Inkjet printing method, treatment liquid for inkjet printing, ink set for inkjet printing, and inkjet printing device

Abstract

To provide an inkjet printing method which enables formation of an image having good wet friction fastness on a fabric, without impairing feeling.SOLUTION: An inkjet printing method coats pigment ink, first treatment liquid and second treatment liquid by an inkjet head, wherein the first treatment liquid contains a coagulant, the inkjet head for discharging the first treatment liquid, the inkjet head for discharging the pigment ink, and the inkjet head for discharging the second treatment liquid are arranged on the same carriage, and form an image in a multipath method, the first treatment liquid, the pigment ink and the second treatment liquid are coated in this order in a forward path, the second treatment link, the pigment ink, and the first treatment liquid are coated in this order in a backward path, the second treatment liquid contains first resin particles having film elongation of 600 to 1,600% and a silicone acrylic resin, and the first treatment liquid, the pigment ink and the second treatment liquid are attached to the same part in the same scanning in an undried manner.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an inkjet textile printing method, an inkjet textile printing treatment liquid, an inkjet textile printing ink set, and an inkjet textile printing apparatus. In particular, the present invention relates to an inkjet textile printing method, an inkjet textile printing treatment liquid, an inkjet textile printing ink set, and an inkjet textile printing apparatus that are capable of forming an image on a fabric that has good wet rub fastness without impairing the texture. [Background technology]

[0002] Conventionally, inkjet textile printing methods using inkjet recording devices (printing devices) have been used as methods for forming images such as letters, pictures, and designs on fabrics such as woven fabrics and nonwoven fabrics (see, for example, Patent Documents 1 and 2). In such inkjet textile printing methods, a pretreatment liquid is typically used to aggregate the colorant ink, thereby retaining the ink on the surface of the fabric, thereby improving color density. Hereinafter, the "colorant ink" used in inkjet textile printing methods will also be simply referred to as "ink."

[0003] In inkjet textile printing methods, successively performing the process of applying a pretreatment liquid and the process of applying ink to dye the substrate can be expected to improve productivity and color development stability. Furthermore, applying the pretreatment liquid using an inkjet head and arranging the inkjet head for ejecting ink on the same carriage has the advantage of allowing the pretreatment liquid to be applied only to the areas of the image printing section that require it, and also allows for miniaturization. For example, Patent Document 2 discloses an inkjet textile printing method in which an inkjet head for ejecting a treatment liquid and an inkjet head for ejecting ink are arranged on the same carriage, and an image is formed using a multi-pass method.

[0004] In the multi-pass method in which the head carriage moves, in order to reduce individual differences between heads, it is common to break down the image into passes and form the image by moving the head back and forth multiple times in a direction transverse to the transport direction of the fabric to be printed. Hereinafter, the multi-pass method in which the head carriage moves is also referred to as the "scan method." [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2022-3175 [Patent Document 2] Japanese Patent Publication No. 2022-162288 Summary of the Invention [Problem to be solved by the invention]

[0006] However, when a treatment liquid such as the above-mentioned pretreatment liquid and ink are loaded in the same carriage, the order in which the treatment liquid and ink are applied is reversed due to the reciprocating movement of the carriage, which causes a problem in that the density on the front surface and the back surface of the fabric changes depending on whether the treatment liquid is applied first and then the ink, or whether the ink is applied first and then the treatment liquid.

[0007] To address this issue, a structure in which treatment liquid heads are located on both sides of the carriage is being considered. When arranging treatment liquid heads on both sides of the carriage, it is desirable to arrange the treatment liquids in the same order within the same carriage, in order of the first treatment liquid, pigment ink, and second treatment liquid, considering printing speed and device miniaturization. For example, on the carriage's outward movement, the order of ejection is the first treatment liquid, pigment ink, and second treatment liquid. Therefore, on the outward movement, if the first treatment liquid contains a coagulant, it is possible to suppress the penetration of resin and pigment in the ink ejection direction (hereinafter also referred to as the "Z direction") from the inkjet head. On the other hand, on the return movement, the pigment ink and first treatment liquid are ejected after the second treatment liquid, which does not contain a coagulant, which increases the penetration of resin and pigment in the Z direction of the fabric, resulting in a loss of texture.

[0008] The present invention has been made in view of the above problems and circumstances. An object of the present invention is to provide an inkjet textile printing method capable of forming an image having good wet rub fastness on a fabric without impairing the texture. Another object of the present invention is to provide an inkjet textile printing treatment liquid, an inkjet textile printing ink set using the same, and an inkjet textile printing apparatus, all of which are used in the inkjet textile printing method. [Means for solving the problem]

[0009] To solve the above-mentioned problems, the inventors conducted extensive research, focusing on the components contained in the second treatment liquid, which is injected first on the return pass of a multi-pass system. As a result, they discovered that even if the second treatment liquid does not contain a flocculant, by adding resin particles with a specific film elongation and a silicone acrylic resin to the second treatment liquid, it is possible to maintain a good texture even when the application order is the return pass described above, and they arrived at the present invention. That is, the above-mentioned problems of the present invention are solved by the following means.

[0010] 1. An inkjet printing method in which a pigment ink, a first treatment liquid, and a second treatment liquid are applied using an inkjet head, the first treatment liquid contains a flocculant and serves to retain at least one of the pigment ink and the second treatment liquid on the surface of the fabric; the inkjet head that ejects the first treatment liquid, the inkjet head that ejects the pigment ink, and the inkjet head that ejects the second treatment liquid are arranged on the same carriage; An image is formed using a multi-pass method. On the outward path, the first treatment liquid is applied, and then the pigment ink and the second treatment liquid are applied in this order; In the return path, after the second treatment liquid is applied, the pigment ink and the first treatment liquid are applied in this order; the second treatment liquid contains first resin particles and a silicone acrylic resin having a film elongation of 600 to 1600%, An inkjet textile printing method, characterized in that the first treatment liquid, the pigment ink, and the second treatment liquid are applied to the same location in the same scanning operation without being dried.

[0011] 2. The pigment ink contains second resin particles and an aqueous solvent, 2. The inkjet printing method described in item 1, wherein at least one of the resin of the first resin particles of the second treatment liquid and the resin of the second resin particles of the pigment ink contains an acrylic resin or a urethane resin.

[0012] 3. The ink-jet printing method described in item 1 or 2, wherein the pigment ink contains a silicone acrylic resin.

[0013] 4. The inkjet printing method described in item 1 or 2, wherein the first treatment liquid contains at least one selected from the group consisting of a compound having a cationic group, a polyvalent metal salt, and an organic acid.

[0014] 5. The ink-jet printing method described in item 4, wherein the compound having a cationic group is a cationic resin.

[0015] 6. The pigment ink contains a pigment and a block copolymer, 3. The inkjet printing method according to item 1 or 2, wherein the block copolymer contains two hydrophilic blocks A that are arranged at both ends of the molecule and that interact or react with at least the flocculant contained in the first treatment liquid, and a hydrophobic block B that is arranged between the two hydrophilic blocks A.

[0016] 7. The ink-jet printing method described in item 6, wherein the block copolymer contains an ABA type block copolymer consisting of two hydrophilic blocks A and one hydrophobic block B.

[0017] 8. The ink-jet printing method described in item 1 or 2, wherein the pigment ink contains a crosslinking agent.

[0018] 9. A treatment liquid for inkjet textile printing as the second treatment liquid used in inkjet textile printing in which a pigment ink, a first treatment liquid, and a second treatment liquid are applied by an inkjet head, the first treatment liquid contains a flocculant for retaining the pigment ink or the second treatment liquid on the surface of the fabric; the inkjet head that ejects the first treatment liquid, the inkjet head that ejects the pigment ink, and the inkjet head that ejects the second treatment liquid are arranged on the same carriage and are used to form an image by a multi-pass method; On the outward path, the first treatment liquid is applied, and then the pigment ink and the second treatment liquid are applied in this order; In the return path, after the second treatment liquid is applied, the pigment ink and the first treatment liquid are applied in this order; the second treatment liquid contains first resin particles and a silicone acrylic resin having a film elongation of 600 to 1600%, The inkjet printing treatment liquid is characterized in that the first treatment liquid, the pigment ink, and the second treatment liquid are applied to the same location in the same scanning operation without drying.

[0019] 10. An inkjet printing ink set comprising a pigment ink, a first treatment liquid, and a second treatment liquid, 10. An ink set for ink-jet textile printing, wherein the second treatment liquid is the treatment liquid for ink-jet textile printing described in item 9.

[0020] 11. An inkjet printing device that applies a pigment ink, a first treatment liquid, and a second treatment liquid using an inkjet head, the first treatment liquid contains a flocculant for retaining the pigment ink or the second treatment liquid on the surface of the fabric; the inkjet head that ejects the first treatment liquid, the inkjet head that ejects the pigment ink, and the inkjet head that ejects the second treatment liquid are arranged on the same carriage; An image is formed using a multi-pass method. On the outward path, the first treatment liquid is applied, and then the pigment ink and the second treatment liquid are applied in this order; In the return path, after the second treatment liquid is applied, the pigment ink and the first treatment liquid are applied in this order; the second treatment liquid contains first resin particles and a silicone acrylic resin having a film elongation of 600 to 1600%, An inkjet textile printing apparatus, characterized in that the first treatment liquid, the pigment ink, and the second treatment liquid are applied to the same location in the same scanning operation while still wet. [Effects of the Invention]

[0021] The above-described means of the present invention can provide a multi-pass inkjet textile printing method capable of forming an image having good wet rub fastness on a fabric without impairing the texture. Also provided are an inkjet textile printing treatment liquid, an inkjet textile printing ink set using the same, and an inkjet textile printing apparatus, which can be suitably used in such an inkjet textile printing method.

[0022] The mechanism by which the effects of the present invention are manifested or the mechanism of action is not clear, but is speculated as follows.

[0023] First, in the forward pass of the multi-pass method, the first treatment liquid, which is injected first onto the fabric, contains a flocculant. Therefore, by applying the first treatment liquid and then the pigment ink and second treatment liquid in sequence, the flocculant flocculates the resin and pigment in the pigment ink and second treatment liquid, effectively suppressing their penetration into the fabric in the Z direction. Therefore, the pigment ink and second treatment liquid applied to the fabric after the first treatment liquid are applied tend to remain on the fabric surface. This prevents the fabric from becoming stiff, allowing the fabric to maintain its good texture.

[0024] On the other hand, in the return pass of the multi-pass method, the second treatment liquid, which is injected first onto the fabric, contains first resin particles with a film elongation of 600 to 1600% and a silicone acrylic resin. The first resin particles with a film elongation of 600 to 1600% are relatively soft resin particles, so even if the first resin particles penetrate into the fabric in the Z direction, they have little effect on the texture, allowing the texture of the fabric to be maintained. Furthermore, the silicone acrylic resin promotes wetting and spreading in the X and Y directions, for example, and thus can suppress penetration in the Z direction. Therefore, the silicone acrylic resin contained in the second treatment liquid also contributes to maintaining the texture of the fabric. Furthermore, in the return pass, the first treatment liquid, which is injected last onto the fabric, contains a flocculant. Therefore, by injecting such a first treatment liquid last, wet rub fastness is also maintained. [Brief explanation of the drawings]

[0025] [Figure 1] FIG. 1 is a schematic diagram illustrating an embodiment of an inkjet textile printing apparatus. [Figure 2] FIG. 1 is a schematic diagram illustrating an example of a main part of a multi-pass inkjet coating device. [Figure 3] 10 is a flowchart showing an example of a process for applying treatment liquid and pigment ink in a multi-pass system. [Figure 4] FIG. 1 is a diagram showing a schematic configuration of an inkjet printing apparatus in which a fabric is attached to a conveying belt and conveyed. DETAILED DESCRIPTION OF THE INVENTION

[0026] One embodiment of the inkjet textile printing method of the present invention is an inkjet textile printing method in which a pigment ink, a first treatment liquid, and a second treatment liquid are applied by an inkjet head. Hereinafter, the inkjet textile printing method of this embodiment will also be simply referred to as a "textile printing method."

