Reaction solution, ink set, and recording method for pigment printing

Abstract

To provide a reactive liquid for pigment dyeing that offers superior color development and friction fastness, can suppress pitting corrosion in a metal component of a recording device, and is used through inkjet dispensing.SOLUTION: A reactive liquid for pigment dyeing according to one embodiment includes a polyvalent metal salt, a cationic polymer, a polyhydric alcohol, an alkali, and water. The alkali is an amine compound. The reactive liquid is used through inkjet dispensing.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a reaction solution for pigment printing, an ink set, and a recording method. [Background technology]

[0002] Conventionally, in textile printing (pigment printing) using ink compositions containing pigments as colorants, a reaction solution that coagulates the ink components is applied to the fabric in order to improve the color development of the colorant. In this context, in a recording method in which the process of applying the reaction solution and ink is performed in a single recording device, the use of an inkjet method to eject the reaction solution has been investigated.

[0003] For example, Patent Document 1 discloses a reaction solution containing a polyvalent metal compound that can be applied to a wet-on-wet recording method in pigment printing, in which the steps from the application of the reaction solution to the application of ink are carried out without a drying step. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2016-089288 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, pigment printing reaction solutions used by inkjet printing have problems such as poor color development and friction fastness, as well as pitting corrosion on the metal components of recording devices. [Means for solving the problem]

[0006] One embodiment of the pigment printing reaction solution according to the present invention is: Polyvalent metal salts, Cationic polymers and Polyhydric alcohols, It contains alkali and water, The alkali is an amine compound, It is used by ejecting it using an inkjet method.

[0007] One embodiment of the ink set according to the present invention is: A textile inkjet ink composition containing pigment, resin particles, and water, The present invention comprises a pigment printing reaction solution according to one embodiment described above.

[0008] One aspect of the recording method according to the present invention is: An ink application process in which an ink composition is applied to the fabric by an inkjet method, The method comprises a reaction solution application step of applying a pigment printing reaction solution according to one embodiment described above to the fabric by an inkjet method. [Brief explanation of the drawing]

[0009] [Figure 1] A schematic perspective view of an inkjet printing apparatus applicable to the recording method according to this embodiment. [Figure 2] A schematic diagram showing an example of the arrangement of inkjet heads in an inkjet textile printing device. [Figure 3] A schematic diagram showing an example of the arrangement of inkjet heads in an inkjet textile printing device. [Figure 4] A schematic diagram showing an example of the arrangement of inkjet heads in an inkjet textile printing device. [Modes for carrying out the invention]

[0010] Embodiments of the present invention will be described below. The embodiments described below are examples of the present invention. The present invention is not limited in any way to the embodiments described below, and includes various modifications that can be implemented without changing the gist of the present invention. Not all of the configurations described below are necessarily essential to the present invention.

[0011] 1. Reaction solution for pigment printing The reaction liquid for pigment printing according to one embodiment of the present invention contains a polyvalent metal salt, a cationic polymer, a polyhydric alcohol, an alkali, and water, wherein the alkali is an amine compound and is used by being ejected by an inkjet method.

[0012] Conventionally, in inkjet pigment printing, in order to improve the color development property of a coloring material, a treatment of attaching a reaction liquid that aggregates the components of the ink to a fabric has been performed. This treatment is usually performed by an immersion method or the like using a device / equipment separate from the inkjet recording device. However, in such a method, not only is it necessary to use a separate device / equipment, but the use of the separate device / equipment complicates the process and requires know-how. In addition, there is waste liquid discharge, which is not preferable from the perspective of environmental load.

[0013] Therefore, in inkjet pigment printing, studies have been made on ejecting not only the ink composition but also the reaction liquid by the inkjet method. In such a mode, there is no need to use a separate device / equipment, the process can be simplified, and waste liquid discharge can be eliminated.

[0014] However, a reaction liquid containing only a polyvalent metal salt can aggregate the ink near the surface of the fabric and improve the color development property, but there is a problem that the ink remaining near the surface of the fabric tends to be inferior in rubbing fastness (especially wet rubbing fastness). Therefore, it has now been found that by further containing a cationic polymer in the reaction liquid, water resistance can be imparted to the fabric and rubbing fastness (especially wet rubbing fastness) can also be improved. On the other hand, when using a cationic polymer, a new problem has occurred that pitting corrosion occurs in metal members such as the recording head of the recording device.

[0015] On the contrary, according to the reaction liquid for pigment printing according to the present embodiment, by further containing an amine compound as a specific alkali component, while improving the color development property and rubbing fastness, pitting corrosion of metal members such as the recording head can be suppressed.

[0016] 1.1 Use The pigment printing reaction solution according to this embodiment is used by being ejected by an inkjet method.

[0017] "For pigment printing" refers to materials used in printing processes that utilize ink compositions containing pigments.

[0018] The "inkjet method" is a recording method in which droplets of ink or reaction solution are ejected from the nozzles of an inkjet head in an inkjet recording device and applied to a recording medium.

[0019] The pigment printing reaction solution according to this embodiment is processed using an inkjet method, which differs from conventional processing methods. Because it is dispensed and used by inkjet, there is no need to use separate equipment or facilities, the process is simplified, and waste liquid discharge can be eliminated. Furthermore, by applying the reaction solution using the inkjet method, the image is less likely to bleed even when a large amount of reaction solution is applied, compared to when it is applied by spraying or other methods that do not use inkjet. This is presumed to be because, with inkjet application, the amount of discharge can be controlled to a small amount, and the ink and the reaction solution can come into immediate contact in a wet-on-wet manner, which facilitates the reaction between the reaction solution and the ink.

[0020] In contrast, with coating methods other than inkjet, such as spraying, it is difficult to control the amount of ink dispensed. Furthermore, a drying process is required, and the ink and reaction solution do not come into immediate contact in a wet-on-wet manner. Therefore, the reaction between the reaction solution and the ink is inferior. In other words, when a large amount of reaction solution is applied to the fabric by spraying and then dried, the reaction solution itself penetrates into the fabric, the reaction between the dried components of the reaction solution and the ink is a solid / liquid reaction, and the cationic polymer has a low ink coagulation effect. As a result, the ink that lands later does not coagulate immediately, leading to ink penetration and bleeding.

[0021] Note that the "reaction solution" is not an ink composition used to color the fabric, but rather an auxiliary solution used together with the ink composition. Furthermore, it is preferable that the reaction solution can agglomerate or thicken the components of the ink composition, and more preferably that it contains components that agglomerate or thicken the components of the ink composition. The reaction solution may contain a colorant, but it is preferable that the amount is 0.2% by mass or less, more preferably 0.1% by mass or less, even more preferably 0.05% by mass or less, and the lower limit is 0% by mass, relative to the total mass of the reaction solution. It is preferable that the reaction solution does not contain a colorant.

[0022] The following describes each component contained in the pigment printing reaction solution according to this embodiment.

[0023] 1.2 Polyvalent metal salts The pigment printing reaction solution according to this embodiment contains a polyvalent metal salt. When the polyvalent metal salt comes into contact with the ink composition, it has an excellent ability to agglomerate the components of the ink composition, causing the ink to agglomerate near the surface of the fabric and resulting in good color development. Furthermore, if the reaction solution contains alkali, the cationic polymer may deteriorate during long-term storage of the reaction solution, but the inclusion of a polyvalent metal salt tends to maintain good color development.

[0024] A polyvalent metal salt is a compound composed of a metal ion with two or more valencies and an anion. Examples of metal ions with two or more valencies include calcium, magnesium, copper, nickel, zinc, barium, aluminum, titanium, strontium, chromium, cobalt, and iron. Among the metal ions that make up these polyvalent metal salts, it is preferable that at least one of calcium ions and magnesium ions is present, given their excellent ability to aggregate the ink components. Furthermore, from the viewpoint of balancing aggregation and frictional fastness, magnesium ions are even more preferable.

[0025] The polyvalent metal salt is preferably a magnesium salt. For example, while calcium salts exhibit excellent cohesiveness, the cohesive reaction is difficult to control, and the friction fastness and granular texture on fabric may be inferior. In contrast, magnesium salts, compared to other salts such as calcium salts, have a milder cohesive reaction with the ink, making the reaction easier to control. Therefore, they tend to provide good color development, as well as good friction fastness and granular texture.

[0026] The anions that make up polyvalent metal salts are either inorganic or organic ions. Examples of inorganic ions include chloride ions, bromide ions, iodide ions, nitrate ions, sulfate ions, and hydroxide ions. Examples of organic ions include organic acid ions, such as carboxylate ions.

[0027] The polyvalent metal salt is preferably a sulfate. For example, the polyvalent metal salt is a halide salt (Cl - , Br - , I - Salts such as (Cl) (and other salts), especially chloride salts (Cl) - If the polyvalent metal salt is a sulfate, pitting corrosion is likely to occur on the metal components of the recording device. The mechanism is as follows: First, a portion of the passive film on the surface of the metal component (e.g., stainless steel) is destroyed by chloride ions. Since the passive film is at a noble potential while the destruction site is at a noble potential, a local galvanic cell is formed and pitting corrosion progresses. Furthermore, chloride ions accumulate in the pitted area, increasing the chlorine concentration and causing the metal to dissolve. This lowers the pH in the pitted area, further promoting metal dissolution. Since these reactions occur locally within the pores of the pitted area, the pitting corrosion progresses continuously. In contrast, if the polyvalent metal salt is a sulfate, these reactions do not occur, and pitting corrosion can be further suppressed. From a similar viewpoint, it is preferable that the concentration of chloride ions in the reaction solution be low.

[0028] Specific examples of polyvalent metal salts are not particularly limited, but include calcium carbonate such as heavy calcium carbonate and light calcium carbonate, calcium nitrate, calcium chloride, calcium sulfate, magnesium sulfate, calcium hydroxide, magnesium chloride, magnesium carbonate, barium sulfate, barium chloride, zinc carbonate, zinc sulfide, aluminum silicate, calcium silicate, magnesium silicate, copper nitrate, calcium acetate, magnesium acetate, and aluminum acetate. These polyvalent metal salts may be used individually or in combination of two or more. Among these, one or more selected from magnesium chloride, magnesium sulfate, magnesium carbonate, magnesium silicate, and magnesium acetate are preferred because they can provide good color development, as well as good friction fastness and granular texture. In particular, one or more selected from magnesium sulfate, magnesium carbonate, magnesium silicate, and magnesium acetate are more preferred because they can further suppress pitting corrosion. These metal salts may contain hydration water in their raw material form.

[0029] The lower limit of the polyvalent metal salt content is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, even more preferably 1.5% by mass or more, particularly preferably 2.0% by mass or more, and most preferably 2.5% by mass or more, relative to the total mass of the reaction solution. The upper limit of the polyvalent metal salt content is preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 6% by mass or less, even more preferably 5% by mass or less, particularly preferably 4% by mass or less, and most preferably 3.5% by mass or less, relative to the total mass of the reaction solution. When the polyvalent metal salt content is within the above range, it tends to be possible to achieve a good balance between color development, friction fastness, and suppression of pitting corrosion.

[0030] 1.3 Cationic polymers The pigment printing reaction solution according to this embodiment contains a cationic polymer. By including a cationic polymer, water resistance can be imparted to the fabric, and friction fastness (especially wet friction fastness) can be improved.

[0031] A cationic polymer is a polymer that possesses cationic properties. Examples of cationic polymers include cationic urethane resins, cationic olefin resins, and cationic amine resins. Among these, cationic amine resins are preferred.

