiment is an anionic alkaline aqueous solution with a pH greater than 8.0.

[0171] An alkaline aqueous solution is considered "anionic" if its pH is greater than 7.

[0172] The pH of the alkaline aqueous solution is not particularly limited as long as it is greater than 8.0, but is preferably 8.3 or higher, more preferably 8.5 or higher, even more preferably 8.7 or higher, and particularly preferably 9.0 or higher. Furthermore, the pH of the alkaline aqueous solution is preferably 12.0 or lower, more preferably 11.0 or lower, and even more preferably 10.0 or lower. From the viewpoint of reducing skin irritation, the pH of the alkaline aqueous solution is preferably 11.0 or lower.

[0173] The following describes the various components contained in the alkaline aqueous solution.

[0174] 1.4.2.1 Alkaline components Alkaline aqueous solutions may contain alkaline components. The alkaline component is not particularly limited as long as it is a substance that dissolves in water and generates hydroxide ions, for example, anionic Examples include resin particles, inorganic alkalis, and organic alkalis. From the viewpoint of efficiently neutralizing excess acid, it is preferable to use an inorganic alkali or an organic alkali. This allows for better suppression of cracking of the coating film. From this viewpoint, it is also preferable to use an inorganic alkali or an organic alkali and not use anionic resin particles. On the other hand, from the viewpoint of neutralizing excess acid and improving the abrasion resistance of the coating film, it is also preferable to use anionic resin particles.

[0175] Since the anionic resin particles are the same as the first anionic resin particles and second anionic resin particles described above, their explanation will be omitted.

[0176] Examples of inorganic alkalis include lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium dihydrogen phosphate, disodium hydrogen phosphate, potassium carbonate, sodium carbonate, sodium bicarbonate, and ammonia.

[0177] Examples of organic alkalis include triethanolamine, diethanolamine, monoethanolamine, trippropanolamine, triisopropanolamine, diisopropanolamine, and trishydroxymethylaminomethane (THAM).

[0178] The alkaline aqueous solution preferably contains one or more alkaline components selected from anionic resin particles, inorganic alkalis, and organic alkalis. When such alkaline components are included, the pH of the alkaline aqueous solution can be stably maintained above 8.0, which tends to lead to better suppression of cracking in the image. The alkaline component content is preferably 0.03% by mass or more, more preferably 0.06% by mass or more, and particularly preferably 0.15% by mass or more, relative to the total amount of the alkaline aqueous solution. There is no particular upper limit to the alkaline component content, but it is preferably 15.0% by mass or less, more preferably 12.0% by mass or less, and particularly preferably 10.0% by mass or less, relative to the total amount of the alkaline aqueous solution. When using inorganic alkali or organic alkali and not using anionic resin particles, it is preferably 2.0% by mass or less, more preferably 1.0% by mass or less, and particularly preferably 0.5% by mass or less.

[0179] 1.4.2.2 Water The alkaline aqueous solution contains water. The same type of water used in the reaction solution described above can be used.

[0180] The water content is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly preferably 60% by mass or more, relative to the total amount of the alkaline aqueous solution. There is no particular upper limit to the water content, but for example, it is preferably 90% by mass or less, and more preferably 80% by mass or less, relative to the total amount of the alkaline aqueous solution.

[0181] 1.4.2.3 Organic Solvents The alkaline aqueous solution may contain an organic solvent. The type and amount of the organic solvent can be the same as in the transparent ink composition described above.

[0182] 1.4.2.4 Surfactants The alkaline aqueous solution may contain a surfactant. The type and amount of surfactant can be the same as in the transparent ink composition described above.

[0183] 1.4.2.5 Other ingredients The alkaline aqueous solution may contain various additives as needed, such as preservatives, fungicides, rust inhibitors, chelating agents, viscosity modifiers, solubilizers, and antioxidants. When this is done, the content is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, and even more preferably 0.1 to 1% by mass, relative to the total amount of the alkaline aqueous solution.