[0027] In the textile printing method of this embodiment, an inkjet head that ejects a first treatment liquid, an inkjet head that ejects a pigment ink, and an inkjet head that ejects a second treatment liquid are arranged on the same carriage, and an image is formed using a multi-pass system. Then, in the forward path of the multi-pass system, the first treatment liquid is applied, followed by the pigment ink and the second treatment liquid, in that order. Meanwhile, in the return path of the multi-pass system, the second treatment liquid is applied, followed by the pigment ink and the first treatment liquid, in that order. The first treatment liquid, which is ejected first in the forward path, contains a flocculant. The first treatment liquid is intended to retain at least one of the pigment ink and the second treatment liquid on the fabric surface. The second treatment liquid, which is ejected first in the return path, contains first resin particles and a silicone acrylic resin, each having a film elongation of 600 to 1600%. The textile printing method of this embodiment is characterized in that the first treatment liquid, the pigment ink, and the second treatment liquid are applied to the same location in the same scanning direction (in other words, the main scanning direction of the ink ejection device) while still wet, using the forward and backward passes of the multi-pass method as described above. This feature is a technical feature common to or corresponding to each of the following embodiments.

[0028] According to the textile printing method of this embodiment, an image having good wet rub fastness can be formed on a fabric without impairing the texture. That is, in the forward pass, after applying a first treatment liquid, the pigment ink and the second treatment liquid are sequentially applied. By using an aggregating agent to aggregate the resins and pigments in the pigment ink and the second treatment liquid, the penetration of the fabric in the Z direction can be effectively suppressed. Therefore, the pigment ink and the second treatment liquid are more likely to remain on the fabric surface, making the fabric less likely to harden and maintaining a good texture. Meanwhile, in the return pass, the second treatment liquid, which is injected first onto the fabric, contains first resin particles having a film elongation of 600 to 1600% and a silicone acrylic resin. Because the first resin particles having a film elongation of 600 to 1600% are relatively soft, even if the first resin particles penetrate the fabric in the Z direction, the impact on the texture is minimal, and the texture of the fabric can be maintained. Furthermore, the silicone acrylic resin promotes wetting and spreading in the X and Y directions, thereby suppressing penetration in the Z direction. Therefore, the silicone acrylic resin contained in the second treatment liquid also contributes to maintaining the texture of the fabric. Furthermore, in the return pass, the first treatment liquid, which is injected last onto the fabric, contains a flocculant, and thus, by injecting this first treatment liquid last, wet friction fastness is also maintained.

[0029] In the textile printing method of this embodiment, the pigment ink preferably contains second resin particles and an aqueous solvent. Furthermore, it is preferable that at least one of the resins of the first resin particles of the second treatment liquid and the second resin particles of the pigment ink contains an acrylic resin or a urethane resin. This configuration has the advantage of providing good flexibility due to the properties of the resin, making it easier to maintain the texture of the fabric.

[0030] In the textile printing method of this embodiment, the pigment ink preferably contains a silicone acrylic resin, which has the advantage that the ink is easily wetted and spreads in the X and Y directions and is less inhibited in the Z direction, resulting in good flexibility and making it easier to maintain the texture of the fabric.

[0031] In the textile printing method of this embodiment, the first treatment liquid preferably contains at least one selected from the group consisting of a compound having a cationic group, a polyvalent metal salt, and an organic acid. The compound having a cationic group is more preferably a cationic resin. This configuration has the advantage of being able to interact or react with the anionic block copolymer, which is the pigment dispersant contained in the pigment ink.

[0032] In the textile printing method of this embodiment, the pigment ink preferably contains a pigment and a block copolymer. The block copolymer preferably contains two hydrophilic blocks A located at both ends of the molecule and a hydrophobic block B located between the two hydrophilic blocks A. The hydrophilic block A interacts or reacts with at least the flocculant contained in the first treatment liquid. More preferably, the block copolymer contained in the pigment ink contains an ABA block copolymer consisting of two hydrophilic blocks A and one hydrophobic block B. This configuration ensures that the pigment ink has good jetting stability and can form an image on the fabric that has good wet rub fastness.

[0033] The pigment ink preferably contains a crosslinking agent. By configuring it in this way, when the pigment ink or the fabric contains a (meth)acrylic resin or a urethane resin having a crosslinkable group, these react with the crosslinking agent to undergo post-crosslinking, which is advantageous in that stickiness of the fabric surface is suppressed and good wet friction fastness is achieved.

[0034] Next, one embodiment of the inkjet textile printing treatment liquid of the present invention will be described. The inkjet textile printing treatment liquid of this embodiment is an inkjet textile printing treatment liquid serving as a second treatment liquid used in inkjet textile printing in which a pigment ink, a first treatment liquid, and a second treatment liquid are applied by an inkjet head. That is, the inkjet textile printing treatment liquid of this embodiment has the same configuration as the second treatment liquid used in the textile printing method of this embodiment described above. Furthermore, one embodiment of the inkjet textile printing ink set of the present invention is an inkjet textile printing ink set including a pigment ink, a first treatment liquid, and a second treatment liquid, characterized in that the second treatment liquid is the inkjet textile printing treatment liquid of this embodiment described above. With this inkjet textile printing treatment liquid and inkjet textile printing ink set, it is possible to form an image on a fabric that has good wet rub fastness without impairing the texture.

[0035] Next, one embodiment of the inkjet textile printing apparatus of the present invention will be described. Hereinafter, the inkjet textile printing method of this embodiment will also be simply referred to as the "textile printing method." The textile printing apparatus of this embodiment is an inkjet textile printing apparatus that applies a pigment ink, a first treatment liquid, and a second treatment liquid using an inkjet head. The first treatment liquid contains a flocculant for retaining the pigment ink or the second treatment liquid on the surface of the fabric. In the textile printing apparatus of this embodiment, an inkjet head that ejects the first treatment liquid, an inkjet head that ejects the pigment ink, and an inkjet head that ejects the second treatment liquid are arranged on the same carriage. The textile printing apparatus of this embodiment forms an image using a multi-pass method. In the forward path of the multi-pass method, the first treatment liquid is applied, followed by the application of the pigment ink and the second treatment liquid in that order. On the other hand, in the return path of the multi-pass method, the second treatment liquid is applied, followed by the application of the pigment ink and the first treatment liquid in that order. The second treatment liquid contains first resin particles and a silicone acrylic resin having a film elongation of 600 to 1600%. The textile printing apparatus of this embodiment is characterized in that the first treatment liquid, pigment ink, and second treatment liquid described above are applied to the same location in the same scan (i.e., main scan) without being dried.

[0036] The present invention, its components, and embodiments and modes for carrying out the present invention will be described in detail below. In this application, the symbol "to" indicating a range of values ​​is used to mean that the values ​​before and after it are included as the lower limit and upper limit.

[0037] [Inkjet printing device] Hereinafter, an embodiment of the inkjet textile printing apparatus of the present invention will be described with reference to the drawings, but the present invention is not limited thereto. Fig. 1 is a schematic diagram showing an embodiment of the inkjet textile printing apparatus of the present invention.

[0038] As shown in FIG. 1, the inkjet printing apparatus 100 includes a fabric payout section 101, a transport section 103, an application section 10, a drying section 105, and a fabric recovery section 102. Hereinafter, the inkjet printing apparatus will also be simply referred to as a "printing apparatus." The fabric payout section 101 is for paying out the fabric T1. The transport section 103 is for transporting the fabric T1 paid out from the fabric payout section 101. The application section 10 is for applying a first treatment liquid P1, a pigment ink In, and a second treatment liquid P2 to the fabric T1. The drying section 105 is for drying the first treatment liquid P1, the pigment ink In, the second treatment liquid, etc. The fabric recovery section 102 is for recovering the printed fabric T3. Hereinafter, the printed fabric T3 will also be referred to as “printed fabric T3.” The printing apparatus 100 further includes a control unit 106 that controls each member.

[0039] Furthermore, in the textile printing apparatus 100, the coating unit 10 has a first treatment liquid head that ejects the first treatment liquid P1, a pigment ink head that ejects the pigment ink In, a second treatment liquid head that ejects the second treatment liquid P2, and a carriage that carries these. The configuration of the coating unit 10 will be described in more detail below with reference to Figure 2. Figure 2 is a schematic diagram that shows an example of the main parts of a multi-pass inkjet coating device.

[0040] The coating unit 10 shown in FIG. 2 has a first treatment liquid head 1P1 as an inkjet head for a first treatment liquid P1 (see FIG. 1). It also has four ink heads 1Y, 1M, 1C, and 1K as inkjet heads for a pigment ink In (see FIG. 1). It also has a second treatment liquid head 1P2 as an inkjet head for a second treatment liquid P2 (see FIG. 1). The ink head 1Y is a head for yellow ink and will hereinafter be referred to as the "yellow ink head 1Y." The ink head 1M is a head for magenta ink and will hereinafter be referred to as the "magenta ink head 1M." The ink head 1C is a head for cyan ink and will hereinafter be referred to as the "cyan ink head 1C." The ink head 1K is a head for black ink and will hereinafter be referred to as the "black ink head 1K." In the coating unit 10, the first treatment liquid head 1P1, four ink heads 1Y, 1M, 1C, and 1K, and the second treatment liquid head 1P2 are mounted on one carriage 22. That is, the first treatment liquid head 1P1, the ink heads 1Y, 1M, 1C, and 1K, and the second treatment liquid head 1P2 are mounted on the same carriage 22. Note that as the inkjet heads for the pigment ink In, further inkjet heads of the same color or different colors may be added, and any number of rows of the above configuration may be used.

[0041] In Fig. 1, the conveying direction of the fabric T1 is indicated by an arrow. In the textile printing apparatus 100, essential components are a first treatment liquid head 1P1 (see Fig. 2), ink heads 1Y, 1M, 1C, and 1K (see Fig. 2), a second treatment liquid head 1P2 (see Fig. 2), and a control unit 106. The textile printing apparatus 100 may have other components in addition to the components shown in Fig. 1 as necessary. Examples of other components include a fixing unit (not shown) provided downstream of the drying unit 105 in the conveying direction. Each component of the textile printing apparatus 100 will be described below.

[0042] <Fabric feeding section> The fabric T1 is placed in a fabric payout unit 101 provided upstream of the applicator 10 in the conveying direction. The fabric payout unit 101 includes a rotating shaft on which the roll-shaped fabric T1 is attached, and a motor (not shown) that drives the rotating shaft to rotate in a predetermined direction. By driving the motor, the fabric payout unit 101 pays out the fabric T1 downstream in the conveying direction as the rotating shaft rotates. Note that the fabric T1 may be a continuous fabric as described above, or may be separated into individual pieces of fabric.

[0043] <Transportation section> The conveying unit 103 conveys the fabric T1 fed from the fabric feeding unit 101. In Fig. 1, the fabric T1 is conveyed by conveying rollers, but for example, the fabric T1 may be attached to a conveying belt and conveyed.

[0044] In the case of a configuration in which the fabric is attached to a conveyor belt and conveyed, the following cleaning process is performed. FIG. 4 is a diagram showing the schematic configuration of an inkjet printing apparatus in which the fabric is attached to a conveyor belt and conveyed. In the case of a configuration in which the fabric is attached to a conveyor belt and conveyed, as shown in FIG. 4, a conveyor belt cleaning unit 4 is disposed below the belt conveying unit 2. The conveyor belt cleaning unit 4 is provided with a plurality of cleaning means and the like arranged in order along the moving direction of the conveyor belt 223. In the belt conveying unit 2, the drive roller 221 is rotated at a predetermined speed in the counterclockwise direction (see the arrow) in FIG. 4 by the rotational drive of the sub-scanning motor, thereby rotating the conveyor belt 223 stretched between the drive roller 221 and the driven roller 222. As a result, the fabric T2 placed on the surface of the conveyor belt 223 is conveyed in the sub-scanning direction, that is, the direction of arrow A in the figure. In FIG. 4, reference numeral 3 denotes a coating unit serving as an inkjet coating device.