[0032] As cationic urethane resins, commercially available products can be used, for example, Hydra Products such as CP-7010, CP-7020, CP-7030, CP-7040, CP-7050, CP-7060, CP-7610 (product names, manufactured by Dainippon Ink and Chemicals, Inc.), Superflex 600, 610, 620, 630, 640, 650 (product names, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and Urethane Emulsion WBR-2120C, WBR-2122C (product names, manufactured by Taisei Fine Chemical Co., Ltd.) can be used.

[0033] Cationic olefin resins have olefins such as ethylene and propylene as their structural framework, and known ones can be appropriately selected and used. Cationic olefin resins may also be in an emulsion state dispersed in a solvent such as water or an organic solvent. Commercially available cationic olefin resins can be used, such as Arrowbase CB-1200 and CD-1200 (trade names, manufactured by Unitika Ltd.).

[0034] As the cationic amine resin, any known resin can be appropriately selected and used, but it is preferable that the structure contains a cationic functional group selected from primary amine groups, secondary amine groups, tertiary amine groups, quaternary ammonium bases, imino groups, and amide groups, and it is particularly preferable that the cationic functional group contains a quaternary ammonium base. Such cationic amine resins tend to have superior color development properties. Furthermore, the cationic amine resin may also contain two or more of the above-mentioned cationic functional groups.

[0035] Cationic amine resins having a primary amine group include polyallylamine, polyallylamine hydrochloride, polyallylamine amide sulfate, methoxycarbonylated allylamine polymer, methylcarbonylated allylamine acetate polymer, ureated polyallylamine polymer, carboxymethylated polyallylamine polymer, and hexamethylenediamine / epichlorohydrin resin.

[0036] Cationic amine resins having primary amine groups can also be commercially available, such as PAA-01, PAA-03, PAA-05, PAA-08, PAA-15C, PAA-25; PAA-HCL-01, PAA-HCL-03, PAA-HCL-05, PAA-HCL-3L, PAA-HCL-10L; PAA-SA; PAA-U5000, PAA-U7030; PAA-AC5050A; PAA-N5000, PAA-N5050CL; PAA-CB-1 (manufactured by Nitto Boseki Medical Co., Ltd.), and Unisense KHE103L (manufactured by Senka Co., Ltd.).

[0037] Cationic amine resins having a secondary amine group include diallylamine polymers, diallylamine hydrochloride polymers, diallylamine hydrochloride / sulfur dioxide copolymers, diallylamine acetate / sulfur dioxide copolymers, diallylamine hydrochloride / acrylamide copolymers, dimethylamine / epichlorohydrin resins, dimethylamine / ammonia / epichlorohydrin resins, and dimethylamine / ethylenediamine / epichlorohydrin polymers.

[0038] Cationic amine resins having secondary amine groups can also be commercially available, such as PAS-21; PAS-21CL; PAS-92; PAS-92A; PAS-2141CL (manufactured by Nitto Boseki Medical Co., Ltd.), Unisense KHE104L; Unisense KHE100L (manufactured by Senka Co., Ltd.), and Catiomaster PE-30 (manufactured by Yokkaichi Gosei Co., Ltd.).

[0039] Cationic amine resins having a tertiary amine group include methyldiallylamine hydrochloride polymer, methyldiallylamine amide sulfate polymer, methyldiallylamine acetate polymer, methyldiallylamine hydrochloride-sulfur dioxide copolymer, and dicyandiamide-poly Examples include alkylene polyamine polycondensates.

[0040] Cationic amine resins having a tertiary amine group can also be commercially available, such as PAS-M-1L, PAS-M-1; PAS-22SA-40; PAS-M-1A; PAS-2201CL (manufactured by Nitto Boseki Medical Co., Ltd.) and Unisense KHP10L (manufactured by Senka Co., Ltd.).

[0041] Furthermore, commercially available cationic amine resins having primary, secondary, or tertiary amine groups include Sparamin C-305 (manufactured by Toho Chemical Industry Co., Ltd.), Arafix 255, 251S (manufactured by Arakawa Chemical Co., Ltd.), Jetfix 38A, 220, 260, N700, 90X (manufactured by Satoda Chemical Co., Ltd.), WS4020, WS4030, WS4027, PA6646, and DK6854 (manufactured by Seikoh PMC Co., Ltd.).

[0042] Cationic amine resins containing a quaternary ammonium base include diallyldimethylammonium chloride polymer, diallylmethylethylammonium ethyl sulfate polymer, diallylmethylethylammonium ethyl sulfate / sulfur dioxide copolymer, diallyldimethylammonium chloride / sulfur dioxide copolymer, and diallyldimethylammonium chloride / acrylamide copolymer.

[0043] Cationic amine resins containing quaternary ammonium bases can also be commercially available, such as PAS-H-1L, PAS-H-5L, PAS-H-10L; PAS-24; PAS-2401; PAS-A-1, PAS-A-5; PAS-J-81L, PAS-J-81, PAS-J-41 (manufactured by Nitto Boseki Medical Co., Ltd.), EP-1137 (manufactured by Takamatsu Oil & Fat Co., Ltd.), Papiogen P-105, Myriogen P-20, Unisense FPA100L, and Unisense KHE107L (manufactured by Senka Co., Ltd.).

[0044] Cationic amine resins having an imino group include polyethyleneimine, octadecyl isocyanate-modified polyethyleneimine, and propylene oxide-modified polyethyleneimine.

[0045] Cationic amine resins containing imino groups can also be commercially available, such as SP-003, SP-006, SP-012, SP-018, SP-200, HM-2000, P-1000, P-3000; RP-20; PP-061 (manufactured by Nippon Shokubai Co., Ltd.), and Lupasol (manufactured by BASF).

[0046] Cationic amine resins containing amide groups include polyamides and polyamide epoxy resins. Commercially available cationic amine resins containing amide groups include, for example, Smirez Resin 633, 630(30), 675A, 6615, 6725, and SLX-1 (manufactured by Taoka Chemical Industries Co., Ltd.).

[0047] Furthermore, the following are examples of cationic amine resins having two or more cationic functional groups.

[0048] Cationic amine resins having primary and secondary amine groups include allylamine-diallylamine copolymers and allylamine acetate-diallylamine acetate copolymers. Commercially available examples include PAA-D11 and PAA-D19A (manufactured by Nitto Boseki Medical Co., Ltd.).

[0049] Cationic amine resins having a primary amine group and a quaternary ammonium base include allylamine-diallyldimethylammonium chloride copolymers, and Examples of commercially available products include PAA-1123 (manufactured by Nitto Boseki Medical Co., Ltd.).

[0050] Cationic amine resins having a tertiary amine group and a quaternary ammonium base include methyldiallylamine-diallyldimethylammonium chloride copolymer and diallyldimethylammonium chloride-3-chloro-2-hydroxypropylated diallylamine hydrochloride copolymer. Commercially available products include, for example, PAA-2223; PAS-880 (manufactured by Nitto Boseki Medical Co., Ltd.).

[0051] Cationic polymers may be used individually or in combination of two or more types.

[0052] Furthermore, it is preferable that the cationic polymer has a structure derived from epihalohydrin. Epihalohydrin is a monomer having an epoxy group and a halogen group. Examples of halogen groups include a fluoro group, a chloro group, a bromo group, an iodine group, and an astat group. It is more preferable that the epihalohydrin is epichlorohydrin, where the halogen group is a chloro group. When the cationic polymer has a structure derived from epihalohydrin, the unreacted epoxy groups remaining in the epihalohydrin can contribute to the crosslinking reaction as crosslinking groups. This means that the ink becomes more viscous and aggregates more easily, improving color development, and the ink layer is strengthened by crosslinking, resulting in a tendency to obtain better friction fastness. Also, when the fabric is cotton, a crosslinking reaction occurs between the crosslinking groups derived from epihalohydrin and the hydroxyl groups of the cotton cellulose, which tends to improve the adhesion between the fabric and the ink layer, resulting in a tendency to obtain better friction fastness.

[0053] As a cationic polymer having a structure derived from epihalohydrin, it is more preferable that it be a cationic amine resin having a structure derived from epihalohydrin. Examples of such polymers include polyamine-epihalohydrin copolymers, polyamide-epihalohydrin copolymers, polyamide-polyamine-epihalohydrin copolymers, and amine-epihalohydrin copolymers.

[0054] Cationic polymers having a structure derived from epihalohydrins may be commercially available, such as Kymene557 (manufactured by SOLENIS), Myriogen P-20, and Unisense FPA. Examples include 100L, Unisense KHE 107L (manufactured by Senka Co., Ltd.), WS-4020, 4030, 4027, TS-4070 (manufactured by Seikoh PMC, polyamide-epichlorohydrin polymer), WS-4011 (manufactured by Seikoh PMC, polyamine-epichlorohydrin polymer), AF-100, 251S, 255, 255LOX, 2500 (manufactured by Arakawa Kogyo Kagaku Co., Ltd., polyamide-polyamine-epichlorohydrin polymer), Kathiomaster PE-30 (manufactured by Yokkaichi Gosei Co., Ltd., dimethylamine-ethylenediamine-epichlorohydrin condensate), and EPA-SK01 (manufactured by Yokkaichi Gosei Co., Ltd., polyamide-polyamine-epichlorohydrin condensate).

[0055] The mass-average molecular weight of the cationic polymer is preferably 100,000 or less, more preferably 80,000 or less, even more preferably 60,000 or less, particularly preferably 40,000 or less, and most particularly preferably 20,000 or less. The lower limit of the mass-average molecular weight of the cationic polymer is not particularly limited, but is preferably 100 or more, more preferably 1,000 or more, and even more preferably 5,000 or more. When the mass-average molecular weight of the cationic polymer is 100,000 or less, the ejection performance when the reaction solution is applied by inkjet tends to be better. The mass-average molecular weight can be measured using gel permeation chromatography (GPC measuring device) with polyethylene glycol as the standard polymer.

[0056] The content of the cationic polymer is preferably 0.5 to 5.0% by mass, more preferably 1.0 to 4.5% by mass, even more preferably 1.5 to 4.0% by mass, particularly preferably 2.0 to 3.5% by mass, and most preferably 2.0 to 3.0% by mass, relative to the total amount of the reaction solution. When the cationic polymer content is 0.5% by mass or more, good frictional fastness tends to be achieved. On the other hand, when the cationic polymer content is 5.0% by mass or less, the viscosity of the reaction solution is more easily made suitable for the inkjet method, and intermittent printing stability tends to be achieved.

[0057] 1.4 Polyhydric alcohols The pigment printing reaction solution according to this embodiment contains a polyhydric alcohol. A polyhydric alcohol is a type of organic solvent. When a cationic polymer is included, the viscosity of the reaction solution tends to increase even if only a small amount of water evaporates from it. Therefore, when a reaction solution containing a cationic polymer is ejected by an inkjet method, the ejection stability (especially intermittent printing stability) tends to be poor. In contrast, when a polyhydric alcohol is included in the reaction solution, the moisture retention of the reaction solution improves, and the ejection stability tends to be improved. Furthermore, it is presumed that the polyhydric alcohol can suppress the degradation of the cationic polymer, and even when the reaction solution is stored for a long period of time, it may be possible to impart water resistance to the fabric and improve friction fastness (especially wet friction fastness). In addition, by including a polyhydric alcohol, the droplets ejected by the inkjet method dry less quickly, and the generation of mist can be suppressed. As a result, the adhesion of the reaction solution near the nozzle surface of the head can be reduced, and the effects of pitting corrosion tend to be reduced.