[0184] Furthermore, the alkaline aqueous solution may contain colorants such as pigments, but it is preferable that the amount is 0.2% by mass or less, more preferably 0.1% by mass or less, even more preferably 0.05% by mass or less, and the lower limit is 0% by mass. It is preferable that the alkaline aqueous solution does not contain colorants. Furthermore, the content of the alkaline component relative to the solid content other than the surfactant in the alkaline aqueous solution is preferably 80.0% by mass or more, more preferably 90.0% by mass or more, even more preferably 95.0% by mass or more, and particularly preferably 99.0% by mass or more.

[0185] 1.4.2.6 Physical Properties The viscosity of the alkaline aqueous solution is preferably 1.0 to 10 mPa·s at 20°C, more preferably 1.5 to 8 mPa·s, even more preferably 3.0 to 8.0 mPa·s, even more preferably 3.0 to 5.0 mPa·s, and particularly preferably 3.0 to 4.0 mPa·s. In particular, a viscosity of 8.0 mPa·s or less tends to yield better ejection stability when ejected by the inkjet method.

[0186] The surface tension of the aqueous alkali solution is preferably 10 to 40 mN / m at 20°C, more preferably 15 to 35 mN / m, still more preferably 20 to 30 mN / m, and particularly preferably 20 to 27 mN / m.

[0187] 1.5 Drying process The inkjet recording method according to this embodiment may have a drying process after the aforementioned anionic solution application process. When the drying process is performed before the anionic solution application process, excessive aggregation is likely to proceed due to the acid not neutralized by the anionic component in the ink, and there is a risk of image cracking. On the other hand, when the drying process is performed after the anionic solution application process, the remaining acid can be neutralized before excessive aggregation proceeds, so it tends to be excellent in suppressing image cracking.

[0188] The drying method in the drying process is not particularly limited, and examples include heat press, belt conveyor oven, normal pressure steam method, high pressure steam method, thermofix method, air blowing, etc. The heat source for drying is not particularly limited, and for example, an infrared lamp can be used. Note that the drying may not involve heating.

[0189] The 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 moisture volatilizes. The drying temperature is, for example, preferably 100°C or higher and 250°C or lower, more preferably 120°C or higher and 230°C or lower, still more preferably 130°C or higher and 200°C or lower, and particularly preferably 130°C or higher and 180°C or lower. Here, the drying temperature in the drying process refers to the surface temperature of an image or the like formed on the fabric. The drying time is not particularly limited, but for example, it is preferably 10 seconds or more and 5 minutes or less, more preferably 20 seconds or more and 3 minutes or less, and still more preferably 60 seconds or more and 3 minutes or less.

[0190] The drying process may be performed while applying pressure by a heat press or the like. The pressure to be applied is not particularly limited, but is 1 to 10 N / cm 2Preferably, the load is 1 to 8 N / cm². 2 It is more preferable that the load is 1-5 N / cm². 2 It is even more preferable that this be the case.

[0191] 1.6 Other processes The inkjet recording method according to this embodiment may include steps such as washing the recorded fabric with water and heating and drying it again. During the washing, if necessary, a soaping treatment may be performed to wash away any ink or other components that were not fixed to the fabric using a hot soap solution or the like.

[0192] 1.7 Inkjet Recording Devices An inkjet recording apparatus that can be preferably used in the inkjet recording method according to this embodiment will be described.

[0193] As an example of an inkjet recording device, Figure 1 shows a perspective view of a serial printer. As shown in Figure 1, the serial printer 20 comprises a transport unit 220 and a recording unit 230. The transport unit 220 transports the recording medium F supplied to the serial printer to the recording unit 230 and discharges the recorded recording medium outside the serial printer after recording. Specifically, the transport unit 220 has feed rollers and transports the fed recording medium F in the transport direction TD.

[0194] Furthermore, the recording unit 230 includes a carriage 234 on which an inkjet head 231 is mounted, having a nozzle for ejecting the above-mentioned reaction solution onto the recording medium F sent from the transport unit 220, a nozzle for ejecting the above-mentioned transparent ink composition, a nozzle for ejecting the above-mentioned colored ink composition, and a nozzle for ejecting the above-mentioned alkaline aqueous solution as needed, and a carriage movement mechanism 235 for moving the carriage 234 in the scanning direction SD of the recording medium F.