[0045] The conveyor belt cleaning unit 4 includes a water sprinkler pipe 41 , a brush roller 42 , a cleaning blade 43 , a cleaning sponge 44 and a heating unit 45 .

[0046] The sprinkler pipe 41 is suspended across the entire width of the conveyor belt 223. A large number of nozzles are arranged along the length of the sprinkler pipe 41 at a position facing the surface of the conveyor belt 223. A cleaning liquid is supplied to the sprinkler pipe 41 via a sprinkler tube 41a by driving a sprinkler pump. The sprinkler pipe 41 sprays the supplied cleaning liquid from the nozzles onto the surface of the conveyor belt 223, thereby cleaning foreign matter adhering to the surface of the conveyor belt 223.

[0047] The brush roller 42 is formed in a roller shape by implanting multiple brush bundles, each consisting of a bundle of brush bristles, around a rotating shaft that spans the entire width of the conveyor belt 223. The tips of the brush bundles are constantly in contact with the surface of the conveyor belt 223, downstream in the rotation direction of the conveyor belt 223 from the position where the sprinkler pipe 41 sprays water. The brush roller 42 rotatably contacts the surface of the conveyor belt 223 and removes foreign matter, such as aggregates, remaining on the surface of the conveyor belt 223. Specifically, the brush roller 42 rotates at a predetermined speed in the same direction as the rotation direction of the drive roller 21 based on the power of a brush drive unit (not shown). As a result, the brush roller 42 moves in a direction opposite to the movement direction of the conveyor belt 223, rubbing the tips of the brush bundles against the surface of the conveyor belt 223. As a result, the brush roller 42 removes foreign matter that was washed away by the spraying of cleaning liquid from the sprinkler pipe 41, which is located upstream in the movement direction of the conveyor belt 223.

[0048] A cleaning tub for storing cleaning liquid may be provided below the brush roller 42. In this case, the lower part of the brush roller 42 is partially immersed in the cleaning liquid, and the cleaning liquid is stirred up as the brush roller 42 rotates, thereby enhancing the effect of removing foreign matter. The cleaning liquid in the cleaning tub may be supplied to the sprinkler pipe 41 via a sprinkler tube 41a. In this case, the cleaning liquid sprayed onto the surface of the conveyor belt 223 and dripping thereon is collected again in the cleaning tub and reused.

[0049] The cleaning blade 43 is provided downstream of the brush roller 42 in the rotation direction of the conveyor belt 223. The cleaning blade 43 is formed in a flat plate shape using, for example, an elastic material such as rubber, a PET sheet, or a straight brush, and is stretched across the entire width of the conveyor belt 223. The cleaning blade 43 is configured so that its tip can come into contact with or be separated from the surface of the conveyor belt 223. The cleaning blade 43 comes into contact with the surface of the conveyor belt 223 and removes foreign matter and cleaning liquid remaining on the surface of the conveyor belt 223 by scraping it off.

[0050] The cleaning sponge 44 is a porous body having water absorption properties, such as a sponge, and is stretched across the entire width of the conveyor belt 223. The surface of the cleaning sponge 44 is configured to be able to come into contact with or separate from the surface of the conveyor belt 223, downstream of the cleaning blade 43 in the rotation direction of the conveyor belt 223. By coming into contact with the surface of the conveyor belt 223, the cleaning sponge 44 absorbs and wipes away cleaning liquid remaining on the surface of the conveyor belt 223.

[0051] The heating unit 45 is a belt heater, and is provided downstream of the cleaning sponge 44 and upstream of the driven roller 222 in the rotation direction of the conveyor belt 223. The heating unit 45 heats and evaporates the cleaning liquid remaining on the surface of the conveyor belt 223.

[0052] <Application part> 1, the applicator 10 is an inkjet applicator for applying a first treatment liquid P1, a pigment ink In, and a second treatment liquid P2 to a fabric T1. In particular, the applicator 10 is a multi-pass inkjet applicator.

[0053] As shown in FIG. 2, an image is formed by a droplet ejection means 20 of an inkjet coating device moving in a scanning direction over fabric T1 while ejecting a first treatment liquid P1 (not shown), pigment inks In of various colors (not shown), and a second treatment liquid P2 (not shown). For example, four colors of ink, yellow ink Y, magenta ink M, cyan ink C, and black ink K, are used as the pigment ink In. In FIG. 2, a plane parallel to the surface of fabric T1 is referred to as the "XY plane." A direction perpendicular to this "XY plane" is referred to as the "Z direction." For example, the direction of ink ejection from pigment ink heads 1Y, 1M, 1C, and 1K mounted on a carriage 22 corresponds to the Z direction. In the XY plane, the main scanning direction is referred to as the "X direction," and the direction perpendicular to the main scanning direction (sub-scanning direction) is referred to as the "Y direction." Hereinafter, the X direction may be referred to as the "main scanning direction X." The Y direction may also be referred to as the "sub-scanning direction Y" or the "conveying direction Y."

[0054] The fabric T1 is sequentially conveyed in a sub-scanning direction Y perpendicular to the scanning direction X by a conveying means (not shown), so that an image can be formed on substantially the entire surface (image forming surface) of the fabric T1.

[0055] The droplet ejection means 20 has a first treatment liquid head 1P1, four ink heads 1Y, 1M, 1C, and 1K, a second treatment liquid head 1P2, and a carriage 22 for arranging and holding these along the scanning direction X. That is, the first treatment liquid head 1P1, the ink heads 1Y, 1M, 1C, and 1K, and the second treatment liquid head 1P2 are mounted on the same carriage 22. Hereinafter, the first treatment liquid head 1P1, the four ink heads 1Y, 1M, 1C, and 1K, and the second treatment liquid head 1P2 will also be collectively referred to as the "head unit 1."

[0056] In the head unit 1, during a forward pass in which the droplet ejection means 20 moves once in the scanning direction X, the first treatment liquid head 1P1, the four ink heads 1Y, 1M, 1C, and 1K, and the second treatment liquid head 1P2 are arranged in the following order: That is, during the forward pass, from the beginning of the scanning direction, the first treatment liquid head 1P1, the yellow ink head 1Y, the magenta ink head 1M, the cyan ink head 1C, the black ink head 1K, and the second treatment liquid head 1P2 are arranged in this order. Conversely, during the return pass, from the beginning of the scanning direction, the second treatment liquid head 1P2, the black ink head 1K, the cyan ink head 1C, the magenta ink head 1M, the yellow ink head 1Y, and the first treatment liquid head 1P1 are arranged in this order.

[0057] Each head has a surface (nozzle surface) facing the surface of the fabric T1, on which a plurality of nozzles (not shown) are arranged along a transport direction Y perpendicular to the scanning direction X. When appropriate pressure is applied to the pigment ink In, the first treatment liquid P1, and the second treatment liquid P2, tiny droplets are ejected from these nozzles. The droplet ejection means 20 is supported such that the nozzle surface of the head unit 1 is spaced a predetermined distance from the surface of the fabric T1 in a direction perpendicular to the surface (height direction).

[0058] The droplet discharge means 20 is scanned in the scanning direction X by the scanning unit 30. The scanning unit 30 includes, for example, rails that support the carriage 22 with the nozzle surface spaced apart from the surface of the fabric T1 in the height direction by the above-mentioned predetermined distance, and allows the carriage 22 to move along the rails that extend along the scanning direction X.

[0059] When the droplet ejection means 20 moves once in the scanning direction X on the outward path, the first treatment liquid P1 is applied at a predetermined width along the scanning direction X of the head unit 1, and immediately after that, each pigment ink In is applied, and immediately after that, the second treatment liquid P2 is applied.

[0060] Thereafter, the fabric T1 moves in the transport direction Y, and the droplet discharge means 20 moves once in the scanning direction X on the return path. When the droplet discharge means 20 moves once in the scanning direction X on the return path, the second treatment liquid P2 is applied to a predetermined width along the scanning direction X of the head unit 1, and immediately after that, each pigment ink In is applied, and immediately after that, the first treatment liquid P1 is applied.

[0061] 2, a multi-pass coating method is performed in which the operation of applying the pigment ink In, the first treatment liquid P1, and the second treatment liquid to the fabric T1 by moving the droplet discharge means 20 once in the scanning direction X is counted as one printing pass, and multiple printing passes are performed on the same area. By performing multiple printing passes like this, a desired image is ultimately formed on the fabric T1.

[0062] In the inkjet printing method of the present invention, for example, an inkjet coating device shown in FIG. 2 is used to apply a first treatment liquid P1, a pigment ink In, and a second treatment liquid P2 to the surface of a fabric T1 using a droplet ejection means 20, respectively, and allow them to coalesce as described above, thereby forming an image.

[0063] The ejection method of the first treatment liquid P1, each pigment ink In, and the second treatment liquid P2 in the head unit 1 is not particularly limited, and the head may be either an on-demand type or a continuous type. Examples of on-demand type heads include electro-mechanical conversion types and electro-thermal conversion types. Examples of electro-mechanical conversion types include single-cavity type, double-cavity type, bender type, piston type, shear mode type, and shared wall type. Examples of electro-thermal conversion types include thermal inkjet type, bubble jet (registered trademark) type, and other electro-thermal conversion types.

[0064] Of the above, an on-demand type head is preferred, and a head using a piezoelectric element as the electromechanical conversion element used in the electromechanical conversion type (also called a "piezo type inkjet head") is preferred.

[0065] <Drying section> The drying section 105 dries the first treatment liquid P1, pigment ink In, and second treatment liquid P2 applied by the application section 10. There are no particular limitations on the drying means, but heating using hot air, a hot plate, a heat roller, or infrared drying is preferred. From the viewpoint of sufficiently removing the solvent component in a short time, heated drying is more preferred. The drying temperature is preferably within the range of 100 to 200°C.

[0066] <Fabric Recovery Department> The fabric recovery section 102 is provided downstream of the drying section 105, and recovers while winding up the printed fabric T3 on which the first treatment liquid P1, the pigment ink In, and the second treatment liquid P2 have been dried in the drying section 105. Alternatively, in the case where the fabric T1 is separated one by one and transported, the fabric recovery section 102 may be a fabric discharge section from which the printed fabric T3 is discharged.

[0067] The types of fibers that make up the fabric include natural fibers (hydrophilic fibers) such as cotton, linen, wool, or silk, chemical fibers such as rayon, vinylon, nylon, acrylic, polyurethane, polyester, or acetate, or blends thereof.

[0068] <Control unit> The control unit 106 controls each of the components of the textile printing apparatus 100 described above. For example, the control unit 106 controls each of the fabric payout unit 101, the conveying unit 103, the drying unit 105, and the fabric recovery unit 102. Furthermore, the control unit 106 may control the application conditions of the first treatment liquid P1 and the second treatment liquid P2 based on fabric information, although this is not particularly limited. Specifically, the control unit 106 may control the application amounts of the first treatment liquid P1 and the second treatment liquid P2 based on fabric information (for example, the fiber ratio, basis weight, fiber type, etc. of the fabric).

[0069] [Inkjet printing method] Next, the inkjet printing method (also simply referred to as the "printing method") of this embodiment will be described in more detail. The printing method of this embodiment is a printing method in which a pigment ink, a first treatment liquid, and a second treatment liquid are applied using an inkjet head. Hereinafter, the first treatment liquid and the second treatment liquid may be collectively referred to simply as the "treatment liquids."