[0058] A polyhydric alcohol is a substance having two or more hydroxyl groups in its molecule, preferably three or more hydroxyl groups. Examples of polyhydric alcohols include alkanediols and polyols, and it is preferable to have one or more selected from these. The state of a polyhydric alcohol at room temperature and pressure may be liquid or solid, but it is preferable to be liquid.

[0059] Alkanediols include, for example, compounds in which an alkane is substituted with two hydroxyl groups. Examples of alkanediols include ethylene glycol (also known as ethane-1,2-diol), propylene glycol (also known as propane-1,2-diol), 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, 1,3-propanediol, 1,3-butylene glycol (also known as 1,3-butanediol), 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, and 2 Examples include 4-pentanediol, 2-methyl-1,3-propanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,3-pentanediol, 3-methyl-1,5-pentanediol, 2-methylpentane-2,4-diol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, and 2-methyl-2-propyl-1,3-propanediol.

[0060] Examples of polyols include condensates formed by the intermolecular condensation of two or more alkanediol molecules via hydroxyl groups, and compounds having three or more hydroxyl groups.

[0061] Examples of condensates formed by the intermolecular condensation of two or more alkanediol molecules at their hydroxyl groups include dialkylene glycols such as diethylene glycol and dipropylene glycol, and trialkylene glycols such as triethylene glycol (standard boiling point 287°C) and tripropylene glycol.

[0062] Compounds having three or more hydroxyl groups are compounds with an alkane or polyether structure as their backbone and containing three or more hydroxyl groups. Examples of compounds having three or more hydroxyl groups include glycerin (standard boiling point 290°C), trimethylolethane, trimethylolpropane, 1,2,5-hexanetriol, 1,2,6-hexanetriol, pentaerythritol, and polyoxypropylenetriol.

[0063] The polyhydric alcohol content is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, even more preferably 15 to 35% by mass, particularly preferably 20 to 35% by mass, and most particularly preferably 20 to 30% by mass, relative to the total amount of the reaction solution. When the polyhydric alcohol content is within the above range, it tends to provide an excellent balance of moisture retention and drying properties, as well as good intermittent printing stability and friction fastness.

[0064] 1.4.1 Polyhydric alcohols with a standard boiling point of 250°C or higher The pigment printing reaction solution according to this embodiment may contain a polyhydric alcohol with a standard boiling point of 250°C or higher. Furthermore, the contained polyhydric alcohol may have a standard boiling point of 250°C or higher. In such cases, the moisture retention of the reaction solution tends to be better, and the discharge stability tends to be improved. Also, from the viewpoint of suppressing the problem of VOCs (volatile organic compounds), it is preferable that the standard boiling point of the polyhydric alcohol be 250°C or higher.

[0065] Examples of polyhydric alcohols with a standard boiling point of 250°C or higher include polyols with a standard boiling point of 250°C or higher, such as triethylene glycol (standard boiling point 287°C), trimethylolpropane (standard boiling point 295°C), and glycerin (standard boiling point 290°C). Among these, glycerin is preferred from the viewpoint of having better moisture retention and superior intermittent printing stability. Also from a similar viewpoint, the polyhydric alcohol with a standard boiling point of 250°C or higher is preferably 260°C or higher, more preferably 270°C or higher, even more preferably 280°C or higher, and particularly preferably 285°C or higher.

[0066] The content of polyhydric alcohols with a standard boiling point of 250°C or higher is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, even more preferably 3.0% by mass or more, even more preferably 5.0% by mass or more, and particularly preferably 10% by mass or more, relative to the total amount of the reaction solution. The upper limit is not particularly limited, but is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, even more preferably 18% by mass or less, and particularly preferably 15% by mass or less. When the content of polyhydric alcohols with a standard boiling point of 250°C or higher is within the above range, there is a tendency to have an excellent balance between moisture retention and drying properties, and both intermittent printing stability and friction fastness can be obtained.

[0067] 1.4.2 Polyhydric alcohols with a standard boiling point of 230°C or less The pigment printing reaction solution according to this embodiment may further contain a polyhydric alcohol with a standard boiling point of 230°C or lower. Polyhydric alcohols with a standard boiling point of 250°C or higher have excellent moisturizing properties, making them difficult to dry and potentially leaving residue on the fabric. This can inhibit the reaction of the cationic polymer, resulting in poor friction fastness. In contrast, the inclusion of a polyhydric alcohol with a standard boiling point of 230°C or lower can mitigate this problem, improving the reactivity of the cationic polymer and potentially resulting in better friction fastness.

[0068] Polyhydric alcohols with a standard boiling point of 230°C or lower include, for example, alkanediols with a standard boiling point of 230°C or lower, such as ethylene glycol (standard boiling point 197°C), propylene glycol (standard boiling point 188°C), 1,2-butanediol (standard boiling point 192°C), 1,2-hexanediol (standard boiling point 223°C), 1,3-propanediol (standard boiling point 213°C), 1,3-butylene glycol (standard boiling point 207°C), and 1,4-butanediol (standard boiling point 23 Examples include 2-ethyl-2-methyl-1,3-propanediol (standard boiling point 226°C), 2-methyl-1,3-propanediol (standard boiling point 214°C), 2,2-dimethyl-1,3-propanediol (standard boiling point 210°C), 3-methyl-1,3-butanediol (standard boiling point 203°C), and 2-methylpentane-2,4-diol (standard boiling point 197°C). Among these, the polyhydric alcohol with a standard boiling point of 230°C or lower is preferably one or more selected from propylene glycol and 1,3-butylene glycol, and more preferably propylene glycol. When the above compounds are used, the inhibition of the reaction of the cationic polymer is further reduced, and the frictional fastness tends to be superior. Furthermore, from a similar viewpoint, polyhydric alcohols with a standard boiling point of 230°C or less are preferably 220°C or less, more preferably 210°C or less, even more preferably 200°C or less, and particularly preferably 190°C or less.

[0069] The content of polyhydric alcohols with a standard boiling point of 230°C or lower is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, even more preferably 3.0% by mass or more, even more preferably 5.0% by mass or more, and particularly preferably 10% by mass or more, relative to the total amount of the reaction solution. The upper limit is not particularly limited, but is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, even more preferably 18% by mass or less, and particularly preferably 15% by mass or less. When the content of polyhydric alcohols with a standard boiling point of 230°C or lower is within the above range, there is a tendency to have an excellent balance between moisture retention and drying properties, and both intermittent printing stability and friction fastness can be obtained.

[0070] 1.5 Alkaline The pigment printing reaction solution according to this embodiment contains an alkali. Examples of alkalis include inorganic alkali compounds such as hydroxides of alkali metals or alkaline earth metals; and organic alkali compounds such as amine compounds. The alkali contained in the pigment printing reaction solution according to this embodiment is an amine compound. While the presence of alkali in the reaction solution can suppress pitting corrosion, the cationic polymer deteriorates during long-term storage of the reaction solution. This makes it impossible to impart water resistance to the fabric, resulting in poor friction fastness (especially wet friction fastness). In contrast, if the alkali is an amine compound, the deterioration of the cationic polymer can be reduced. Therefore, even when the reaction solution is stored for a long period of time, water resistance can be imparted to the fabric, friction fastness (especially wet friction fastness) can be improved, and pitting corrosion of metal components such as recording heads can be suppressed.

[0071] Examples of amine compounds include primary amines, secondary amines, and tertiary amines. Ammonia is also included as an amine compound. The amine compounds are different from the cationic polymers mentioned above. The molecular weight of the amine compound is not particularly limited, but is preferably 500 or less, more preferably 300 or less, even more preferably 250 or less, and particularly preferably 200 or less. The lower limit of the molecular weight is not particularly limited, but is preferably 40 or more, more preferably 80 or more, and even more preferably 120 or more.

[0072] The alkali preferably contains one or more selected from primary, secondary, and tertiary amines, and more preferably contains a tertiary amine. In particular, when the alkali contains a tertiary amine, the degradation of the cationic polymer tends to be further reduced. Therefore, even when the reaction solution is stored for a long period of time, it is possible to impart water resistance to the fabric, improve friction fastness (especially wet friction fastness), and suppress pitting corrosion of metal components such as recording heads.

[0073] Furthermore, if the reaction solution contains a cationic polymer, the viscosity of the reaction solution tends to increase even if only a small amount of water evaporates from it. Therefore, reaction solutions containing cationic polymers When ejecting by inkjet method, ejection stability (especially intermittent printing stability) tends to be poor. In contrast, when the alkali contains a tertiary amine, the tertiary amine is less likely to dry out, which tends to improve the moisture retention of the reaction solution. Therefore, when the alkali contains a tertiary amine, ejection stability (especially intermittent printing stability) tends to be improved.

[0074] Examples of primary amines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, and tert-butylamine.

[0075] Examples of secondary amines include N,N-dimethylamine, N,N-diethylamine, N,N-di-n-propylamine, N,N-diisopropylamine, N,N-di-n-butylamine, N,N-diisobutylamine, and N,N-di-sec-butylamine.

[0076] Examples of tertiary amines include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, triisopropanolamine, and trishydroxymethylaminomethane.

[0077] Alkali may be used alone or in combination of two or more types.

[0078] The pKa of the alkali contained in the pigment printing reaction solution according to this embodiment is preferably 7.0 to 11.0, more preferably 7.0 to 10.5, even more preferably 7.0 to 10.0, particularly preferably 7.0 to 9.5, even more preferably 7.0 to 9.0, and especially preferably 7.5 to 8.5. When the pKa of the alkali is within the above range, the degradation of the cationic polymer tends to be further reduced. Therefore, even when the reaction solution is stored for a long period of time, water resistance can be imparted to the fabric, friction fastness (especially wet friction fastness) can be improved, and pitting corrosion of metal components such as recording heads tends to be suppressed.

[0079] In this invention, "pKa" refers to the acid dissociation constant with respect to water. Furthermore, the base dissociation constant pKb can be converted from the self-dissociation constant of the solvent if the acid dissociation constant pKa is known. In particular, when the solvent is water, the equation pKa + pKb = 14 holds true.

[0080] The alkali content in the pigment printing reaction solution according to this embodiment is preferably 0.1 to 3.0% by mass, more preferably 0.3 to 2.5% by mass, even more preferably 0.5 to 2.0% by mass, even more preferably 0.7 to 1.5% by mass, and particularly preferably 0.8 to 1.2% by mass, based on the total amount of the reaction solution. When the alkali content is within the above range, pitting corrosion can be effectively suppressed, and the degradation of the cationic polymer tends to be further reduced. In other words, even when the reaction solution is stored for a long period of time, water resistance can be imparted to the fabric, friction fastness (especially wet friction fastness) can be improved, and pitting corrosion of metal components such as recording heads tends to be suppressed.

[0081] 1.6 Water The pigment printing reaction solution according to this embodiment contains water. Examples of water include pure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water, as well as ultrapure water, which has reduced ionic impurities. Furthermore, using water sterilized by ultraviolet irradiation or the addition of hydrogen peroxide can suppress the growth of bacteria and fungi when the reaction solution is stored for a long period of time.