[0195] Figure 2 shows an example of the nozzle rows on the nozzle surface of the inkjet head 231. In Figure 2, the inkjet head 231 has multiple nozzle rows consisting of multiple nozzles arranged along the direction in which the inkjet head 231 moves (scanning direction SD) and the direction intersecting it (transport direction TD), namely rows A to H and rows A' to B' along the scanning direction SD. In this case, when the nozzle row for discharging the reaction solution is projected along the scanning direction SD, by arranging it so that at least a portion of it overlaps with the nozzle row for discharging the transparent ink composition in the transport direction TD, the reaction solution and the transparent ink composition can be applied to the same area of ​​the fabric within the same scan. Similarly, the reaction solution and the colored ink composition can be applied to the same area of ​​the fabric within the same scan. The inks to be dispensed from each nozzle row are selected as appropriate, but for example, it is preferable to select rows A to B as nozzles that dispense the reaction solution, rows C to D as nozzles that dispense the transparent ink composition, rows E to H as nozzles that dispense the colored ink composition, and rows A' to B' as nozzles that dispense the alkaline aqueous solution.

[0196] In a serial printer, the inkjet head 231 has a length smaller than the width of the recording medium, and recording is performed as the head moves in a scanning direction SD that intersects the transport direction TD of the recording medium F. In a serial printer, the head 231 is mounted on a carriage 234 that moves in a predetermined direction, and as the carriage moves, the head moves, ejecting the ink composition, reaction solution, and optionally an alkaline aqueous solution onto the recording medium. The recording medium may be transported between scans.

[0197] Furthermore, the inkjet device is not limited to the serial printer described above, but may also be a line printer. Figure 3 shows a schematic side view of a line printer as another example of an inkjet recording device. As shown in Figure 3, the line printer 1 comprises a feeding unit 100, a transport mechanism 200 for transporting the recording medium in the transport direction, a line head 300 for ejecting and adhering ink to the recording medium, a control unit 500, and an ejection unit 700.

[0198] The transport mechanism is a mechanism that transports the recording medium in the transport direction. In Figure 3, a roll-shaped recording medium F is supplied from the feeding unit 100 to the transport mechanism 200, and the transport mechanism 200 is supplied from the feeding unit 1 The system is configured to transport the recording medium F sent from 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 sent recording medium F to the line head 300 on the downstream side in the transport direction. As for the transport method of the transport mechanism 200, conventionally known methods can be used as appropriate, and one or more rollers, or a belt that is fed by rollers may be used.

[0199] The line printer 1 has a line head 300 having a length corresponding to the width of the recording medium F. The line head 300 may be composed of multiple line jets, and in Figure 3, the line head 300 is composed of a first line head 310, a second line head 320, a third line head 330, and a fourth line head 340. When it is not necessary to distinguish between the first line head 310, the second line head 320, the third line head 330, and the fourth line head 340, it is simply referred to as the line head 300.

[0200] The line head 300 has cavities for containing a reaction solution, a transparent ink composition, a colored ink composition, and optionally an alkaline aqueous solution (ink, etc.), an ejection drive unit provided for each cavity, and a nozzle for ejecting the ink, etc. Multiple cavities, and the ejection drive units and nozzles provided for each cavity, may be provided on a single 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 bubbles in the ink by generating heat and ejecting it.

[0201] Preferably, the line head 300 is configured such that the reaction solution is discharged from the first line head 310 and the transparent ink composition is discharged from the second line head 320. This allows the reaction solution and the transparent ink composition to be applied to the same area of ​​the fabric within the same scanning area. Alternatively, it is preferable that the colored ink composition is discharged from the third line head 330 and the alkaline aqueous solution is discharged from the fourth line head 340.

[0202] In line printers, the print head is fixed (almost) without moving, and recording is performed in a single scan of the inkjet head. Line printers have an advantage over serial printers in that they have a faster recording speed.

[0203] 2. Examples The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" below refers to mass.