[0070] The textile printing method of this embodiment uses, for example, the textile printing apparatus 100 shown in FIG. 1 described above, and forms an image by applying the pigment ink In, the first treatment liquid P1, and the second treatment liquid P2 using an inkjet head. In particular, the textile printing method of this embodiment arranges an inkjet head that ejects the first treatment liquid, an inkjet head that ejects the pigment ink, and an inkjet head that ejects the second treatment liquid on the same carriage, and forms an image using a multi-pass printing method. More specifically, in the forward pass of the multi-pass printing method, the first treatment liquid is applied, followed by the application of the pigment ink and the second treatment liquid, in that order. Meanwhile, in the return pass of the multi-pass printing method, the second treatment liquid is applied, followed by the application of the pigment ink and the first treatment liquid, in that order. This process can be performed using, for example, the inkjet coating device shown in FIG. 2. That is, using the inkjet coating device shown in FIG. 2, the first treatment liquid P1, the pigment ink In, and the second treatment liquid P2 are applied to the surface of the fabric T1 using the droplet ejection means 20, respectively, and then coalesced to form an image. The configurations of the textile printing apparatus 100 shown in FIG. 1 and the inkjet coating apparatus shown in FIG. 2 are as described in the embodiment of the textile printing apparatus.

[0071] For example, as for the process of applying treatment liquid and pigment ink, as shown in the flowchart in Figure 3, on the return path of the multi-pass method, a first treatment liquid application process S01 on outgoing path 1, a pigment ink application process S02 on outgoing path 2, and a second treatment liquid application process S03 on outgoing path 3 are performed. After that, a fabric transport process S04 is performed in which the fabric is transported in the transport direction Y, and then on the return path of the multi-pass method, a second treatment liquid application process S05 on return path 1, a pigment ink application process S06 on return path 2, and a second treatment liquid application process S07 on return path 3 are performed. Here, Figure 3 is a flowchart showing an example of the process of applying treatment liquid and pigment ink in the multi-pass method.

[0072] In the textile printing method of this embodiment, the first treatment liquid P1 (see FIG. 1, the same applies below) that is injected first on the forward pass contains a flocculant. The first treatment liquid P1 is intended to retain at least one of the pigment ink In (see FIG. 1, the same applies below) and the second treatment liquid P2 (see FIG. 1, the same applies below) on the fabric surface. The second treatment liquid P2 that is injected first on the backward pass contains first resin particles and a silicone acrylic resin having a film elongation of 600 to 1600%. The textile printing method of this embodiment is characterized in that the first treatment liquid P1, the pigment ink In, and the second treatment liquid P2 are applied to the same location in the same scanning direction (main scanning direction) without drying, using the forward and backward passes of the multi-pass method described above.

[0073] In the textile printing method of the present embodiment, after the first treatment liquid P1, the pigment ink In, and the second treatment liquid P2 are applied as described above, the applied first treatment liquid P1, the pigment ink In, and the second treatment liquid P2 may be dried by the drying section 105 of the textile printing apparatus 100 as shown in FIG.

[0074] Thereafter, if necessary, the volatile components in the first treatment liquid P1, the pigment ink In, and the second treatment liquid P2 are removed in the drying section 105 of the printing apparatus 100 by a fixing section, and the remaining components are then fixed to the fabric T1 by further heating or the like.

[0075] Furthermore, the printed fabric T3 after printing and drying in the drying section 105 is wound up and collected by the fabric recovery section T3 of the printing apparatus 100.

[0076] By using the above-described textile printing method, an image having good wet rub fastness can be formed on a fabric without impairing the texture. The first treatment liquid, the second treatment liquid, and the pigment ink used in the textile printing method of this embodiment will be described below.

[0077] <First processing liquid> The first treatment liquid contains a flocculant.

[0078] (flocculant) The type of aggregating agent may be any agent that aggregates pigments contained in the ink, etc. The aggregation may be achieved by utilizing a change in pH or by utilizing an electrical effect.

[0079] Examples of flocculants that cause flocculation by changing the pH include organic acids, such as carboxylic acids having 6 or less carbon atoms, saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, and hexanoic acid, and hydroxy acids such as lactic acid, malic acid, and citric acid.

[0080] Examples of the flocculant that causes aggregation by electrical action include compounds having cationic groups and polyvalent metal salts. These flocculants can interact or react with the anionic block copolymer that serves as the pigment dispersant contained in the ink.

[0081] Examples of the cationic group in the compound having a cationic group include a secondary amino group, a tertiary amino group, a quaternary ammonium base, etc. Examples of the compound having a cationic group include a cationic resin and a cationic surfactant, and a cationic resin is preferred.

[0082] Examples of cationic resins include cationic urethane resins, cationic olefin resins, and cationic alkylamine resins. Examples of commercially available products include MPT-60 (manufactured by Mitsubishi Pencil Co., Ltd.), Unisense KHE100L (manufactured by Senka Co., Ltd.), and MZ477 (urethane resin, manufactured by Takamatsu Oil & Fat Co., Ltd.). Among them, the cationic alkylamine resins MPT-60 and Unisense KHE100L (manufactured by Senka Co., Ltd.) are preferred from the viewpoint of more easily interacting or reacting with the block copolymer.

[0083] Polyvalent metal salts can be water-soluble compounds having a divalent or higher polyvalent metal ion and an associated anion. Examples of polyvalent metal ions include Ca 2+ , Cu 2+ , Ni 2+ , Mg 2+ , Zn 2+ , Ba 2+Divalent metal ions such as Al 3+ , Fe 3+ , Cr 3+ Examples of anions include trivalent metal ions such as Cl - , I - , Br - , SO4 2- , ClO 3- , NO 3- , and HCOO - , CH3COO - Examples of such polyvalent metal salts include metal salts of organic acids such as calcium salts, magnesium salts, nickel salts, and aluminum salts, such as zinc acetate dihydrate, magnesium nitrate, calcium chloride, magnesium chloride, aluminum chloride, magnesium sulfate, and acetic acid. Of these, calcium salts and magnesium salts are preferred, and calcium nitrate and calcium chloride are more preferred.

[0084] Among these, compounds having a cationic group or organic acids are preferred, and compounds having a cationic group are more preferred.

[0085] The content of the flocculant in the first treatment liquid is not particularly limited, but is preferably 0.1 to 15% by mass, and more preferably 0.5 to 8% by mass, relative to the first treatment liquid.

[0086] <Second processing liquid> (Silicone acrylic resin) The second treatment liquid contains a silicone acrylic resin. The silicone acrylic resin is a silicone acrylic resin that exists in a dispersed state as resin particles in an aqueous medium. The second treatment liquid is an aqueous treatment liquid containing water and an arbitrary water-soluble organic solvent. Therefore, the silicone acrylic resin is also contained as resin particles in the second treatment liquid. Whether the silicone acrylic resin exists as resin particles can be confirmed by whether or not a peak corresponding to the silicone acrylic resin is present when the dispersed particle size (Z average) of the second treatment liquid is measured using a particle size measuring device. An example of a particle size measuring device is the "Zataizer Nano S90" manufactured by Melvern.

[0087] The silicone acrylic resin is a copolymer containing structural units derived from polyorganosiloxane and structural units derived from other polymerizable monomers (including macromonomers) copolymerizable therewith.

[0088] The copolymer may be, for example, a graft copolymer in which a structural unit derived from polyorganosiloxane is graft-polymerized with a polymerizable monomer such as a (meth)acrylic acid ester. The copolymer may also be, for example, a copolymer in which the side chains or ends of a (meth)acrylic resin or the like are modified with a polyorganosiloxane. Among these, a graft copolymer in which a (meth)acrylic acid ester or the like is graft-polymerized with a polymer containing a structural unit derived from polyorganosiloxane is preferred. Such a graft copolymer has a structure in which the polyorganosiloxane portion forms the trunk and the (meth)acrylic acid ester or the like forms the branches, making it more compatible with the binder resin contained in the ink layer and therefore preferred. The form of copolymerization is not limited to graft copolymerization, and may be random copolymerization or block copolymerization.

[0089] The silicone acrylic resin may also have an ionic group. The ionic group of the silicone acrylic resin may be an ionic group that forms a pair with the ionic group of the fabric (or the ionic group of the flocculant attached to the fabric). For example, since flocculants usually have a cationic group, the silicone acrylic resin may be an anionic silicone acrylic resin that has an anionic group. Examples of the anionic group include a carboxy group, a sulfonic acid group, and a phosphonic acid group.

[0090] That is, the silicone acrylic resin preferably contains a structural unit derived from a polyorganosiloxane having a radical polymerizable group and a structural unit derived from another polymerizable monomer copolymerizable therewith.

[0091] Examples of polyorganosiloxanes having a radical polymerizable group include polyorganosiloxanes represented by the following formula (1).

[0092] [ka]

[0093] In the above formula (1), R 1 , R 2 and R 3 are each independently a hydrocarbon group having 1 to 10 carbon atoms.

[0094] In the above formula (1), Y is a radical polymerizable group selected from the group consisting of a vinyl group, an allyl group, and a γ-(meth)acryloxypropyl group.

[0095] In the above formula (1), X 1 and X 2 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group represented by the formula (2): SiR 4 R 5 R 6 It is a group represented by the formula: m is an integer of 1 to 10000. n is an integer of 1 or more. The siloxane chain may be branched.

[0096] In addition, the above formula (2): SiR 4 R 5 R 6 In R 4 and R 5 are each independently a hydrocarbon group having 1 to 10 carbon atoms. 6 is a radical polymerizable group selected from the group consisting of a vinyl group, an allyl group, and a γ-(meth)acryloxypropyl group, or a hydrocarbon group having 1 to 10 carbon atoms.

[0097] Other polymerizable monomers include (meth)acrylic acid esters. In this specification, (meth)acrylic refers to acrylic, methacrylic, or both.

[0098] The (meth)acrylic acid ester is an alkyl ester, hydroxyalkyl ester, or alkoxyalkyl ester of (meth)acrylic acid. Examples of the (meth)acrylic acid ester include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate. Other examples of the (meth)acrylic acid ester include 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-methoxyethyl (meth)acrylate. Among these, methyl methacrylate and 2-hydroxyethyl methacrylate are preferred.

[0099] The content of structural units derived from polyorganosiloxane in the silicone acrylic resin is preferably 50% by mass or more, more preferably 60% by mass or more and 95% by mass or less, based on the total amount of structural units constituting the silicone resin. When the content of structural units derived from polyorganosiloxane is 50% by mass or more, the effect of reducing the friction coefficient derived from polysiloxane is more easily achieved, and wet rub fastness can be further improved. When the content of structural units derived from polyorganosiloxane is 95% by mass or less, affinity with other compounds and other resins is more easily improved.

[0100] The silicone acrylic resin may further contain structural units derived from other polymerizable monomers than those mentioned above. Examples of other polymerizable monomers than those mentioned above include ethylenically unsaturated carboxylic acids such as (meth)acrylic acid, styrenes, etc. For example, from the viewpoint of exhibiting anionic properties, the silicone acrylic resin may further contain structural units derived from ethylenically unsaturated carboxylic acids such as (meth)acrylic acid.

[0101] The graft copolymerization can be carried out by a known method, for example, by emulsifying and dispersing the polyorganosiloxane represented by the above formula (1) and a copolymerizable compound such as a (meth)acrylic acid ester in water, and polymerizing them in the presence of a radical polymerization initiator.

[0102] Examples of commercially available silicone-(meth)acrylic copolymers include Charine LC190, Charine R-170, R170S, Charine FE-230N, FE-502, and R-170BX (manufactured by Nissin Chemical Industry Co., Ltd.).

[0103] The second treatment liquid contains the silicone acrylic resin described above, but if, for example, the amount of surfactant is increased in place of the silicone acrylic resin in the second treatment liquid, the ionic bond between anions and cations may be inhibited, resulting in poor wet friction. Furthermore, if the amount of surfactant is increased, the surface friction coefficient may also increase, resulting in poor dry friction.