[0082] The water content is preferably 30% by mass or more, and 40% by mass or more, relative to the total amount of the reaction solution. More preferably, 45% by mass or more is preferred, even more preferably 50% by mass or more is preferred, particularly preferably 55% by mass or more is preferred, and most particularly preferred 60% by mass or more is preferred. By having the water content within the above range, the reaction solution for pigment printing can be made relatively low viscosity. Furthermore, there is no particular upper limit to the water content, but it is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, relative to the total amount of the reaction solution.

[0083] 1.7 Content ratio In the pigment printing reaction solution according to this embodiment, when M1 is the content of polyhydric alcohols with a standard boiling point of 250°C or higher relative to the total amount of the reaction solution, and M2 is the content of polyhydric alcohols with a standard boiling point of 230°C or lower relative to the total amount of the reaction solution, the content ratio (M2 / M1) is preferably 0.1 to 10. The upper limit of the content ratio (M2 / M1) is more preferably 8 or less, even more preferably 6 or less, even more preferably 4 or less, particularly preferably 3 or less, even more preferably 2 or less, and especially preferably 1.5 or less. The lower limit of the content ratio (M2 / M1) is preferably 0.2 or more, more preferably 0.4 or more, even more preferably 0.6 or more, and particularly preferably 0.8 or more. When the content ratio (M2 / M1) is within the above range, there is a good balance between moisture retention and drying properties, and both intermittent printing stability and friction fastness tend to be good.

[0084] In the pigment printing reaction solution according to this embodiment, when M1 is the content of polyhydric alcohol with a standard boiling point of 250°C or higher relative to the total amount of the reaction solution, and M3 is the content of cationic polymer relative to the total amount of the reaction solution, the content ratio (M1 / M3) is preferably 0.5 to 20. The upper limit of the content ratio (M1 / M3) is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less. The lower limit of the content ratio (M1 / M3) is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more. When the content ratio (M1 / M3) is within the above range, there is a good balance between the reactivity and moisture retention of the cationic polymer, and both intermittent printing stability and friction fastness tend to be good.

[0085] In the pigment printing reaction solution according to this embodiment, when the content of the cationic polymer relative to the total amount of the reaction solution is M3 and the content of the polyvalent metal salt relative to the total amount of the reaction solution is M4, the content ratio (M3 / M4) is preferably 0.1 to 3.0. The upper limit of the content ratio (M3 / M4) is preferably 2.0 or less, more preferably 1.5 or less, even more preferably 1.2 or less, and even more preferably 1.0 or less. The lower limit of the content ratio (M3 / M4) is preferably 0.2 or more, more preferably 0.3 or more, even more preferably 0.4 or more, particularly preferably 0.5 or more, and even more particularly preferably 0.6 or more. When the content ratio (M3 / M4) is within the above range, it may be possible to achieve a good balance of color development, friction fastness, and intermittent printing stability.

[0086] In the pigment printing reaction solution according to this embodiment, when the content of alkali relative to the total amount of the reaction solution is M5 and the content of cationic polymer relative to the total amount of the reaction solution is M3, the content ratio (M5 / M3) is preferably 0.1 to 3.0. The upper limit of the content ratio (M5 / M3) is preferably 2.0 or less, more preferably 1.5 or less, even more preferably 1.0 or less, particularly preferably 0.8 or less, and most particularly preferably 0.6 or less. The lower limit of the content ratio (M5 / M3) is preferably 0.2 or more, and more preferably 0.3 or more. When the content ratio (M5 / M3) is within the above range, it tends to be possible to achieve a good balance between frictional fastness and suppression of pitting corrosion.

[0087] 1.8 Organic Solvents The pigment printing reaction solution according to this embodiment may contain organic solvents other than the polyhydric alcohols mentioned above. Examples of such organic solvents include alcohols, alkylene glycol ethers, esters, cyclic esters, and nitrogen-containing solvents. Examples of nitrogen-containing solvents include cyclic amides and acyclic amides. Examples of acyclic amides include alkoxyalkylamides.

[0088] Examples of alcohols include compounds in which one hydrogen atom of an alkane is replaced by a hydroxyl group. Alkanes may be linear or branched. Examples of alcohols include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, 2-butanol, tert-butanol, iso-butanol, n-pentanol, 2-pentanol, 3-pentanol, and tert-pentanol.

[0089] Alkylene glycol ethers are also called penetrating solvents because of their excellent penetrating properties. The alkylene glycol ethers can be monoethers or diethers of alkylene glycols, with alkyl ethers being preferred.Specific examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether (BTG, standard boiling point 278°C), tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene Examples include alkylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, and alkylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol methyl butyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and tripropylene glycol dimethyl ether.

[0090] When glycol ethers are used, the number of carbon atoms is preferably 12 or less, preferably 8 or less, and preferably 6 or less. The lower limit is preferably 2 or more, more preferably 3 or more, and even more preferably 5 or more. The number of carbon atoms refers to the number of carbon atoms in the molecule.

[0091] Esters include glycol monoacetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, methoxybutyl acetate, and other ethylene glycol monoethyl ether acetates. Examples of glycol diesters include ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, ethylene glycol acetate propionate, ethylene glycol acetate butyrate, diethylene glycol acetate butyrate, diethylene glycol acetate propionate, diethylene glycol acetate butyrate, propylene glycol acetate propionate, propylene glycol acetate butyrate, dipropylene glycol acetate butyrate, and dipropylene glycol acetate propionate.

[0092] Examples of cyclic esters include cyclic esters (lactones) such as β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, β-butyrolactone, β-valerolactone, γ-valerolactone, β-hexanolactone, γ-hexanolactone, δ-hexanolactone, β-heptanolactone, γ-heptanolactone, δ-heptanolactone, ε-heptanolactone, γ-octanolactone, δ-octanolactone, ε-octanolactone, δ-nonalactone, ε-nonalactone, and ε-decanolactone, as well as compounds in which the hydrogen atoms of the methylene group adjacent to the carbonyl group are substituted with alkyl groups having 1 to 4 carbon atoms.

[0093] Examples of cyclic amides include lactams, such as pyrrolidones including 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone.

[0094] Examples of alkoxyalkylamides include 3-methoxy-N,N-dimethylpropionamide, 3-methoxy-N,N-diethylpropionamide, 3-methoxy-N,N-methylethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-diethylpropionamide, 3-ethoxy-N,N-methylethylpropionamide, 3-n-butoxy-N,N-dimethylpropionamide, 3-n-butoxy-N,N-diethylpropionamide, 3-n-butoxy-N,N-methylethylpropionamide, 3-n-propoxy-N, Examples include N-dimethylpropionamide, 3-n-propoxy-N,N-diethylpropionamide, 3-n-propoxy-N,N-methylethylpropionamide, 3-iso-propoxy-N,N-dimethylpropionamide, 3-iso-propoxy-N,N-diethylpropionamide, 3-iso-propoxy-N,N-methylethylpropionamide, 3-tert-butoxy-N,N-dimethylpropionamide, 3-tert-butoxy-N,N-diethylpropionamide, 3-tert-butoxy-N,N-methylethylpropionamide, etc.

[0095] Organic solvents may be used individually or in combination of two or more types.

[0096] 1.9 Surfactants The pigment printing reaction solution according to this embodiment may contain a surfactant. The surfactant is not particularly limited, but examples include acetylene glycol-based surfactants, fluorine-based surfactants, and silicone-based surfactants, and it is preferable to contain at least one of these, and among these, it is more preferable to contain an acetylene glycol-based surfactant.

[0097] Acetylene glycol-based surfactants are not particularly limited, but examples include Surfinol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA Examples include DF110D (all product names, manufactured by Air Products Japan Co., Ltd.), Orfin B, Y, P, A, STG, SPC, E1004, E1010, PD-001, PD-002W, PD-003, PD-004, EXP.4001, EXP.4036, EXP.4051, AF-103, AF-104, AK-02, SK-14, AE-3 (all product names, manufactured by Nisshin Chemical Industry Co., Ltd.), and Acetyleneol E00, E00P, E40, E100 (all product names, manufactured by Kawaken Fine Chemical Co., Ltd.).

[0098] While not particularly limited, polysiloxane compounds are preferred as silicone-based surfactants. Examples of such polysiloxane compounds include polyether-modified organosiloxanes. Examples of commercially available polyether-modified organosiloxanes include BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-348 (all trade names, manufactured by BIC Chemie Japan Co., Ltd.), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0099] As the fluorine-based surfactant, it is preferable to use a fluorine-modified polymer, and a specific example is BYK-340 (trade name, manufactured by BYK-Chemie Japan Co., Ltd.).

[0100] If a surfactant is included, its content is preferably 0.1% by mass or more and 5.0% by mass or less, preferably 0.3% by mass or more and 3.0% by mass or less, and more preferably 0.5% by mass or more and 1.5% by mass or less, relative to the total amount of the reaction solution.

[0101] 1.10 Metal encapsulants The pigment printing reaction solution according to this embodiment may contain a metal sealant. The metal sealant can remove specific ions from the reaction solution.

[0102] Examples of metal encapsulants include ethylenediaminetetraacetic acid and its salts such as EDTA, EDTA-2Na (ethylenediaminetetraacetic acid disodium dihydrogen salt), EDTA-3Na (ethylenediaminetetraacetic acid trisodium monohydrogen salt), EDTA-4Na (ethylenediaminetetraacetic acid tetrasodium salt), and EDTA-3K (ethylenediaminetetraacetic acid tripotassium monohydrogen salt), as well as DTPA, DTPA-2Na (diethylenetriaminepentaacetic acid disodium salt), and DTPA-5Na (diethylenetriaminepentaacetic acid pentasodium salt). Examples include diethylenetriaminepentaacetic acid and its salts (such as pentasodium nitrate), nitrilotriacetic acid and its salts such as NTA, NTA-2Na (disodium nitrilotriacetate), and NTA-3Na (trisodium nitrilotriacetate), ethylenediamine-N,N'-disuccinic acid and its salts, 3-hydroxy-2,2'-iminodisuccinic acid and its salts, L-aspartic acid-N,N'-diacetic acid and its salts, and N-(2-hydroxyethyl)iminodiacetic acid and its salts.

[0103] Examples of metal encapsulants other than acetate analogs include ethylenediaminetetramethylenephosphonic acid and its salts, ethylenediaminetetrametaphosphate and its salts, ethylenediamine pyrophosphate and its salts, and ethylenediamine metaphosphate and its salts.

[0104] Metal sealants may be used individually or in combination of two or more types.

[0105] If a metal sealant is included, its content should be, for example, 0.0% of the total volume of the reaction solution. The amount can be 0.5% by mass or more and 0.1% by mass or less, preferably 0.01% by mass or more and 0.05% by mass or less.

[0106] 1.11 Antimicrobial agents The pigment printing reaction solution according to this embodiment may contain an antibacterial agent. Examples of antibacterial agents include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL-2, Proxel IB, and Proxel TN (all manufactured by Lonza Japan, trade names), and 4-chloro-3-methylphenol (such as Preventol CMK from Bayer).

[0107] If an antibacterial agent is included, its content may be, for example, 0.05% by mass or more and 1.0% by mass or less, preferably 0.1% by mass or more and 0.5% by mass or less, relative to the total amount of the reaction solution.

[0108] 1.12 Other ingredients The pigment printing reaction solution according to this embodiment may also appropriately contain various additives other than those mentioned above, such as softeners, solubilizers, viscosity modifiers, ultraviolet absorbers, antioxidants, and corrosion inhibitors.