[0204] 2.1 Preparation of reaction solution, transparent ink composition, colored ink composition and alkaline aqueous solution Each component was placed in a container to obtain the compositions shown in Table 1 (Figure 4), mixed and stirred, and then filtered through a 5 μm membrane filter to obtain the reaction solutions (composition R1, composition R2), transparent ink composition (composition G1), colored ink composition (composition W1), and alkaline aqueous solutions (composition N1, composition N2) for each example. Unless otherwise specified, the numerical values ​​for each component shown in the table represent mass percent. In the table, the mass percent for pigment and resin particles represent the solid content concentration, and deionized water was added so that the total mass of the composition was 100% by mass.

[0205] As the pigment, a titanium dioxide dispersion prepared in advance by the following procedure was used. 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. Three parts by mass of pigment were mixed with one part by mass of dispersant and ten parts by mass of ion-exchanged water. The resulting mixture was premixed and then dispersed using a bead mill disperser (manufactured by Kotobuki Kogyo Co., Ltd., UAM). Using -015), the mixture was dispersed with zirconia beads with a diameter of 0.03 mm at a peripheral speed of 10 m / s and a liquid temperature of 30°C for 15 minutes. The coarse particles were then centrifuged using a centrifuge (Model-3600, manufactured by Kuboyama Shoji Co., Ltd.) to obtain a titanium oxide dispersion (cationically responsive).

[0206] Further explanation is provided regarding the information in Table 1. • Takerack WS-6021 (product name, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.; the urethane resin in Table 2 also uses this product) • BYK-348 (product name, manufactured by BYK, silicone-based surfactant) • Orphine E1010 (product name, manufactured by Nisshin Chemical Industry Co., Ltd., acetylene glycol-based surfactant)

[0207] Viscosity was measured using a viscoelasticity tester MCR-300 (product name, manufactured by Pysica) at a temperature of 20°C. Surface tension was measured using an automatic surface tension meter CBVP-Z (product name, manufactured by Kyowa Interface Science Co., Ltd.) by checking the surface tension when a platinum plate was wetted with the composition at a temperature of 25°C.

[0208] In Example 7 of Table 2 (Figure 5), as the alkaline aqueous solution, composition G1' was used, which was the same as composition G1, except that the pH was adjusted to 8.3 by adjusting the alkaline component and water content in the composition of transparent ink 1 (composition G1).

[0209] 2.2 Recording Conditions Using the reaction solutions (Composition R1, Composition R2), transparent ink composition (Composition G1), colored ink composition (Composition W1), and alkaline aqueous solutions (Composition N1, Composition N2) obtained by the above preparation, based on the following conditions and the conditions described in Tables 2 (Figure 5) to Table 3 (Figure 6), the inkjet recording methods according to each example and each comparative example were performed to obtain recorded materials.

[0210] · Printer: Modified SC-F2200 (manufactured by Seiko Epson Corporation) · Drying: The fabric was dried under the conditions of 160 °C for 3 minutes using a belt conveyor oven (manufactured by M&R, Fusion R 36-6-4). · Fabric: 100% cotton, black T-shirt (Printstar), L in the colored part * Value 12

[0211] 〔Coating conditions〕 · Image resolution: 1200 × 600 dpi · Driving duty for each column: 100% · CR (carriage) movement speed: 6 - 40 inch / s · Head drive frequency: 3 - 60 kHz · Coating amount adjustment: Adjusted by CR movement speed and drive frequency · Printed image pattern (solid pattern): (1 inch × 10 inch)

[0212] The head nozzle configuration was as shown in Figure 2, with nozzle columns for discharging the reaction solution in columns A - B, the transparent ink composition in columns C - D, the colored ink composition in columns E - H, and the alkaline aqueous solution in columns A' - B'.

[0213] In "(1) - (3)" in the "Printing order" in Tables 2 - 3, it indicates the following order. (1): In the first scan, the reaction solution and the transparent ink composition are made to adhere to the same region on the fabric within the same scan. In the second scan, the reaction solution and the colored ink composition are made to adhere to the region on the fabric where the transparent ink composition has adhered within the same scan. In the third scan, an alkaline aqueous solution is applied to the area of ​​the fabric where the colored ink composition is attached.