[0104] Furthermore, it is preferable that the second treatment liquid does not intentionally contain a flocculant like the first treatment liquid described above. If the second treatment liquid intentionally contains a flocculant, the coefficient of friction of the surface to which the second treatment liquid is applied increases, the dry rub fastness decreases, and the surface may become sticky.

[0105] (First resin particles with film elongation of 600-1600%) The second treatment liquid contains first resin particles having a film elongation of 600 to 1600%. The first resin particles having a film elongation of 600 to 1600% are present in a dispersed state in an aqueous medium. Hereinafter, the first resin particles having a film elongation of 600 to 1600% may be simply referred to as "first resin particles."

[0106] The first resin particles contained in the second treatment liquid are not particularly limited in terms of the type of resin as long as they have a film elongation of 600 to 1600%, but examples include urethane resin, acrylic resin, and ester resin. The resin constituting the first resin particles preferably contains urethane resin or acrylic resin. The inclusion of urethane resin or acrylic resin has the advantage of providing good flexibility and making it easier to maintain the texture of the fabric. Suitable examples of the urethane resin and acrylic resin constituting the first resin particles include the urethane resin and acrylic resin exemplified in the "water-dispersible resin: second resin particles" contained in the pigment ink described below.

[0107] The film elongation (%) of the first resin particles was measured as follows. First, a resin consisting of resin particles to be measured was applied to a polytetrafluoroethylene sheet so that the film thickness after drying was 500 μm. The applied resin was then dried for 15 hours at room temperature and atmospheric pressure, i.e., 20°C and 65% RH, and then further dried for 6 hours at 80°C and 20 minutes at 120°C. After that, the resin was peeled off from the sheet to produce a resin film. The film elongation (%) of the resulting resin film was measured using a tensile tester at a measurement temperature of 20°C and a measurement speed of 200 mm / min. Specifically, the resin film was stretched under the above conditions, and the length of elongation until the resin film broke was measured. The ratio of this length to the original length of the resin film, expressed as a percentage, was defined as the film elongation (%) of the first resin particles. As the tensile tester, for example, a Tensilon universal tester "RTC-1225A (product name)" manufactured by Orientec Co., Ltd. or an equivalent can be used.

[0108] The film elongation of the first resin particles may be 600 to 1600%.

[0109] There are no particular restrictions on the respective contents of the first resin particles and silicone acrylic resin in the second treatment liquid. For example, the content of the silicone acrylic resin in the second treatment liquid is preferably 0.1 to 2.0 mass% relative to the second treatment liquid, and more preferably 0.5 to 1.0 mass%. Furthermore, for example, the content of the first resin particles in the second treatment liquid is preferably 5.0 to 15.0 mass% relative to the second treatment liquid, and more preferably 7.5 to 12.5 mass%.

[0110] <Pigment ink> Pigment ink contains a pigment and water.

[0111] (pigment) The pigment is not particularly limited, but examples thereof include organic pigments or inorganic pigments having the following numbers listed in the Color Index.

[0112] Examples of red or magenta pigments include Pigment Red 3, 5, 19, 22, 31, 38, 43, 48:1, 48:2, 48:3, 48:4, 48:5, 49:1, 53:1, 57:1, 57:2, 58:4, 63:1, 81, 81:1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 254, and 257; Pigment Violet 3, 19, 23, 29, 30, 37, 50, and 88; and Pigment Orange. 13, 16, 20, 34, 36, and 43. Alternatively, they may be mixed crystals.

[0113] Examples of blue or cyan pigments include Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36, 60.

[0114] Examples of green pigments include Pigment Green 7, 26, 36, and 50.

[0115] Examples of yellow pigments include Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, and 193.

[0116] Examples of black pigments include Pigment Black 7, 28, and 26.

[0117] Commercially available examples of pigments include Cromofine Yellow 2080, 5900, 5930, AF-1300, 2700L, Cromofine Orange 3700L, 6730, Cromofine Scarlet 6750, Cromofine Magenta 6880, 6886, 6891N, 6790, 6887, Cromofine Violet RE, Cromofine Red 6820, 6830, Cromofine Blue HS-3, 5187, 5108, 5197, 5085N, SR-5020, 5026, 5050, 4920, 4927, 4937, 4824, 4933GN-EP, 4940, 4973, 5205, 5208, 5214, 5221, 5000P, Chrome Fine Green 2GN, 2GO, 2G-550D, 5310, 5370, 6830, Chrome Fine Black A-1103, Seika Fast Yellow 10GH, A-3, 2035, 2054, 2200, 2270, 2300, 2400(B), 2500, 2600, ZAY-260, 2700(B), 2770, Se Squidfast Red 8040, C405(F), CA120, LR-116, 1531B, 8060R, 1547, ZAW-262, 1537B, GY, 4R-4016, 3820, 3891, ZA-215, Seikafast Carmine 6B1476T-7, 1483LT, 3840, 3870, Seikafast Bordeaux 10B-430, Seikalite Rose R40, Seikalite Violet B800, 7805, Seikafast Maroon 460N, Seikafast Orange 900, 2900, Seikalite Blue C718, A612, Cyanine Blue 4933M, 4933GN-EP, 4940, 4973 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.); KET Yellow 401, 402, 403, 404, 405, 406, 416, 424, KET Orange 501, KET Red 301, 302, 303, 304, 305, 306, 307, 308, 309, 310, 336, 337, 338, 346, KET Blue 101, 102, 103, 104, 105, 106, 111, 118, 124, KET Green 201 (manufactured by Dainippon Ink and Chemicals Co., Ltd.);Colortex Yellow 301, 314, 315, 316, P-624, 314, U10GN, U3GN, UNN, UA-414, U263, Finecol Yellow T-13, T-05, Pigment Yellow1705, Colortex Orange 202, Colortex Red101, 103, 115, 116, D3B, P-625, 102, H-1024, 105C, UFN, UCN, UBN, U3BN, URN, UGN, UG276, U456, U457, 105C, USN, Colortex Maroon601, Colortex BrownB610N, Colortex Violet600, Pigment Red 122, Colortex Blue516, 517, 518, 519, A818, P-908, 510, Colortex Green 402, 403, Colortex Black 702, U905 (manufactured by Sanyo Dye Co., Ltd.); Lionol Yellow 1405G, Lionol Blue FG7330, FG7350, FG7400G, FG7405G, ES, ESP-S (manufactured by Toyo Ink Co., Ltd.); Toner Magenta E02, Permanent Rubin F6B, Toner Yellow HG, Permanent Yellow GG-02, Hostapearm Blue B2G (manufactured by Hoechst Industrie); Novoperm P-HG, Hostaperm Pink E, Hostaperm Blue B2G (manufactured by Clariant); carbon black #2600, #2400, #2350, #2200, #1000, #990, #980, #970, #960, #950, #850, MCF88, #750, #650, MA600, MA7, MA8, MA11, MA100, MA100R, MA77, #52, #50, #47, #45, #45L, #40, #33, #32, #30, #25, #20, #10, #5, #44, and CF9 (manufactured by Mitsubishi Chemical Corporation).

[0118] (self-dispersing pigment) The pigment may be a self-dispersing pigment. A self-dispersing pigment is a pigment particle whose surface is modified with a group having a hydrophilic group. A self-dispersing pigment has pigment particles and hydrophilic groups bonded to the surface of the pigment particles.

[0119] Examples of hydrophilic groups include carboxy groups, sulfonic acid groups, and phosphorus-containing groups, and examples of phosphorus-containing groups include phosphoric acid groups, phosphonic acid groups, phosphinic acid groups, phosphite groups, and phosphate groups.

[0120] Commercially available examples of self-dispersing pigments include Cabot's Cab-0-Jet® 200K, 250C, 260M, and 270V (sulfonic acid group-containing self-dispersing pigments). Other commercially available examples of self-dispersing pigments include Cabot's Cab-0-Jet® 300K (carboxylic acid group-containing self-dispersing pigments) and Cab-0-Jet® 400K, 450C, 465M, 470V, and 480V (phosphate group-containing self-dispersing pigments).

[0121] The pigment content is not particularly limited, but from the viewpoint of easily adjusting the ink viscosity within the above range and enabling the formation of high-density images, it is preferably in the range of 1.5 to 15% by mass of the ink. A pigment content of 1.5% by mass or more makes it easy to form high-density images, and a pigment content of 15% by mass or less prevents the ink viscosity from becoming too high, making it less likely to impair ejection stability. From the same viewpoint, the pigment content is more preferably in the range of 5 to 15% by mass of the ink.

[0122] (Water dispersible resin: second resin particles) The pigment ink may further contain a water-dispersible resin. The water-dispersible resin has the function of fixing the pigment and the like to the fabric. The water-dispersible resin may be contained in the ink as resin particles (second resin particles).

[0123] Examples of water-dispersible resins include urethane resins, butadiene resins, acrylic resins, and polystyrene. Examples of butadiene resins include styrene-butadiene copolymers and acrylonitrile-butadiene copolymers. Examples of acrylic resins include acrylic ester copolymers, styrene-acrylic copolymers, silicone-acrylic copolymers, and acrylic-modified fluororesins. Among these, urethane resins and acrylic ester copolymers and styrene-acrylic copolymers are preferred. These are presumed to bond with the block copolymer through intermolecular hydrogen bonds, which makes it easier to improve the adhesion of the pigment to fabrics and the abrasion resistance.

[0124] Examples of styrene-acrylic copolymers include styrene-(meth)acrylic acid copolymers and styrene-(meth)acrylic acid-(meth)acrylic acid ester copolymers. Examples of (meth)acrylic acid esters include benzyl (meth)acrylate, cyclohexyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, phenol EO-modified (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate.

[0125] Urethane resins are polymers obtained by reacting polyols with polyisocyanates. Examples of polyols include polypropylene glycol, polyethylene glycol, polytetramethylene glycol, poly(ethylene adipate), poly(diethylene adipate), poly(propylene adipate), poly(tetramethylene adipate), poly(hexamethylene adipate), poly-ε-caprolactone, poly(hexamethylene carbonate), and silicone polyols. Examples of isocyanates include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, and hexamethylene diisocyanate. Other examples of isocyanates include hydrogenated tolylene diisocyanate, hydrogenated 4,4-diphenylmethane diisocyanate, isophorone diisocyanate, and tetramethylxylylene diisocyanate.

[0126] The average particle size of the water-dispersible resin is not particularly limited, but from the viewpoint of preventing nozzle clogging of the inkjet head, it is preferably 300 nm or less, and more preferably 130 nm or less. The average particle size of the water-dispersible resin can be measured by laser diffraction / scattering particle size distribution measurement.

[0127] The content of the water-dispersible resin is preferably 1 to 15% by mass relative to the ink. When the content of the water-dispersible resin is 1% by mass or more, the viscosity of the ink is easily increased to a suitable level, which not only improves the ejection stability but also improves the adhesion of the resulting image to the fabric and the abrasion resistance. When the content of the water-dispersible resin is 15% by mass or less, the viscosity of the ink does not become too high, which makes it less likely to cause nozzle clogging and the like. From the same perspective, the content of the water-dispersible resin is more preferably 2 to 10% by mass relative to the ink.

[0128] (Silicone acrylic resin) The pigment ink may further contain a silicone acrylic resin, which may preferably be one having the same composition as the silicone acrylic resin contained in the first treatment liquid described above.

[0129] (Block copolymer) The pigment ink may contain a pigment and a block copolymer. The block copolymer preferably contains two hydrophilic blocks A at both ends of the molecule, which interact or react with the flocculant, and a hydrophobic block B located between the two hydrophilic blocks A. It is particularly preferable that the block copolymer contains an ABA block copolymer consisting of two hydrophilic blocks A and one hydrophobic block B. The block copolymer may be included as a pigment dispersant or as a fixing resin. For example, in this embodiment, the block copolymer is included as a pigment dispersant.