[0109] 1.13 Method for producing a reaction solution for pigment printing and its physical properties The pigment printing reaction solution according to this embodiment is obtained by mixing the above-mentioned components in any order and removing impurities by filtration or other means as necessary. A preferred method for mixing the components is to sequentially add the materials to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and then stir-mix them.

[0110] In this embodiment, the pigment printing reaction solution preferably has a surface tension of 20 to 40 mN / m at 20°C, more preferably 22 to 35 mN / m, and even more preferably 25 to 30 mN / m, from the viewpoint of reliability when ejected by the inkjet method. In particular, when the surface tension of the pigment printing reaction solution at 20°C is 25 to 30 mN / m, it tends to suppress the generation of mist. This tends to reduce the adhesion of the reaction solution near the nozzle surface of the head, and to further reduce the effects of pitting corrosion.

[0111] Furthermore, from the viewpoint of reliability when ejected by the inkjet method, the viscosity of the pigment printing reaction solution at 20°C is preferably 2 to 10 mPa·s, more preferably 2.5 to 8 mPa·s, even more preferably 3 to 6 mPa·s, and particularly preferably 3.5 to 5 mPa·s. In order to bring the surface tension and viscosity within the above range, the types of polyhydric alcohols and surfactants mentioned above, and the amounts of these and water added can be adjusted as appropriate.

[0112] Furthermore, the surface tension can be measured using the Wilhelmy method. For measuring surface tension, a surface tensimeter such as the CBVP-7 manufactured by Kyowa Interface Science Co., Ltd. can be used. Viscosity can be measured at 20°C using a viscoelasticity tester such as the MCR-300 manufactured by Pysica, with a shear rate of 10 [s]. -1 ] to 1000[s -1 Increase it to ] and Shear Rate 200[s -1 The viscosity can be measured by reading the viscosity at [this point].

[0113] The pH of the pigment printing reaction solution according to this embodiment at 20°C is preferably 5.0 to 10.0, more preferably 6.0 to 9.5, and 6.5 to 9.0. More preferably, 7.0 to 8.5 is particularly preferred, and 7.5 to 8.0 is even more preferred. When the pH of the reaction solution is within the above range, pitting corrosion can be effectively suppressed, and the degradation of the cationic polymer tends to be further reduced. In other words, even when the reaction solution is stored for a long period of time, water resistance can be imparted to the fabric, frictional fastness (especially wet frictional fastness) can be improved, and pitting corrosion of metal components such as recording heads tends to be suppressed.

[0114] 2. Ink Set An ink set according to one embodiment of the present invention comprises a textile printing inkjet ink composition containing a pigment, resin particles, and water, and the above-mentioned pigment textile printing reaction solution.

[0115] According to this embodiment, since the ink set is equipped with the above-mentioned pigment printing reaction solution, it is possible to suppress pitting corrosion of metal components such as recording heads while maintaining good color development and friction fastness.

[0116] In this invention, an ink set is a set of ink and reaction solution, comprising at least a textile printing inkjet ink composition and a pigment textile printing reaction solution. The textile printing inkjet ink composition included in the ink set may be one type only or two or more types may be used in combination. The same applies to the pigment textile printing reaction solution included in the ink set.

[0117] 2.1 Reaction solution for pigment printing The ink set according to this embodiment includes the pigment printing reaction solution described above. Since the pigment printing reaction solution is as described above, its explanation will be omitted.

[0118] 2.2 Textile inkjet ink composition The ink set according to this embodiment comprises a textile inkjet ink composition containing a pigment, resin particles, and water.

[0119] The following describes each component of the inkjet printing ink composition included in the ink set according to this embodiment. Note that the inkjet printing ink composition can be prepared independently of the pigment printing reaction solution described above.

[0120] Furthermore, in the following explanation, "printing inkjet ink composition" may also be referred to as "inkjet ink composition," "ink composition," or "ink."

[0121] 2.2.1 Pigments The inkjet ink composition of the ink set according to this embodiment contains a pigment. For example, inorganic pigments and organic pigments can be used as the pigment. Note that a pigment is a type of colorant. Examples of colorants include pigments and dyes.

[0122] Inorganic pigments are not particularly limited, but examples include carbon blacks such as furnace black, lamp black, acetylene black, and channel black; and white inorganic oxides such as iron oxide, titanium oxide, zinc oxide, and silica.

[0123] Examples of carbon blacks include CI (Colour Index Generic Name) Pigment Black 1, 7, and 11. Commercially available carbon blacks may also be used, such as Mitsubishi Chemical's No. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, and No. 2200B; Columbia Carbon's Raven® 5750, 5250, 5000, 3500, 1255, and 700; and CABOT's Rega1® 400R. Examples include 330R, 660R, Mogul(registered trademark) L, Monarch(registered trademark) 700, 800, 880, 900, 1000, 1100, 1300, 1400, etc., as well as Degussa's Color Black FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Printex(registered trademark) 35, U, V, 140U, and SpecialBlack 6, 5, 4A, 4.

[0124] Examples of organic pigments include quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, ancenthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimimidazolone pigments, isoindolinone pigments, azomethine pigments, or azo pigments.

[0125] Specific examples of organic pigments include the following:

[0126] Examples of cyan pigments include CI Pigment Blue 1, 2, 3, 15:3, 15:4, 15:34, 16, 22, 60, etc.; CI Bat Blue 4, 60, etc. Preferably, one or more mixtures selected from the group consisting of CI Pigment Blue 15:3, 15:4, and 60 can be exemplified.

[0127] Examples of magenta pigments include CI Pigment Red 5, 7, 12, 48(Ca), 48(Mn), 57(Ca), 57:1, 112, 122, 123, 168, 184, 202, and CI Pigment Violet 19. Preferably, one or more mixtures selected from the group consisting of CI Pigment Red 122, 202, and 209, and CI Pigment Violet 19 can be exemplified.

[0128] Examples of yellow pigments include CI Pigment Yellow 1, 2, 3, 12, 13, 14C, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 119, 110, 114, 128, 129, 138, 150, 151, 154, 155, 180, 185, etc. Preferably, one or more mixtures selected from the group consisting of CI Pigment Yellow 74, 109, 110, 128, 138, 150, and 180 can be exemplified.

[0129] Other colored pigments can also be used. For example, orange pigment and green pigment can be used.

[0130] Pigments may be used individually or in combination of two or more types.

[0131] Furthermore, to improve the dispersibility of the pigment in the ink composition, it is preferable to surface-treat the pigment or to incorporate a dispersant.

[0132] Pigment surface treatment refers to a process that directly or indirectly attaches functional groups, such as carbonyl groups, carboxyl groups, aldehyde groups, hydroxyl groups, sulfone groups, ammonium groups, and salts thereof, to the surface of a pigment through physical or chemical treatment.

[0133] When a dispersant is added to an ink composition, it is preferable to use a dispersant that has both a hydrophobic portion (hydrophobic group) and a hydrophilic portion (hydrophilic group) in its molecular structure. Such a dispersant has the effect of the hydrophobic portion adsorbing to the surface of the pigment particles and the hydrophilic portion orienting towards the aqueous medium side of the ink composition. This effect tends to make it possible to include the pigment more stably in the ink composition as a dispersion. Such dispersants are not particularly limited, but examples include acrylic resins, styrene-(meth)acrylic acid copolymers, styrene-(meth)acrylic acid-(meth)acrylate copolymers and other styrene-acrylic resins, styrene-maleic acid resins, and their salts, formalin condensates of aromatic sulfonates, and one or more selected from this group can be used. Commercially available dispersants may also be used.

[0134] Alternatively, a method may be used in which the pigment particles are coated with a resin or other material to impart dispersibility. Possible methods for coating the pigment particles include acid precipitation, phase inversion emulsification, and miniemulsion polymerization.

[0135] The pigment content can be adjusted as appropriate depending on the application, but is preferably 0.1% to 17.0% by mass, more preferably 0.2% to 15.0% by mass, even more preferably 1.0% to 10.0% by mass, and particularly preferably 2.0% to 5.0% by mass, relative to the total amount of the ink composition. When the pigment content is within the above range, the ejection performance when ejecting by the inkjet method tends to be improved.

[0136] Furthermore, the ink composition may contain dyes as colorants other than the pigments mentioned above. Examples of dyes include acid dyes, reactive dyes, and direct dyes.

[0137] 2.2.2 Resin particles The inkjet ink composition provided in the ink set according to this embodiment contains resin particles. Resin particles are particles containing resin and are also called "resin dispersions" or "resin emulsions."

[0138] Examples of resins include urethane resin, polycarbonate resin, (meth)acrylic resin, styrene resin, silicone resin, styrene-acrylic resin, fluorene resin, polyolefin resin, rosin-modified resin, terpene resin, polyester resin, polyamide resin, epoxy resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, and ethylene vinyl acetate resin. These resins may be used individually or in combination of two or more.

[0139] Among these, the resin particles are preferably urethane resin, polycarbonate resin, (meth)acrylic resin, and styrene resin, more preferably urethane resin and (meth)acrylic resin, and even more preferably urethane resin. In particular, when the resin particles are urethane resin, the cation polymer contained in the aforementioned reaction solution can react with the urethane resin, which may result in better color development, friction fastness, and bleeding resistance.

[0140] Urethane resin is a resin that has urethane bonds within its molecule. From the viewpoint of storage stability of the ink, it is preferable that the urethane resin is an anionic urethane resin having anionic functional groups such as carboxyl groups, sulfo groups, and hydroxyl groups.

[0141] Examples of urethane resins include polyether-type urethane resins containing ether bonds in the main chain, polyester-type urethane resins containing ester bonds in the main chain, and polycarbonate-type urethane resins containing carbonate bonds in the main chain. Multiple types of these urethane resins can be used in combination.

[0142] Commercially available urethane resin products include ETERNACOLL UW-1501F, UW-1527F, UW-5002 (all product names from Ube Industries), and Takelac WS-5000, W-6061, W-6110, WS-5984, WS-5100 (all manufactured by Mitsui Chemicals). Examples include Permarin UA-150, UA-200, U-Coat UX-390 (all product names manufactured by Sanyo Chemical Industries), and Hydran WLS-210 (product name manufactured by DIC Corporation).

[0143] Polycarbonate resin is a resin that has polycarbonate bonds within its molecule. When urethane resin is not used, it is preferable to use polycarbonate resin instead.

[0144] Examples of commercially available (meth)acrylic resins include Movinyl 966A and 6760 (product names of Nippon Synthetic Chemical Co., Ltd.), which are acrylic resins.

[0145] (Meth)acrylic resin refers to a resin having a (meth)acrylic skeleton. While not particularly limited, examples of (meth)acrylic resins include polymers of (meth)acrylic monomers such as (meth)acrylic acid and (meth)acrylic acid esters, and copolymers of (meth)acrylic monomers with other monomers. Other monomers include vinyl monomers such as styrene. In this specification, "(meth)acrylic" refers to acrylic or methacrylic, and "(meth)acrylate" refers to acrylate or methacrylate.

[0146] Commercially available silicone resins include POLON-MF014, POLON-MF-18T, POLON-MF-33, KM-2002-T (all product names from Shin-Etsu Silicone Co., Ltd.), WACKER FINISH WR1100, NP2406, POWERSOFT FE 55, and TS2406 (all product names from Asahi Kasei Corporation).

[0147] The acid value of the resin contained in the resin particles is not particularly limited, but is preferably 1 to 300 KOH mg / g, more preferably 10 to 200 KOH mg / g, and even more preferably 20 to 100 KOH mg / g.