[0214] (2): In the first scan, the reaction solution and the transparent ink composition are applied to the same area of ​​the fabric within the same scan. In the second scan, the colored ink composition is applied to the area of ​​the fabric where the transparent ink composition has been applied. In the third scan, an alkaline aqueous solution is applied to the area of ​​the fabric where the colored ink composition is attached.

[0215] (3): In the first scan, the reaction solution, the transparent ink composition, and the colored ink composition are applied to the same area of ​​the fabric within the same scan. In the second scan, an alkaline aqueous solution is applied to the area of ​​the fabric where the colored ink composition is attached.

[0216] Note that the coating weight of the reaction solution in Tables 2 and 3 is the total amount of reaction solution applied during the first and second scans, assuming the printing sequence is (1).

[0217] 2.3 Evaluation Method 2.3.1 Color development In the recording obtained above, a fluorescence spectrometer (Konica Minolta, Inc., FD-7) was used to measure L * The value (whiteness) was measured, and the color development (whiteness) was determined according to the following criteria. (Judgment criteria) AA:L * 85[-] or higher A:L * 74-84[-] B:L * 65-74[-] C:L * Less than 65[-]

[0218] 2.3.2 Cracks in images The printed images obtained from the above-mentioned materials were observed using a digital microscope (VHX-5000 / Keyence) to determine the number of cracks within a 1-inch square of the ink coating. Cracks in the image (white ink layer) were judged according to the following criteria. (Judgment criteria) A: No cracks in the ink coating (1 inch x 1 inch). B: The number of cracks in the ink coating (1 inch x 1 inch) is 4 or less. C: 5 or more cracks within the ink coating (1 inch x 1 inch)

[0219] 2.3.3 Ink bleeding The boundary between the printed and unprinted areas was observed using a digital microscope (VHX-5000 / Keyence) on the records obtained as described above. If bleeding of colored ink into the unprinted area was observed, the distance perpendicular to the boundary line was measured. The bleeding of the ink (white ink) was judged according to the following criteria. The judgment was made in units of 1 mm, and decimal values ​​were rounded to the nearest whole number. If the bleeding was 1 mm or less, it was judged as not bleeding. (Judgment criteria) A: No bleeding into non-printed areas. B: Smudges on non-printed areas are 2mm-4mm. C: Smudges of 5mm or more into the non-printed area

[0220] 2.4 Evaluation Results The evaluation results are shown in Tables 2 and 3. From the results shown in Tables 2 to 3, an acidic reaction liquid containing an acid and water is adhered to a fabric by an inkjet method, an anionic transparent ink composition containing first anionic resin particles and water is adhered to the fabric by an inkjet method, an anionic colored ink composition containing a pigment, second anionic resin particles and water is adhered to the region where the transparent ink composition has adhered by an inkjet method, and an anionic solution coating step of adhering an anionic alkaline aqueous solution with a pH exceeding 8.0 to the region where the colored ink composition has adhered. In any of the inkjet recording methods according to the respective examples, the suppression of image cracking and the suppression of ink bleeding were good.

[0221] On the other hand, the inkjet recording methods according to the respective comparative examples that do not satisfy the above configuration were inferior in at least one of the suppression of image cracking and the suppression of ink bleeding.

[0222] The following content is derived from the above-described embodiments.

[0223] One aspect of the inkjet recording method is an acidic reaction liquid adhesion step of adhering an acidic reaction liquid containing an acid and water to a fabric by an inkjet method, an anionic transparent ink adhesion step of adhering an anionic transparent ink composition containing first anionic resin particles and water to the fabric by an inkjet method, an anionic colored ink adhesion step of adhering an anionic colored ink composition containing a pigment, second anionic resin particles and water to the region where the transparent ink composition has adhered by an inkjet method, and an anionic solution coating step of adhering an anionic alkaline aqueous solution with a pH exceeding 8.0 to the region where the colored ink composition has adhered.