[0130] Conventionally, the pigment dispersant contained in pigment inks has been, for example, a random copolymer or an AB block copolymer. For example, a random copolymer is a copolymer that randomly contains sites that interact or react with a flocculant. For example, an AB block copolymer is a copolymer that has a block (usually a hydrophilic block A) that contains many sites that interact or react with a flocculant at only one end of the molecule.

[0131] Random copolymers do not have blocks containing many sites that interact or react with flocculants, and therefore are less likely to interact or react with flocculants. AB-type block copolymers have blocks containing many sites that interact or react with flocculants, but because the block is located at only one end of the molecule, there may be fewer bonding points available for bonding to fabric. This may make it difficult to obtain adhesion of the copolymer to fabric, resulting in poor wet and dry rubbing fastness. Furthermore, because the copolymer can bond continuously (film-like) to the fabric at one bonding point, the fabric also tends to become hard.

[0132] In contrast, the above-mentioned block copolymers, such as ABA type, contain blocks at both ends of the molecule that contain many sites that interact or react with the flocculant. Because these blocks are present at at least two locations on both ends of the molecule, there are many bonding points available for bonding with the fabric, making the bond with the fabric stronger. This improves adhesion to the fabric and increases wet and dry friction fastness. Furthermore, because the copolymer can bond intermittently with the fabric at multiple bonding points, the fabric is less likely to become hard than if the copolymer were continuously bonded at a single bonding point. The block containing many sites that interact or react with the flocculant is a hydrophilic block.

[0133] That is, the block copolymer preferably contains two hydrophilic blocks A arranged at both ends of the molecule and a hydrophobic block B arranged between the two hydrophilic blocks A.

[0134] The "hydrophilic block A" is a block that enhances the affinity with the aqueous solvent contained in the pigment ink and contains a site that interacts or reacts with the flocculant attached to the fabric, and refers to the block that has the highest affinity with water among the blocks constituting the copolymer. The number of hydrophilic blocks is preferably two.

[0135] The hydrophilic block A contains structural units derived from a monomer having a hydrophilic functional group (hereinafter referred to as a "hydrophilic monomer"), such as a hydroxyl group, a carboxyl group, and a sulfonic acid group.

[0136] Examples of the hydrophilic monomer constituting the hydrophilic block A include vinyl-based monomers containing a hydrophilic functional group. Examples of such vinyl-based monomers include unsaturated polycarboxylic acids such as (meth)acrylic acid and maleic acid, and monomers containing a carboxy group or an acid anhydride group such as maleic anhydride. Other examples include monomers containing a sulfonic acid group such as styrenesulfonic acid and 4-(methacryloyloxy)butylsulfonic acid. Still other examples include ethylene oxide-modified (meth)acrylic acid ester monomers such as ethylene oxide-modified (meth)acrylic acid alkyl ester. Of these, the hydrophilic monomer is preferably (meth)acrylic acid from the viewpoint of imparting appropriate water solubility to the hydrophilic block A.

[0137] The content of the structural units derived from hydrophilic monomers in the hydrophilic block A should be higher than the content of the structural units derived from hydrophilic monomers in the hydrophobic block B. Specifically, the content of the structural units derived from hydrophilic monomers in the hydrophilic block A is preferably 5% by mass or more relative to 100% by mass of the hydrophilic block A. When the content of the structural units derived from hydrophilic monomers is 5% by mass or more, not only is the dispersibility in aqueous solvents more likely to be improved, but the interaction or reaction with the flocculant is also more likely to be enhanced, which makes it easier to improve adhesion to fabrics. From the same viewpoint, the content is more preferably 10 to 40% by mass.

[0138] The hydrophilic block A may further contain structural units derived from other monomers besides the hydrophilic monomer. Examples of other monomers include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate and tert-butyl (meth)acrylate. Among these, alkyl esters having two or more carbon atoms, such as butyl (meth)acrylate, are preferred. This is because the glass transition temperature (Tg) of the block copolymer is low, and the fabric is less likely to become stiff. However, the other monomers do not include hydrophobic monomers, which will be described later.

[0139] The "hydrophobic block B" is a portion that adsorbs to the pigment, and is the block that has the lowest affinity for the aqueous solvent contained in the ink among the blocks that make up the copolymer. The number of hydrophobic blocks B is preferably one.

[0140] The hydrophobic block B contains structural units derived from a monomer having a hydrophobic functional group (hereinafter referred to as "hydrophobic monomer"). Examples of the monomer having a hydrophobic functional group include vinyl monomers containing an aromatic ring group or an alicyclic hydrocarbon group.

[0141] Examples of vinyl monomers containing an aromatic ring group include (meth)acrylates having an aromatic ring group, such as benzyl (meth)acrylate, phenyl (meth)acrylate, and phenoxyethyl (meth)acrylate. Other examples include aromatic vinyl monomers such as styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, and 1-vinylnaphthalene. Among these vinyl monomers containing an aromatic ring group, preferred are, but are not limited to, vinyl monomers having an aromatic ring group with 6 to 15 carbon atoms.

[0142] Examples of vinyl monomers having an alicyclic alkyl group include (meth)acrylates having an alicyclic alkyl group. Examples of such (meth)acrylates include cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, and cyclododecyl (meth)acrylate. Other examples include bornyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentenyloxyethyl (meth)acrylate. Although not particularly limited, among these vinyl monomers having an alicyclic alkyl group, vinyl monomers having an alicyclic alkyl group having 6 to 15 carbon atoms are preferred.

[0143] Of these, from the viewpoint of improving the adsorption onto the pigment, the hydrophobic monomer is preferably a vinyl monomer having an aromatic ring group with 6 to 15 carbon atoms, such as styrene.

[0144] The content of structural units derived from hydrophobic monomers in the hydrophobic block B is preferably 80% by mass or more relative to the hydrophobic block B. When the content is 80% by mass or more, the adsorption to pigments is likely to be enhanced. From the same viewpoint, the content is more preferably more than 90% by mass, and even more preferably 95% by mass or more.

[0145] The hydrophobic block B may further contain structural units derived from monomers other than hydrophobic monomers. Examples of the other monomers include the above-mentioned other monomers and hydrophilic monomers. However, when the hydrophobic block B contains structural units derived from hydrophilic monomers, the content of the structural units derived from hydrophilic monomers in the hydrophobic block B is lower than that in the hydrophilic block A. Specifically, the content of the structural units derived from hydrophilic monomers is preferably 20% by mass or less, more preferably less than 10% by mass, and even more preferably 5% by mass or less, relative to the hydrophobic block B. In other words, of the two hydrophilic blocks A and B, the content of the structural units derived from hydrophilic monomers (molar number of hydrophilic functional groups) in the hydrophobic block B is the lowest.

[0146] The content of the hydrophobic block B in the ABA block copolymer is preferably 20% by mass or more and 80% by mass or less, and more preferably 20% by mass or more and 50% by mass or less, based on the total mass of the block copolymer. When the content is 20% by mass or more, the content of the hydrophilic block A is low (or the molecular weight is small), which makes it easier to suppress crosslinking aggregation. On the other hand, when the content is 80% by mass or less, the content of the hydrophilic block A is high (or the molecular weight is large), which makes it easier to increase affinity for aqueous solvents.

[0147] When the hydrophilic block is A and the hydrophobic block is B, examples of the structure of the block copolymer include an ABA type, an ABABA type, etc. Among these, the block copolymer is preferably an ABA type block copolymer consisting of two hydrophilic blocks A located at both ends of the molecule and a hydrophobic block B located between them.

[0148] The types and compositional ratios of monomers in the multiple blocks A contained in the block copolymer may be the same or different from one another. Furthermore, when the block copolymer contains multiple blocks B, the types and compositional ratios of monomers in the multiple blocks B may be the same or different from one another. In particular, it is preferable that the two hydrophilic blocks A have the same monomer composition.

[0149] The weight-average molecular weight of the block copolymer is preferably 5,000 to 70,000, and more preferably 7,000 to 30,000. The larger the weight-average molecular weight, the easier it is to increase the dispersibility of the pigment in an aqueous solvent, and the smaller the weight-average molecular weight, the easier it is to suppress crosslinking and aggregation between dispersed pigments. The weight-average molecular weight of the block copolymer can be measured in polystyrene equivalent terms by gel permeation chromatography.

[0150] The molecular weight distribution (PDI) (weight average molecular weight (Mw) of the block copolymer) / (number average molecular weight (Mn) of the block copolymer) is preferably 2.0 or less, and more preferably 1.8 or less. A lower PDI means a narrower and more uniform molecular weight distribution, resulting in better dispersibility.

[0151] The acid value of the block copolymer is, for example, preferably 40 to 400 mgKOH / g, more preferably 40 to 300 mgKOH / g, and even more preferably 40 to 190 mgKOH / g. An acid value of 40 mgKOH / g or higher can enhance the hydrophilicity of the pigment dispersant and further improve the dispersibility of the pigment. Furthermore, an acid value of 400 mgKOH / g or lower can further prevent the hydrophilicity of the pigment dispersant from becoming excessively high, thereby further improving the water resistance of the resulting image-formed product. The acid value can be measured in accordance with the measurement method of JIS K0070:1992.

[0152] The content of the block copolymer is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, relative to the pigment. A content of 10% by mass or more can further enhance the dispersibility of the pigment in the pigment dispersion. Furthermore, a content of the pigment dispersant of 50% by mass or less can further suppress an increase in the viscosity of the pigment dispersion due to an excessive amount of pigment dispersant. Here, the pigment dispersion refers to a dispersion in which a pigment is dispersed in a pigment dispersant.

[0153] The method for synthesizing the block copolymer is not particularly limited, but for example, it can be obtained by sequentially polymerizing vinyl monomers that constitute the blocks by living radical polymerization.

[0154] (Water-soluble organic solvent) The pigment ink, first treatment liquid, and second treatment liquid preferably further contain a water-soluble organic solvent, which can further improve ejection stability by inkjet printing.

[0155] The water-soluble organic solvent is not particularly limited as long as it is compatible with water, and examples thereof include polyhydric alcohols (for example, dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and polypropylene glycol, and trihydric or higher alcohols such as glycerin, trimethylolpropane, and hexanetriol); polyhydric alcohol ethers (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and diethylene glycol dimethyl ether); ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether); monohydric alcohols (e.g., methanol, ethanol, propanol, pentanol, hexanol, cyclohexanol, benzyl alcohol); amines (e.g., ethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine); amides (e.g., formamide, N,N-dimethylformamide, N,N-dimethylacetamide); heterocycles (e.g., 2-pyrrolidone, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidine), sulfoxides (e.g., dimethyl sulfoxide); and sulfones (e.g., sulfolane).

[0156] Furthermore, from the viewpoint of further improving ejection stability by inkjet printing, the water-soluble organic solvent preferably contains a water-soluble organic solvent having a boiling point of 180°C or higher, preferably 190°C or higher, and more preferably 200°C or higher. Examples of water-soluble organic solvents having a boiling point of 180°C or higher include dihydric alcohols and trihydric or higher alcohols. Examples of dihydric alcohols include ethylene glycol (boiling point 197°C), 1,3-butanediol (boiling point 208°C), 1,6-hexanediol (boiling point 223°C), and polypropylene glycol. Examples of trihydric or higher alcohols include glycerin (boiling point 290°C) and trimethylolpropane (boiling point 295°C).

[0157] The content of the water-soluble organic solvent in the second treatment liquid is preferably, for example, 10% by mass or more and 65% by mass or less, and more preferably 20% by mass or more and 45% by mass or less.

[0158] The content of water in the second treatment liquid is 30% by mass or more and 85% by mass or less, and preferably 50% by mass or more and 75% by mass or less.

[0159] (Other ingredients) The pigment ink, the first treatment liquid, and the second treatment liquid may further contain other components in addition to those described above, as necessary. Examples of such other components include surfactants, preservatives, etc.