[0148] The resin particle content is preferably 1.0% by mass or more, more preferably 2.0 to 20% by mass, and even more preferably 3.0 to 10% by mass, based on the solid content relative to the total amount of the ink composition. When the resin particle content is within the above range, it tends to be possible to obtain recordings with excellent color development and excellent friction fastness.

[0149] 2.2.3 Water The inkjet ink composition for textile printing provided in the ink set according to this embodiment contains water. The water used is the same as the water contained in the pigment textile printing reaction solution described above, and the amount of water can also be the same.

[0150] 2.2.4 Organic Solvents The inkjet ink composition for textile printing provided in the ink set according to this embodiment may contain a polyhydric alcohol or an organic solvent other than a polyhydric alcohol as an organic solvent. Such an organic solvent can be the same as the organic solvents that can be contained in the aforementioned pigment textile printing reaction solution.

[0151] The content of polyhydric alcohols with a standard boiling point of 250°C or higher is not particularly limited, but is preferably 5.0% by mass or more, more preferably 10% by mass or more, even more preferably 12% by mass or more, and even more preferably 15% by mass or more, relative to the total amount of the ink composition. The upper limit is not particularly limited, but is preferably 30% by mass or less, more preferably 27% by mass or less, even more preferably 25% by mass or less, even more preferably 22% by mass or less, and particularly preferably 20% by mass or less. If the content of polyhydric alcohols with a standard boiling point of 250°C or higher is within the above range, It has an excellent balance of moisture and dryness, and tends to exhibit good intermittent printing stability and friction resistance.

[0152] As organic solvents other than polyhydric alcohols, alkylene glycol ethers are preferred, and alkylene glycol monoalkyl ethers are more preferred. The content of organic solvents other than polyhydric alcohols is not particularly limited, but is preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, and even more preferably 0.5 to 1.5% by mass, relative to the total amount of the ink composition.

[0153] 2.2.5 Surfactants The inkjet ink composition for textile printing provided in the ink set according to this embodiment may contain a surfactant. Such a surfactant can be the same as the surfactant that can be contained in the pigment textile printing reaction solution described above, and the content can also be the same.

[0154] 2.2.6 pH adjusters The inkjet ink composition comprising the ink set according to this embodiment may contain a pH adjuster. The pH adjuster is not particularly limited, but appropriate combinations of acids, bases, weak acids, and weak bases are possible. Examples of acids and bases used in such combinations include, as inorganic acids, sulfuric acid, hydrochloric acid, nitric acid, etc.; as inorganic bases, lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium dihydrogen phosphate, disodium hydrogen phosphate, potassium carbonate, sodium carbonate, sodium bicarbonate, ammonia, etc.; as organic bases, triethanolamine, diethanolamine, monoethanolamine, trippropanolamine, triisopropanolamine, diisopropanolamine, trishydroxymethylaminomethane (THAM), etc.; and as organic acids, adipic acid, citric acid, succinic acid, lactic acid, N,N-bis(2-hydroxymethylaminomethane). Good's buffers such as thioethyl)-2-aminoethanesulfonic acid (BES), 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES), morpholinoethanesulfonic acid (MES), carbamoylmethyliminobisacetic acid (ADA), piperazine-1,4-bis(2-ethanesulfonic acid) (PIPES), N-(2-acetamide)-2-aminoethanesulfonic acid (ACES), cholamine hydrochloride, N-tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid (TES), acetamidoglycine, tricine, glycinamide, bicine, etc., as well as phosphate buffers, citrate buffers, Tris buffers, etc., may also be used. Furthermore, the alkali contained in the aforementioned pigment printing reaction solution may be used as a pH adjuster.

[0155] The ink composition may use one pH adjusting agent alone or two or more in combination. When using a pH adjusting agent, the total content relative to the total mass of the ink composition is, for example, 0.05% by mass or more and 3.0% by mass or less, and more preferably 0.1% by mass or more and 1.0% by mass or less.

[0156] 2.2.7 Other Ingredients The ink printing ink composition of the ink set according to this embodiment may also appropriately contain various additives other than those mentioned above, such as lubricants, softeners, solubilizers, viscosity modifiers, antioxidants, antibacterial agents such as Proxel XL2 (product name of Arch Chemicals), corrosion inhibitors, and metal encapsulants (e.g., sodium ethylenediaminetetraacetate) for capturing metal ions that affect dispersion.

[0157] 2.2.8 Manufacturing and physical properties of ink compositions The inkjet ink composition provided in the ink set according to this embodiment is obtained by mixing the above-mentioned components in any order and removing impurities by filtration or other means as necessary. Methods for mixing the components include using a mechanical stirrer or a magnetic stirrer. A preferred method involves sequentially adding the materials to a container equipped with a stirring device and then stirring and mixing them.

[0158] From the viewpoint of reliability when ejected by the inkjet method, the inkjet ink composition for textile printing provided in the ink set according to this embodiment preferably has a surface tension of 20 to 40 mN / m at 20°C, and more preferably 22 to 35 mN / m. Similarly, from the same viewpoint, the viscosity of the ink composition at 20°C is preferably 1.5 to 10 mPa·s, more preferably 8 mPa·s or less, and even more preferably 2 to 8 mPa·s. To bring the surface tension and viscosity within the above ranges, the types of organic solvents and surfactants mentioned above, and the amounts of these and water added can be appropriately adjusted.

[0159] 3. Recording Method A recording method according to one embodiment of the present invention comprises an ink application step of applying an ink composition to a fabric by an inkjet method, and a reaction solution application step of applying the above-mentioned pigment printing reaction solution to the fabric by an inkjet method.

[0160] According to the recording method of this embodiment, since it includes the above-mentioned pigment printing reaction solution, it is possible to suppress pitting corrosion of metal members such as the recording head while maintaining good color development and friction fastness.

[0161] The recording method according to this embodiment is performed on a fabric. The material constituting the fabric is not particularly limited and includes, for example, natural fibers such as cotton, linen, wool, and silk; synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, and polyurethane; biodegradable fibers such as polylactic acid; and blends thereof.

[0162] It is preferable that the fabric has hydroxyl groups. Examples of such fabrics include cotton, linen, and other cellulose-containing fabrics, as well as polyurethane-containing fabrics. When the fabric has hydroxyl groups, a crosslinking reaction may occur between the cationic polymer contained in the reaction solution and the hydroxyl groups of the fabric, which may result in improved color development due to thickening and aggregation, and improved friction fastness due to improved adhesion between the fabric and the ink layer.

[0163] The fabric may be made from the above-mentioned fibers in any form, such as woven, knitted, or nonwoven. Furthermore, the basis weight of the fabric used in this embodiment is not particularly limited and may be between 1.0 oz and 10.0 oz, preferably between 2.0 oz and 9.0 oz, more preferably between 3.0 oz and 8.0 oz, and even more preferably between 4.0 oz and 7.0 oz. Good recording can be achieved if the basis weight of the fabric is within this range. Moreover, the recording method according to this embodiment can be applied to multiple types of fabrics with different basis weights, and good printing can be achieved.

[0164] In this embodiment, examples of the form of the fabric include fabrics, clothing, and other accessories. Fabrics include woven fabrics, knitted fabrics, non-woven fabrics, etc. Clothing and other accessories include sewn T-shirts, handkerchiefs, scarves, towels, tote bags, cloth bags, curtains, sheets, bed covers, and furniture such as wallpaper, as well as fabrics before and after cutting as parts before sewing. Examples of these forms include long ones rolled in a roll shape, those cut into a predetermined size, and those in a product shape.

[0165] As the fabric, a cotton fabric pre-colored with a dye may be used. Examples of the dye with which the fabric is pre-colored include water-soluble dyes such as acid dyes and basic dyes, disperse dyes used in combination with a dispersant, reactive dyes, etc. When using a cotton fabric as the fabric, it is preferable to use a reactive dye suitable for dyeing cotton.

[0166] Hereinafter, each step of the recording method according to this embodiment will be described.

[0167] 3.1 Ink adhesion step The recording method according to this embodiment has an ink adhesion step of adhering an ink composition to a fabric by an inkjet method.

[0168] As the ink composition, the above-described resist inkjet ink composition can be preferably used.

[0169] The inkjet method is a recording method in which droplets such as ink are ejected from the nozzles of an inkjet head such as an inkjet recording device and applied to a recording medium.

[0170] The adhesion amount of the ink composition is preferably 10 - 21 mg / inch per unit area of the recording area of the fabric, 2 more preferably 12 - 20 mg / inch, 2 even more preferably 14 - 19 mg / inch, 2 further more preferably 15 - 18 mg / inch, 2It is particularly preferable that this be the case.

[0171] 3.1.1 Process interval In the recording method according to this embodiment, it is preferable that the time difference between the ink application step and the reaction solution application step, which will be described later, be within 5 seconds. When the ink application step and the reaction solution application step are performed with such a time difference, a wet-on-wet method can be used in which the second droplet, which is applied later, is applied before the first droplet, which is applied first, dries. Note that if the first droplet is an ink composition, the second droplet is a reaction solution, and if the first droplet is a reaction solution, the second droplet is an ink composition. While the wet-on-wet method has advantages in terms of miniaturization and high speed of the device, it has problems such as being prone to bleeding, poor color development, and poor friction fastness. However, according to the recording method according to this embodiment, even with such a wet-on-wet method, it is possible to achieve excellent color development, poor friction fastness, and suppress bleeding. In addition, in the recording method according to this embodiment, when the time difference between the above steps is within 5 seconds, the reaction between the ink and the reaction solution proceeds more easily, and there is a tendency for better color development and poor friction fastness.

[0172] In this invention, the time difference between the ink application process and the reaction solution application process refers to the time difference from when the reaction solution is last dispensed until when the ink composition is first dispensed.

[0173] Furthermore, in the following explanation, "alternating printing" refers to applying the ink composition and reaction solution to the same scanning area of ​​the fabric using the same main scan (moving the inkjet head perpendicular to the fabric transport direction), thereby forming layers containing the ink composition and reaction solution. "Pre-printing" refers to applying the ink composition and reaction solution to the same scanning area of ​​the fabric using different main scans, thereby forming layers containing the reaction solution and the ink composition. In particular, when the layer containing the reaction solution is formed first, followed by the layer containing the ink composition, it is called "reaction solution pre-printing."

[0174] The time difference between the ink application process and the reaction solution application process is preferably 1 second or less, more preferably 0.8 seconds or less, even more preferably 0.6 seconds or less, and particularly preferably 0.4 seconds or less in the case of alternating printing. The lower limit is not particularly limited, but is preferably 0.1 seconds or more, and more preferably 0.2 seconds or more. In the case of alternating printing, the time difference between the ink application process and the reaction solution application process is particularly preferably 0.3 seconds. With such a time difference, the reaction between the ink and the reaction solution proceeds more easily, and tends to result in better color development and friction fastness.

[0175] The time difference between the ink application process and the reaction solution application process is 4.9 in the case of reaction solution application first. The time difference is preferably 4.8 seconds or less, more preferably 4.7 seconds or less, and particularly preferably 4.6 seconds or less. The lower limit is not particularly limited, but is preferably 3.0 seconds or more, more preferably 3.5 seconds or more, more preferably 4.0 seconds or more, particularly preferably 4.2 seconds or more, and most particularly preferably 4.4 seconds or more. In the case of pre-applied reaction solution, the time difference between the ink application process and the reaction solution application process is particularly preferably 4.5 seconds. With such a time difference, the reaction between the ink and the reaction solution proceeds more easily, and the color development and friction fastness tend to be superior.