[0224] In one aspect of the above inkjet recording method, In the acidic reaction solution application step, the amount of the reaction solution applied to the fabric per unit area (X) is, In the anionic transparent ink application step, the neutralization power (Y) of the transparent ink composition applied to the fabric with respect to the reaction solution is, In the anionic colored ink application step, the neutralization power (Z) of the colored ink composition applied to the fabric with respect to the reaction solution may satisfy the following relationship. X - (Y + Z) ≥ 0 ... Equation (1)

[0225] In any embodiment of the above inkjet recording method, Furthermore, X, Y and Z, In the anionic solution coating step, the neutralization power (W) of the alkaline aqueous solution attached to the area to which the colored ink composition is attached to the reaction solution may satisfy the following relationship. W≧X-(Y+Z) ...Equation (2)

[0226] In any embodiment of the above inkjet recording method, The acid may be a compound having 1 to 3 carboxyl groups.

[0227] In any embodiment of the above inkjet recording method, The aforementioned alkaline aqueous solution may contain one or more alkaline components selected from anionic resin particles, inorganic alkalis, and organic alkalis.

[0228] In any embodiment of the above inkjet recording method, The anionic solution coating step may be carried out by an inkjet method.

[0229] In any embodiment of the above inkjet recording method, A drying step may be included after the anionic solution coating step.

[0230] In any embodiment of the above inkjet recording method, The pH of the aforementioned alkaline aqueous solution may be 11.0 or less.

[0231] The present invention is not limited to the embodiments described above, and various modifications are possible. For example, the present invention includes configurations that are substantially identical to the configurations described in the embodiments, for example, configurations that have the same function, method and result, or configurations that have 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. Furthermore, the present invention includes configurations that produce the same effects or achieve the same purpose as the configurations described in the embodiments. Furthermore, the present invention includes configurations that add known technology to the configurations described in the embodiments. [Explanation of Symbols]

[0232] 20...Serial printer, 220...Transport unit, 230...Recording unit, 231...Inkjet head, 234...Carriage, 235...Carriage movement mechanism, 1...Line printer, 100...Feeding unit, 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 unit, Y...Feeding direction, F...Recording medium, SD...Scanning direction, TD...Transport direction.

Claims

1. An acidic reaction solution application step in which an acidic reaction solution containing acid and water is applied to the fabric by an inkjet method, An anionic transparent ink application step in which an anionic transparent ink composition containing primary anionic resin particles and water is applied to the fabric by an inkjet method, An anionic colored ink application step involves applying an anionic colored ink composition containing a pigment, secondary anionic resin particles, and water to an area on which the transparent ink composition is attached by an inkjet method. An inkjet recording method comprising an anionic solution coating step of applying an anionic alkaline aqueous solution with a pH greater than 8.0 to an area to which the colored ink composition is attached.

2. In the acidic reaction solution application step, the amount of the reaction solution applied to the fabric per unit area (X) is, In the anionic transparent ink application step, the neutralization power (Y) of the transparent ink composition applied to the fabric with respect to the reaction solution is, The inkjet recording method according to claim 1, wherein, in the anionic colored ink attachment step, the neutralization power equivalent value (Z) of the colored ink composition attached to the fabric with respect to the reaction solution satisfies the following relationship. X-(Y+Z)≧0...Formula (1)

3. Furthermore, X, Y and Z, The inkjet recording method according to claim 2, wherein, in the anionic solution coating step, the neutralization power (W) of the alkaline aqueous solution attached to the area to which the colored ink composition is attached satisfies the following relationship. W≧X-(Y+Z)...Formula (2)

4. The inkjet recording method according to claim 1 or claim 2, wherein the acid is a compound having 1 to 3 carboxyl groups.

5. The inkjet recording method according to claim 1 or claim 2, wherein the alkaline aqueous solution contains one or more selected from anionic resin particles, inorganic alkalis, and organic alkalis as an alkaline component.

6. The inkjet recording method according to claim 1 or claim 2, wherein the anionic solution coating step is performed by an inkjet method.

7. The inkjet recording method according to claim 1 or claim 2, further comprising a drying step after the anionic solution coating step.

8. The inkjet recording method according to claim 1 or claim 2, wherein the pH of the alkaline aqueous solution is 11.0 or less.

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