[0160] The surfactant can reduce the surface tension of the pigment ink, the first treatment liquid, and the second treatment liquid, thereby increasing the wettability of the pigment ink, the first treatment liquid, and the second treatment liquid to the fabric. The type of surfactant is not particularly limited, but can be, for example, an acetylene glycol surfactant, a silicone surfactant, a fluorine surfactant, or the like.

[0161] Examples of the preservative or antifungal agent include aromatic halogen compounds (eg, Preventol CMK), methylene dithiocyanate, halogen-containing nitrogen-sulfur compounds, 1,2-benzisothiazolin-3-one (eg, PROXEL GXL), and the like.

[0162] The pigment ink may further contain a crosslinking agent for crosslinking the resin that constitutes the resin particles. The crosslinking agent is preferably a compound having at least two functional groups in the molecule that react with the crosslinkable groups (hydroxyl groups, carboxyl groups, and ketone groups) of the resin particles. Examples of crosslinking groups that react with hydroxyl groups include isocyanate groups and blocked isocyanate groups. Examples of crosslinking groups that react with carboxyl groups include oxazolyl groups, aziridine groups, and carbodiimide groups. Examples of crosslinking groups that react with ketone groups include hydrazide groups.

[0163] Specifically, examples of crosslinking agents that react with hydroxyl groups include Fixer N (a blocked isocyanate-based crosslinking agent, manufactured by Matsui Pigment Chemical Industry Co., Ltd.). Examples of crosslinking agents that react with carboxyl groups include Fixer F (an aziridine-based crosslinking agent, manufactured by Matsui Pigment Chemical Industry Co., Ltd.). Examples of crosslinking agents that react with ketone groups include adipic acid dihydrazide (ADH, a hydrazine-based crosslinking agent).

[0164] For example, as a crosslinking agent contained in a pigment ink, adipic acid dihydrazide is most preferable from the viewpoint of long-term storage at room temperature and ability to crosslink at room temperature, and a combination of adipic acid dihydrazide with a crosslinking monomer that reacts with diacetone acrylamide (DAAM) is most preferable. There are no particular restrictions on the content of the crosslinking agent in the pigment ink.

[0165] <Preparation of pigment ink, first treatment liquid, and second treatment liquid> The pigment ink, the first treatment liquid, and the second treatment liquid can be prepared by any method so as to contain the components described above. For example, the pigment ink can be produced by mixing the pigment, water, any dispersant, and the like.

[0166] [Inkjet textile printing treatment liquid and inkjet textile printing ink set] Next, one embodiment of the inkjet textile printing treatment liquid of the present invention will be described. The inkjet textile printing treatment liquid of this embodiment is an inkjet textile printing treatment liquid serving as a second treatment liquid used in inkjet textile printing in which a pigment ink, a first treatment liquid, and a second treatment liquid are applied by an inkjet head. That is, the inkjet textile printing treatment liquid of this embodiment has the same configuration as the second treatment liquid used in the textile printing method of this embodiment described above. Furthermore, one embodiment of the inkjet textile printing ink set of the present invention is an inkjet textile printing ink set including a pigment ink, a first treatment liquid, and a second treatment liquid, characterized in that the second treatment liquid is the inkjet textile printing treatment liquid of this embodiment described above. With this inkjet textile printing treatment liquid and inkjet textile printing ink set, it is possible to form an image on a fabric that has good wet rub fastness without impairing the texture. [Example]

[0167] The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In the following examples, unless otherwise specified, operations were performed at room temperature (25°C). Unless otherwise specified, "%", "ppm", and "parts" mean "% by mass", "ppm by mass", and "parts by mass", respectively. In the following examples, "dispersion" refers to a dispersion in which resin particles, pigments, etc. are dispersed in a dispersant.

[0168] [Preparation of first treatment liquid] <Preparation of First Treatment Solution A-1> The following components were mixed in 100% by mass to prepare a first treatment liquid A-1. MPT-60 (Mitsubishi Pencil Co., Ltd., flocculant): 4 parts by mass Glycerin: 10 parts by weight Propylene glycol: 30 parts by weight Proxel GXL(S) (preservative): 0.05 parts by weight Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd., surfactant): 0.1 parts by mass Ion-exchanged water: 55.85 parts by weight

[0169] <Preparation of first treatment solutions A-2 and A-3> First treatment liquids A-2 and A-3 were prepared in the same manner, except that the type and content of the flocculant were changed as shown in Table 1 and the amount of ion-exchanged water was adjusted so that the total amount was 100 parts by mass.

[0170] Table 1 shows the compositions of the first treatment liquids A-1 to A-3.

[0171] [Table 1]

[0172] MPT-60: Mitsubishi Pencil Co., Ltd., alkylamine-epichlorohydrin adduct quaternary salt

[0173] [Preparation of second treatment liquid] <Preparation of Resin Dispersion> (Synthesis of Resin Dispersion Q-1) A separable flask equipped with a stirrer, temperature sensor, condenser, and argon gas inlet was charged with an activator solution prepared by dissolving 2.52 g of anionic activator and 0.58 g of sodium carbonate in 553 g of ion-exchanged water. The anionic activator was sodium dodecylbenzenesulfonate (SDS). The internal temperature of the separable flask was then raised to 80°C while stirring at a speed of 330 rpm under an argon gas flow. Separately, a monomer solution was prepared by dissolving 162 g of n-butyl acrylate (BA), 54 g of methyl methacrylate (MMA), 12 g of diacetone acrylamide (DAAM), and 12 g of methacrylic acid (MAA).

[0174] Next, a solution was prepared by dissolving 0.16 g of a polymerization initiator (potassium persulfate: KPS) in 3.06 g of ion-exchanged water, and the solution was added to a solution (activator solution) heated to 80° C. Next, the monomer solution prepared above was added dropwise to this solution over 60 minutes and stirred to produce a dispersion of resin particles.

[0175] After the monomer solution was added dropwise, the mixture was heated and stirred for 120 minutes. A solution of 0.16 g of a polymerization initiator (potassium persulfate: KPS) dissolved in 3.06 g of ion-exchanged water was then added, and the mixture was stirred for 60 minutes. The mixture was then cooled to 40°C to obtain a dispersion of resin particles (Resin Dispersion Q-1). Resin Dispersion Q-1 had a resin concentration of 20% by mass.

[0176] (Resin dispersion Q-2~Q-7) Table 2 shows the product names of Resin Dispersions Q-2 to Q-7 and the film elongation of Resin Dispersions Q-1 to Q-7. The film elongation was measured by the following method. First, each of Resin Dispersions Q-1 to Q-7 was applied to a polytetrafluoroethylene sheet so that the film thickness after drying would be 500 μm. The applied Resin Dispersions Q-1 to Q-7 were then dried at 23°C for 15 hours, then further dried at 80°C for 6 hours and at 120°C for 20 minutes, and then peeled off from the sheet to produce a resin film. Using a Tensilon universal testing machine "RTC-1225A" (manufactured by Orientec Co., Ltd.), the resulting resin film was stretched at a measurement temperature of 20°C and a measurement speed of 200 mm / min, and the length stretched until the resin film broke was measured. The ratio of the measured length to the original length of the resin film, expressed as a percentage, was defined as the film elongation (%) of the first resin particles.

[0177] [Table 2]

[0178] Superflex 460: Daiichi Kogyo Seiyaku Co., Ltd. Impranil DLP-R: manufactured by Sumika Covestro Urethane Co., Ltd. Impranil DLH: manufactured by Sumika Covestro Urethane Co., Ltd. Takelac W-6061: Mitsui Chemicals Superflex 420: Daiichi Kogyo Seiyaku Co., Ltd. Takelac W-6010: Mitsui Chemicals

[0179] <Preparation of second treatment liquid B-1> The following components were mixed in a 100% by mass conversion to prepare a first treatment liquid B-1. ·Resin dispersion Q-1: 10 parts by mass Chaline E-370 (Nissin Chemical Industry Co., Ltd., silicone acrylic resin): 0.8 parts by weight Glycerin: 10 parts by weight Propylene glycol: 20 parts by weight Proxel GXL(S) (preservative): 0.05 parts by weight Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd., surfactant): 0.1 parts by mass Ion-exchanged water: 55.85 parts by weight

[0180] <Preparation of second treatment solutions B-2 to B-6> Second treatment liquids B-2 to B-12 were prepared in the same manner as second treatment liquid B-1, except that the types and parts by mass of the resin dispersion and silicone acrylic resin were changed as shown in Table 3 and the amount of ion-exchanged water was adjusted so that the total amount was 100 parts by mass.

[0181] Table 3 shows the compositions of the second treatment liquids B-1 to B-12.

[0182] [Table 3]

[0183] [Preparation of pigment ink] <Preparation of polymer for dispersant> (Preparation of Block Copolymer P-1) The following components were placed in a flask equipped with an argon gas inlet tube and a stirring blade, and the mixture was allowed to react at 60° C. for 18 hours, thereby obtaining a prepolymer (hydrophilic block A, weight average molecular weight (Mw): 6920). n-Butyl methacrylate: 138.8g Methyl methacrylate: 73.5g Methacrylic acid: 59.6g Ethyl 2-methyl-2-n-butyltellanyl propionate: 23.3g Dibutyl ditelluride: 14.3g 2,2'-Azobisisobutyronitrile: 2.6g Methyl ethyl ketone: 166.1g Acetonitrile: 166.1g

[0184] Hereinafter, n-butyl methacrylate will also be referred to as "BMA." Similarly, methyl methacrylate will also be referred to as "MMA." Methacrylic acid will also be referred to as "MAA." Ethyl-2-methyl-2-n-butyltellanyl-propionate will also be referred to as "BTEE." Dibutyl ditelluride will also be referred to as "DBDT." 2,2'-Azobisisobutyronitrile will also be referred to as "AIBN."

[0185] A mixed solution of 233 g of benzyl methacrylate (hereinafter referred to as "BzMA"), 23.3 g of MAA, 2.6 g of AIBN, 98.0 g of methyl ethyl ketone, and 98.0 g of acetonitrile, which had been previously purged with argon, was added to the reaction solution, and the mixture was reacted at 60° C. for 9 hours. This yielded a prepolymer (weight average molecular weight (Mw): 9910) containing a hydrophilic block A and a hydrophobic block B.

[0186] A mixed solution of 138.8 g of BMA, 73.5 g of MMA, 59.6 g of MAA, 1.3 g of AIBN, 61.1 g of methyl ethyl ketone, and 388.5 g of acetonitrile, which had been previously purged with argon, was added to the reaction solution, and the mixture was reacted at 60° C. for 23 hours. As a result, a block copolymer P-1 (weight average molecular weight (Mw): 13,800, acid value: 100) containing a hydrophilic block A, a hydrophobic block B, and a hydrophilic block A was obtained.

[0187] After the reaction was completed, 3.6 kg of methyl ethyl ketone was added to the reaction solution, and the mixture was poured into 21 L of heptane with stirring. The precipitated polymer was filtered by suction and dried to obtain a block copolymer P-1.

[0188] (Preparation of Random Copolymer P-2) A random copolymer P-2 (weight average molecular weight (Mw): 15,500, acid value: 96) having a monomer composition of BMA / BzMA / MMA / MAA=36 / 30 / 19 / 15 was obtained by known radical polymerization.

[0189] <Preparation of pigment dispersion> (Preparation of Pigment Dispersion O-1) To 20.0 parts by mass of carbon black pigment, 20 parts by mass of block copolymer P-1 (addition amount relative to the pigment: 30% by mass), 20 parts by mass of propylene glycol, and 5 parts by mass of 1,2-hexanediol were added as a pigment dispersant. Ion-exchanged water was then added and mixed to obtain an aqueous pigment dispersion with a pigment concentration of 20.0%, yielding a pigment dispersion precursor. Hereinafter, propylene glycol will also be referred to as "PG." 1,2-hexanediol will also be referred to as "1,2-HD."