[0176] 3.1.2 Adhesion Method 3.1.2.1 Alternating strokes In the recording method according to this embodiment, the reaction solution attachment step and the ink attachment step, which will be described later, are performed by an inkjet method, and the inkjet method involves performing multiple main scans by moving the inkjet head in a direction perpendicular to the transport direction of the fabric, and it is preferable that the reaction solution and the ink composition are attached to the same scanning area of ​​the fabric by the same main scan, and that the same main scan is performed multiple times on the same scanning area.

[0177] This allows for alternating printing. That is, one main scan can adhere a layer containing the ink composition and reaction solution to a certain area on the fabric, and then another main scan can adhere another layer containing the ink composition and reaction solution on top of it. As a result, the reaction solution and ink composition are layered alternately (like a mille-feuille), which makes it easier for the components of both to mix and for the reaction to proceed, resulting in a tendency for better color development, friction fastness, and suppression of bleeding.

[0178] When the same main scan is performed multiple times on the same scanning area, the main scan that applies the ink composition and reaction solution will pass over the same area of ​​the fabric multiple times. The more scans performed, the more the ink and reaction solution can be applied to the desired area in multiple passes, which tends to improve the image quality of the resulting recording.

[0179] Furthermore, when recording an arbitrary area, the number of times the inkjet head passes over that area is also called a "pass." For example, if the main scan that deposits the ink composition and reaction solution is performed four times over the same area, the number of passes is called 4 passes. For example, in Figure 3, if the length of one sub-scan in the sub-scanning direction SS is one-quarter the length of the nozzle row in the sub-scanning direction SS, then four scans will be performed on a rectangular scanning area that is the length of one sub-scan in the sub-scanning direction SS and extends in the main scanning direction MS. The number of scans in this view is called the number of scans or the number of passes. The number of scans is 2 or more, preferably 3 or more, and more preferably 4 or more. Also, the number of scans is preferably 10 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferably 4 or less. According to the recording method of this embodiment, even if the number of scans is within the above range, there is a tendency for superior color development, friction fastness, and suppression of bleeding.

[0180] Furthermore, in the alternating printing described above, a layer containing the reaction solution may be formed by a main scan different from the main scan that forms the layer containing the ink composition and reaction solution, and the layer containing the ink composition and reaction solution and the layer containing the reaction solution may be laminated together. By forming a layer containing the reaction solution in this way, the color development and friction fastness may be further improved. The formation of the layer containing the reaction solution may be performed before or after the formation of the layer containing the ink composition and reaction solution, but it is preferable that it be performed before.

[0181] 3.1.2.2 Pre-emptive strike In the recording method according to this embodiment, the reaction solution adhesion step and the ink adhesion step, which will be described later, The process is carried out by an inkjet method, in which an inkjet method is performed by moving an inkjet head perpendicular to the transport direction of the fabric to perform multiple main scans for recording, and the reaction solution and ink composition may be attached to the same scanning area of ​​the fabric by different main scans.

[0182] In this configuration, pre-printing is possible, and a layer containing a reaction solution and a layer containing an ink composition can be laminated to form the record. In the recording method according to this embodiment, even with such pre-printing, good color development, friction fastness, and suppression of bleeding can be achieved.

[0183] In pre-application, the order in which the ink composition and reaction solution are applied is not restricted as long as they are applied by different main scans; however, it is more preferable to apply the reaction solution first and then apply the ink composition on top of it.

[0184] In the pre-printing stage, multiple main scans may be performed on the same scanning area to apply the ink composition and the reaction solution to the scanning area. For example, the reaction solution could be recorded in four passes, followed by the ink composition in four passes. The number of passes in the pre-printing stage may be set independently for the ink composition and the reaction solution.

[0185] 3.1.2.3 Other adhesion methods The alternating printing and pre-printing methods described above use serial inkjet heads, but it is also acceptable to use line-type inkjet heads to perform the ink application process and the reaction solution application process.

[0186] In other words, in the recording method according to this embodiment, the reaction solution application step and the ink application step, which will be described later, are performed by an inkjet method, and the inkjet method may involve using an inkjet head (line head) having a length greater than or equal to the recording width of the fabric, and performing one scan with the inkjet head on the fabric being transported.

[0187] This line-type recording method allows the ink composition and reaction solution to be dispensed and adhered to the fabric while the line head and the fabric are moved relative to each other in a scanning direction (the vertical direction of the fabric, the transport direction) that intersects the width direction of the fabric.

[0188] 3.2 Reaction solution adhesion process The recording method according to this embodiment includes a reaction solution application step in which the above-mentioned pigment printing reaction solution is applied to the fabric by an inkjet method.

[0189] The amount of reaction solution adhering to the fabric is 10-21 mg / inch per unit area of ​​the recording area. 2 Preferably, it is 12-20 mg / inch 2 It is more preferable that the concentration be 14-19 mg / inch 2 It is even more preferable that the concentration be 15-18 mg / inch 2 It is particularly preferable that this be the case.

[0190] 3.2.1 Process interval As described above, in the recording method according to this embodiment, it is preferable that the time difference between the ink application step and the reaction solution application step is within 5 seconds. The preferred time difference in the case of alternating printing or reaction solution application first is as described above and will not be explained further.

[0191] 3.2.2 Adhesion Method As described above, the recording method according to this embodiment is preferably alternating, and may involve pre-printing or using a line-type inkjet head to perform the ink application process and the reaction solution application process. That is also acceptable.

[0192] 3.3 Other processes The recording method according to this embodiment may include a step of heating the ink, etc., attached to the fabric after the ink attachment step and reaction solution attachment step described above. The heating method is not particularly limited, but examples include the heat press method, atmospheric pressure steam method, high-pressure steam method, and thermofix method. The heat source for heating is not particularly limited, but for example, an infrared lamp can be used. The heating temperature is preferably the temperature at which the resin particles of the ink are fused and the medium such as water volatilizes. For example, it is preferably about 100°C to about 200°C, more preferably 170°C or lower, and even more preferably 160°C or lower. Here, the heating temperature in the heating step refers to the surface temperature of the image, etc., formed on the fabric. The heating time is not particularly limited, but for example, it is 30 seconds to 20 minutes.

[0193] The process may include a step of washing and drying the printed fabric after the heating step. During washing, if necessary, a soaping treatment may be performed to wash away any ink or other components that were not fixed to the fabric using a hot soap solution or the like.

[0194] 3.4 Inkjet Textile Printing Equipment An example of an inkjet printing apparatus equipped with an inkjet head, applicable to the recording method according to this embodiment, will be described with reference to Figure 1.

[0195] The inkjet printing apparatus used in the following description is a serial printer in which a recording inkjet head is mounted on a carriage that moves in a predetermined direction, and droplets are ejected onto the fabric as the inkjet head moves along with the movement of the carriage. The inkjet printing apparatus applicable to the recording method according to this embodiment is not limited to a serial printer, but may also be a line printer. A line printer is a type of printer in which the inkjet head is formed to be wider than the width of the fabric, and droplets are ejected onto the fabric without the inkjet head moving.

[0196] An inkjet printing apparatus is a device that prints by depositing tiny droplets of ink composition or reaction solution onto fabric using an inkjet head, which acts as a liquid ejection unit. Figure 1 is a schematic perspective view showing an inkjet printing apparatus used in an embodiment.

[0197] As shown in Figure 1, in this embodiment, the printer 1 includes an inkjet head 3, a carriage 4, a main scanning mechanism 5, a platen roller 6, and a control unit (not shown) that controls the operation of the entire printer 1. The carriage 4 mounts the inkjet head 3 and has removable liquid cartridges 7a, 7b, 7c, 7d, 7e, and 7f that contain the ink composition and reaction solution supplied to the inkjet head 3.

[0198] The main scanning mechanism 5 includes a timing belt 8 connected to the carriage 4, a motor 9 that drives the timing belt 8, and a guide shaft 10. The guide shaft 10 is mounted in the scanning direction of the carriage 4, i.e., the main scanning direction MS, as a support member for the carriage 4. The carriage 4 is driven by the motor 9 via the timing belt 8 and is capable of reciprocating along the guide shaft 10. Thus, the main scanning mechanism 5 has the function of moving the carriage 4 back and forth in the main scanning direction MS.

[0199] The platen roller 6 has the function of transporting the fabric 2 to be printed in the sub-scanning direction SS, which is perpendicular to the main scanning direction MS, that is, in the longitudinal direction of the fabric 2. As a result, the fabric 2 is transported in the sub-scanning direction SS. The carriage 4 on which the inkjet head 3 is mounted transports the fabric The inkjet head 3 is capable of reciprocating movement in the main scanning direction MS, which is approximately the same as the width direction of 2, and is configured to scan relative to the fabric 2 in both the main scanning direction MS and the sub-scanning direction SS.

[0200] The liquid cartridges 7a, 7b, 7c, 7d, 7e, and 7f are six independent liquid cartridges. These liquid cartridges can contain the ink composition and reaction solution used in the recording method of this embodiment. Each of these liquid cartridges individually contains ink composition and reaction solution exhibiting colors such as black, cyan, magenta, yellow, white, and orange, and can be used in any combination. While Figure 1 shows six liquid cartridges, the number is not limited to this. The bottom of each liquid cartridge 7a, 7b, 7c, 7d, 7e, and 7f is provided with a supply port (not shown) for supplying the ink composition or reaction solution contained in each cartridge to the inkjet head 3.

[0201] The inkjet head 3 is a means for spraying and adhering ink compositions and reaction solutions supplied from liquid cartridges 7a, 7b, 7c, 7d, 7e, and 7f onto the fabric 2 from multiple nozzles under the control of a control unit (not shown). The inkjet head 3 has multiple nozzles on the surface facing the fabric 2 to which the ink compositions and reaction solutions are to be applied, for ejecting and adhering the ink compositions and reaction solutions to the fabric 2. These multiple nozzles are arranged in a row to form a nozzle row, and the nozzle row is individually arranged corresponding to each color ink composition and reaction solution. Each color ink composition and reaction solution is supplied to the inkjet head 3 from each liquid cartridge and ejected as droplets from the nozzles by an actuator (not shown) inside the inkjet head 3. The ejected droplets of ink compositions and reaction solutions land on the fabric 2, and the adhesion process to the fabric 2 and the formation of images, text, patterns, colors, etc. by ink in the printing area of ​​the fabric 2. Note that multiple inkjet heads 3 may be provided on the carriage 4.

[0202] Here, the inkjet head 3 uses a piezoelectric element as the actuator, which is the driving means, but the system is not limited to this method. For example, an electromechanical conversion element that displaces a diaphragm as an actuator by electrostatic adsorption, or an electrothermal conversion element that ejects the ink composition as droplets by generating bubbles through heating may be used.

[0203] The inkjet head 3 has a group of reaction solution nozzles for ejecting the reaction solution and a group of ink composition nozzles for ejecting the ink composition. The group of nozzles that eject refers to the group of nozzles used for recording in the recording method. When performing the main scan, if there is an image to be recorded in the area of ​​the fabric opposite the group of nozzles, it is a group of nozzles that can eject ink, etc., from the nozzles, and is a group of nozzles that is continuous in the sub-scanning direction SS. Therefore, nozzle groups that exist but are not used for recording in the recording method are not included in the group of nozzles that eject.