[0190] The pigment dispersion precursor was dispersed using a horizontal media disperser (Labostar Mini LMZ015, zirconia bead diameter 0.3 mm, manufactured by Ashizawa Finetech Co., Ltd.) to prepare pigment dispersion O-1 with a pigment concentration of 20.0%. The volume-based average particle size of pigment dispersion O-1 was 120 nm. The volume-based average particle size of the pigment particles was measured using a particle size distribution analyzer (Zeta Nanosizer 1000HS, manufactured by Malvern Instruments).

[0191] (Preparation of Pigment Dispersion O-2) Pigment dispersion O-2 with a pigment concentration of 20.0% was prepared in the same manner as in the preparation of pigment dispersion O-1, except that block copolymer P-1 was replaced with random copolymer P-2. The volume-based average particle size of pigment dispersion O-2 was 120 nm.

[0192] (Preparation of Pigment Dispersion O-3) Pigment Dispersion O-3 was prepared in the same manner as in the preparation of Pigment Dispersion O-1, except that Cabo-Jet-4107K (pigment concentration 15% by mass) manufactured by Cabot Corporation was used as the pigment dispersion.

[0193] <Preparation of Pigment Ink C-1> The following components were mixed in 100% by mass to prepare pigment ink C-1. Pigment Dispersion O-1: 3.5 parts by weight ·Resin dispersion Q-2: 10 parts by mass Chaline E-370 (Nissin Chemical Industry Co., Ltd., silicone acrylic resin): 0.5 parts by weight Glycerin: 10 parts by weight Propylene glycol: 20 parts by weight Proxel GXL(S) (preservative): 0.05 parts by weight Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd., surfactant): 0.1 parts by mass Ion-exchanged water: 55.85 parts by weight

[0194] <Preparation of Pigment Inks C-2 to C-5> Pigment inks C-2 to C-5 were prepared in the same manner as pigment ink C-1, except that the type of pigment dispersion and the parts by mass of silicone acrylic resin and crosslinking agent were changed as shown in Table 4 and the amount of ion-exchanged water was adjusted so that the total amount was 100 parts by mass. In pigment ink C-5, Meikanate NS-1 manufactured by Meisei Chemical Industry Co., Ltd. was used as the crosslinking agent.

[0195] Table 4 shows the compositions of pigment inks C-1 to C-5.

[0196] [Table 4]

[0197] [Image formation and evaluation] The inkjet printing methods of Examples 1 to 10 and Comparative Examples 1 to 4 were carried out using the treatment liquids and pigment inks corresponding to the formulations of the first treatment liquid, pigment ink, and second treatment liquid shown in Table 5, in accordance with the method of forming a textile print image described below.

[0198] <Textile printing image formation> As the fabric, cotton satin (100% cotton: product name 60 Cotton Satin, manufactured by Okadaya Co., Ltd.) was prepared.

[0199] The inkjet head in the printing device was a scan type, and a Konica Minolta Pro120 equipped with an inkjet head KM1024i (Konica Minolta) was used. In the textile printing methods of Examples 1 to 10 and Comparative Examples 1 to 4, the first treatment liquid head was filled with first treatment liquids A-1 to A-3 corresponding to the first treatment liquid formulations shown in Table 5. The pigment ink head was filled with pigment inks C-1 to C-5 corresponding to the pigment ink formulations shown in Table 5. The second treatment liquid head was filled with second treatment liquids B-1 to B-12 corresponding to the second treatment liquid formulations shown in Table 5. Using the first treatment liquid head, pigment ink head, and second treatment liquid head described above, the first treatment liquids A-1 to A-3, pigment inks C-1 to C-5, and second treatment liquids B-1 to B-12 shown in Table 5 were applied to fabric by inkjet printing. The applied first treatment liquid, pigment ink, and second treatment liquid were then dried to obtain a printed textile image. The first treatment liquid, pigment ink, and second treatment liquid were ejected from the inkjet head at a main scanning speed of 540 dpi and a sub-scanning speed of 720 dpi. dpi represents the number of ink droplets (dots) per 2.54 cm. The ejection frequency was 22.4 kHz. The image was printed in a forward / reverse pass sequence, and created in two passes (two scans). The image was then dried at 150°C for 3 minutes in a belt-conveying dryer to obtain a 200 mm x 200 mm 100% solid printed textile image. The deposition amount of the first treatment liquid, pigment ink, and second treatment liquid was 10 g / m, respectively. 2 , 20g / m 2 and 10 g / m 2 These adhesion amounts were each determined from the amount of treatment liquid ejected.

[0200] <Evaluation of texture> A sensory evaluation of the texture of the printed fabric was carried out by five people. The texture of the fabric was evaluated according to the following criteria based on the number of people who felt that the printed fabric was stiffer than the unprinted fabric. The evaluation results are shown in Table 5.

[0201] A: The number of people who felt that the fabric became stiffer after printing was 0 to 1. B: Two or three people felt that the fabric became stiffer after printing. C: Four people felt that the fabric was stiffer after printing. D: Five people felt that the fabric was stiffer after printing.

[0202] <Evaluation of wet rubbing fastness> The wet rub fastness of the image formed on the fabric was evaluated using a crock meter (rubbing tester type I) in accordance with the wet test of JIS L 0849.

[0203] Specifically, a 100 mm × 100 mm area of ​​the formed image was rubbed back and forth 100 times with a 200 g load using a white cotton rubbing cloth. The white cotton rubbing cloth was wetted with water to approximately 100% wetness. After rubbing, the staining grade was determined visually in accordance with Clause 10 (Determination of Color Fastness) of JIS L 0801. Color transfer to the white cotton rubbing cloth was observed and the wet rubbing fastness was evaluated according to the following criteria. The evaluation results are shown in Table 5. According to the following criteria, A and B were considered acceptable. The color change criteria were based on a staining gray scale, with "Grade 1" indicating the most severe staining.

[0204] (Evaluation criteria for wet rubbing fastness) A: Color change of grade 3 or higher. B: Color change is grade 2 to 3 (grades 2 and 3 are not included). C: Color change is grade 2. D: Color change is grade 1-2 (grade 2 not included).

[0205] [Table 5]

[0206] (result) In the inkjet printing methods of Examples 1 to 10, printed images were formed using a second treatment liquid containing first resin particles and a silicone acrylic resin having a film elongation of 600 to 1600%. The printed images formed by the inkjet printing methods of Examples 1 to 10 showed good results in both evaluations of texture and wet rubbing fastness.

[0207] On the other hand, when the film elongation of the first resin particles contained in the second treatment liquid is less than 600%, it was confirmed that the texture and wet rub fastness tend to deteriorate, as in Comparative Examples 1 and 2. Furthermore, when the second treatment liquid does not contain a silicone acrylic resin, as in Comparative Example 3, and when the second treatment liquid contains a silicone acrylic resin but does not contain specific resin particles, as in Comparative Example 4, it was confirmed that the texture and wet rub fastness tend to deteriorate in both cases. [Industrial Applicability]

[0208] According to the present invention, it is possible to provide an inkjet printing method that can form an image having good wet rub fastness on a fabric without impairing the texture. [Explanation of symbols]

[0209] 1 head unit 1P1 First processing liquid head 1P2 Second processing liquid head 1Y Yellow ink head 1M magenta ink head 1C Cyan ink head 1K black ink head 2 Belt conveyor 3. Application section 4. Conveyor belt cleaning section 10 Application section 20 Droplet discharge means 22 Carriage 30 Scanning unit 41 Sprinkler pipe 41a Watering tube 42 Brush Roller 43 Cleaning blade 44 Cleaning sponge 45 Heating section 100 Inkjet printing device 101 Fabric payout section 102 Fabric Recovery Department 103 Conveyor 105 Drying section 106 Control Unit 221 Drive roller 222 driven roller 223 Conveyor Belt T1, T2 fabric T3 printed fabric

Claims

1. An inkjet textile printing method in which a pigment ink, a first treatment liquid, and a second treatment liquid are applied by an inkjet head, the first treatment liquid contains a flocculant and serves to retain at least one of the pigment ink and the second treatment liquid on the surface of the fabric; the inkjet head that ejects the first treatment liquid, the inkjet head that ejects the pigment ink, and the inkjet head that ejects the second treatment liquid are arranged on the same carriage; An image is formed using a multi-pass method. In the outward path, the first treatment liquid is applied, and then the pigment ink and the second treatment liquid are applied in this order; In the return path, after the second treatment liquid is applied, the pigment ink and the first treatment liquid are applied in this order; the second treatment liquid contains first resin particles and a silicone acrylic resin having a film elongation of 600 to 1600%, an ink-jet printing method, characterized in that the first treatment liquid, the pigment ink, and the second treatment liquid are applied to the same location in the same scanning operation without drying.

2. the pigment ink contains second resin particles and an aqueous solvent; 2. The ink-jet printing method according to claim 1, wherein at least one of the resin of the first resin particles of the second treatment liquid and the resin of the second resin particles of the pigment ink contains an acrylic resin or a urethane resin.

3. 3. The ink-jet printing method according to claim 1, wherein the pigment ink contains a silicone acrylic resin.

4. 3. The inkjet printing method according to claim 1, wherein the first treatment liquid contains at least one selected from the group consisting of a compound having a cationic group, a polyvalent metal salt, and an organic acid.

5. 5. The ink-jet printing method according to claim 4, wherein the compound having a cationic group is a cationic resin.

6. the pigment ink contains a pigment and a block copolymer; 3. The inkjet printing method according to claim 1, wherein the block copolymer contains two hydrophilic blocks A that are arranged at both ends of the molecule and that interact or react with at least the flocculant contained in the first treatment liquid, and a hydrophobic block B that is arranged between the two hydrophilic blocks A.

7. 7. The ink-jet printing method according to claim 6, wherein the block copolymer contains an ABA type block copolymer consisting of the two hydrophilic blocks A and one hydrophobic block B.

8. 3. The ink-jet printing method according to claim 1, wherein the pigment ink contains a crosslinking agent.

9. A treatment liquid for inkjet textile printing as the second treatment liquid used in inkjet textile printing in which a pigment ink, a first treatment liquid, and a second treatment liquid are applied by an inkjet head, the first treatment liquid contains a flocculant for retaining the pigment ink or the second treatment liquid on the surface of the fabric; the inkjet head that ejects the first treatment liquid, the inkjet head that ejects the pigment ink, and the inkjet head that ejects the second treatment liquid are disposed on the same carriage and are used to form an image by a multi-pass method; In the outward path, the first treatment liquid is applied, and then the pigment ink and the second treatment liquid are applied in this order; In the return path, after the second treatment liquid is applied, the pigment ink and the first treatment liquid are applied in this order; the second treatment liquid contains first resin particles and a silicone acrylic resin having a film elongation of 600 to 1600%, The inkjet printing treatment liquid is characterized in that the first treatment liquid, the pigment ink, and the second treatment liquid are applied to the same location in the same scanning operation without drying.

10. An inkjet printing ink set comprising a pigment ink, a first treatment liquid, and a second treatment liquid, 10. An ink set for ink-jet textile printing, wherein the second treatment liquid is the treatment liquid for ink-jet textile printing according to claim 9.

11. An inkjet printing apparatus that applies a pigment ink, a first treatment liquid, and a second treatment liquid using an inkjet head, the first treatment liquid contains a flocculant for retaining the pigment ink or the second treatment liquid on the surface of the fabric; the inkjet head that ejects the first treatment liquid, the inkjet head that ejects the pigment ink, and the inkjet head that ejects the second treatment liquid are arranged on the same carriage; An image is formed using a multi-pass method. In the outward path, the first treatment liquid is applied, and then the pigment ink and the second treatment liquid are applied in this order; In the return path, after the second treatment liquid is applied, the pigment ink and the first treatment liquid are applied in this order; the second treatment liquid contains first resin particles and a silicone acrylic resin having a film elongation of 600 to 1600%, An inkjet textile printing apparatus, characterized in that the first treatment liquid, the pigment ink, and the second treatment liquid are applied to the same location in the same scanning operation while still wet.

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