[0204] Figures 2, 3, and 4 show examples of the arrangement of the inkjet heads 3. In Figure 2, inkjet heads 3a and 3b are arranged from upstream to downstream in the transport direction (sub-scanning direction SS). In Figure 3, inkjet heads 3a and 3b are in the same position in the sub-scanning direction SS and are arranged side by side. In Figure 4, inkjet heads 3a and 3b are arranged from upstream to downstream in the transport direction (sub-scanning direction SS) with overlapping portions.

[0205] In the recording method according to this embodiment, it is preferable that the inkjet head 3 has a group of nozzles for the reaction solution used for recording located upstream of or overlapping with the group of nozzles for the ink composition used for recording in the fabric transport direction. Also, from a similar viewpoint, the head that ejects the reaction solution is located in the same position as the head that ejects the ink composition in the fabric transport direction. It is preferable that the head is either present or located upstream of the head that ejects the ink composition in the direction of fabric transport. With such a configuration, droplets can adhere by alternating tapping or pre-tapping of the reaction solution, allowing the components of the ink composition and the reaction solution to mix more easily and the reaction to proceed more smoothly, which tends to result in superior color development, friction fastness, and suppression of bleeding.

[0206] For example, in the example shown in Figure 2, by using the inkjet head 3a as a head that ejects the reaction solution and the inkjet head 3b as a head that ejects the ink composition, the nozzle group for the reaction solution used for recording can be positioned upstream of the nozzle group for the ink composition used for recording with respect to the fabric transport direction (sub-scanning direction SS). In such a case, the reaction solution adheres to the fabric before the ink composition. That is, the reaction solution can be applied first, forming a layer containing the reaction solution, and then a layer containing the ink composition can be laminated and formed.

[0207] For example, in the example shown in Figure 3, if inkjet head 3a is used to eject the reaction solution and inkjet head 3b is used to eject the ink composition, and there is an overlapping portion between the nozzle group for the reaction solution used for recording and the nozzle group for the ink composition used for recording, then alternating printing is possible. In other words, it is possible to create a layered structure (mille-feuille-like layering) in which the reaction solution and the ink composition are layered alternately.

[0208] The "overlapping portion" refers to the portion of the nozzle group for the ink composition used for recording and the nozzle group for the reaction solution used for recording that is located in the same position in the sub-scanning direction SS. As a result, the ink composition and the reaction solution overlap and adhere to the fabric during the same main scan.

[0209] For example, in the example shown in Figure 4, if the inkjet head 3a is used to eject the reaction solution and the inkjet head 3b is used to eject the ink composition, and there is an overlapping portion between the nozzle group for the reaction solution used for recording and the nozzle group for the ink composition used for recording, then alternating printing can be used. Alternatively, if the inkjet head 3a is used to eject the reaction solution and the inkjet head 3b is used to eject the ink composition, and there is no overlapping portion between the nozzle group for the reaction solution used for recording and the nozzle group for the ink composition used for recording, and the nozzle group for the reaction solution used for recording is located upstream of the nozzle group for the ink composition used for recording in the fabric transport direction (sub-scanning direction SS), then reaction solution printing can be used first.

[0210] The printer 1 may be equipped with drying means and heating means (neither of which are shown). The drying means and heating means are means for efficiently drying the reaction liquid and ink adhering to the fabric 2. The installation position of the drying means and heating means is not particularly limited, as long as they are installed in a position where the fabric 2 can be dried and heated. In order to efficiently dry the ink and reaction liquid adhering to the fabric 2, for example, in Figure 1, the drying means and heating means can be installed in a position facing the inkjet head 3.

[0211] Examples of drying and heating means include a print heater mechanism that heats the fabric 2 by bringing it into contact with a heat source, a mechanism that irradiates infrared rays or microwaves, which are electromagnetic waves with a maximum wavelength of approximately 2,450 MHz, and a dryer mechanism that blows hot air. Heating of the fabric 2 is performed before or when the droplets ejected from the nozzles of the inkjet head 3 adhere to the fabric 2. The control of various heating conditions, such as the timing of heating, heating temperature, and heating time, is performed by the control unit.

[0212] Furthermore, the drying and heating means may be installed downstream of the fabric 2 in the conveying direction. In this case, the fabric 2 is heated after the ink or reaction liquid discharged from the nozzle adheres to the fabric 2 and an image is formed. This improves the drying efficiency of the ink or reaction liquid adhering to the fabric 2.

[0213] 4. Examples The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "%" below refers to mass.

[0214] 4.1 Preparation of reaction solution for pigment printing Each component was placed in a container to achieve the composition shown in Tables 1-3 below. Pure water was added so that the total volume of each reaction solution reached 100% by mass. The mixture was then stirred with a magnetic stirrer for 2 hours, and then thoroughly mixed by dispersion treatment in a bead mill filled with 0.3 mm diameter zirconia beads. After stirring for 1 hour, the mixture was filtered using a 5 μm PTFE membrane filter to obtain the pigment printing reaction solutions for each example and comparative example. The values ​​for cationic polymers in Tables 1-3 below represent the mass percentage of the solid content, which is the active ingredient.

[0215] [Table 1]

[0216] [Table 2]

[0217] [Table 3]

[0218] The following explanations will be provided regarding the descriptions in Tables 1-3 above. <Composition of reaction solution> [Cationic polymer] Kymene 557: A product name manufactured by SOLENIS, an epichlorohydrin-based resin. [Penetrating solvent] BTG: Triethylene glycol monobutyl ether. 〔others〕 Olphine E1010: A product name manufactured by Nisshin Chemical Industry Co., Ltd., an acetylene glycol-based surfactant. EDTA·2Na: Disodium dihydrogen dihydrogen salt of ethylenediaminetetraacetate. Proxel XL2: A product name manufactured by Lonza Japan Co., Ltd.

[0219] <term> "Boiling point": Indicates the standard boiling point. "pKa": Indicates the acid dissociation constant with respect to water. "bp230℃ or less / bp250℃ or more": Content of polyhydric alcohols with a standard boiling point of 230℃ or less / Content of polyhydric alcohols with a standard boiling point of 250℃ or more. "bp250℃ or higher / cationic polymer": Content of polyhydric alcohols with a standard boiling point of 250℃ or higher / Content of cationic polymers. "Bk": Ink with the composition listed in Table 4 below. "IJ": Coating using the inkjet method.

[0220] pH was measured using a benchtop pH meter (model number: F-72, manufacturer: HORIBA). The temperature for pH measurement was 20°C.

[0221] 4.2 Preparation of Textile Inkjet Ink Composition Each component was placed in a container to obtain the composition shown in Table 4 below. The mixture was then mixed and stirred with a magnetic stirrer for 2 hours, and then thoroughly mixed by dispersion treatment in a bead mill filled with 0.3 mm diameter zirconia beads. After stirring for 1 hour, the ink composition was obtained by filtration using a 5 μm PTFE membrane filter. Pure water was added so that the total amount of the ink composition was 100% by mass.

[0222] The pigment was prepared by first mixing a pigment dispersant (a styrene-acrylic water-soluble resin not listed in the table) and the pigment in water at a mass ratio of pigment:pigment dispersant = 2:1, stirring, and then using this pigment dispersion for ink preparation.

[0223] [Table 4]

[0224] 4.3 Preparation of Printed Materials Using a modified PX-H8000 (manufactured by Seiko Epson Corporation), printing was performed on a 100% cotton white broadcloth recording medium under the conditions described in Tables 1-3 above. By performing multiple main scans (4 times) on the same scanning area, a solid pattern image was formed on the A4-sized fabric recording medium. Subsequently, the printed materials for each example and comparative example were produced by heating and drying in an oven at 160°C for 3 minutes. A "solid pattern image" refers to an image in which dots are recorded for all pixels in the smallest recording unit area defined by the recording resolution (Duty 100%).

[0225] • The inkjet head has a nozzle-to-nozzle distance of 600 dpi in the width direction of the recording medium, and the number of nozzles 600 head units were used. The nozzle group for the reaction solution and the nozzle group for the ink composition have portions located in the same position in the sub-scanning direction, and the head arrangement shown in Figure 3 was used. This ensures that the reaction solution and ink composition are applied to the same scanning area of ​​the fabric with the same main scan. The time difference between ink adhesion and reaction solution adhesion was limited to within 5 seconds. Regarding the reaction solution, the recording resolution was 1200 x 600 dpi, the droplet mass was 24.2 ng, and the injection rate was 17.4 mg / inch. 2 That's what I decided. Regarding the ink, the recording resolution is 1200 x 600 dpi, the droplet mass is 24.2 ng, and the ink density is 17.4 mg / inch. 2 That's what I decided.

[0226] 4.4 Evaluation Method 4.4.1 Intermittent Printing Stability The PX-H8000 (manufactured by Seiko Epson Corporation) was modified and filled with the pigment printing reaction solutions obtained above. After a 3-minute idle run, the number of missing nozzles was counted using a nozzle check pattern, and the intermittent printing stability was evaluated according to the following criteria. If the evaluation result is C or higher, it can be said that good intermittent printing stability has been achieved. (Evaluation Criteria) A: The number of non-discharging nozzles is less than 4. B: Number of non-discharging nozzles is 4 or more but less than 7 C: Number of non-discharging nozzles is 7 or more but less than 11 D: Number of non-discharging nozzles is 11 or more

[0227] 4.4.2 Color development The OD values ​​of the black printed materials obtained above were measured using a fluorescence spectrophotometer ("FD-7", manufactured by Konica Minolta), and the color development was evaluated according to the following criteria. A result of B or higher indicates that good color development has been achieved. (Evaluation Criteria) A: OD value is 1.45 or higher B: OD value is 1.40 or higher and less than 1.45 C:OD value is 1.35 or higher and less than 1.40 D:OD value is less than 1.35

[0228] 4.4.3 Smudging For the evaluation of bleeding, the same printed materials used in the "Wet Friction Fastness" test described below were used. The bleeding of ink within the solid patterns of the printed materials (spots or streaky unevenness within the solid patterns) was observed visually and evaluated according to the evaluation criteria below. If the evaluation result was B or higher, it was judged that there was no bleeding. On the other hand, if the evaluation result was C, it was judged that there was bleeding. (Evaluation Criteria) A: No bleeding was observed within the solid pattern. B: Slight bleeding was observed within the solid color pattern. C: Significant bleeding was observed throughout the solid color pattern.

[0229] 4.4.4 Wet friction fastness The printed materials obtained above were tested for friction fastness using a test method compliant with ISO 105-X12, and the initial wet friction fastness was evaluated according to the following criteria. Furthermore, the accelerated wet friction fastness was evaluated according to the following criteria, except that the pigment printing reaction solution was pre-treated by standing in a 60°C constant temperature bath for 5 days. A result of C or higher indicates good friction fastness. (Evaluation Criteria) A: Friction fastness grade 3 or higher B: Friction fastness grade 2-3 or higher but less than grade 3 C: Friction fastness is grade 2 or higher but less than grade 2-3. D: Friction fastness is less than grade 2.

[0230] 4.4.5 Pitting corrosion The inkjet head was immersed in each of the pigment printing reaction solutions obtained above, and left to stand at 60°C to check whether pitting corrosion occurred. If the evaluation result was C or higher, it was determined that there was no pitting corrosion. On the other hand, if the evaluation result was D, it was determined that pitting corrosion was present. Even if pitting corrosion was present, the printer was still usable. (Evaluation Criteria) A: It did not pit even after being left for over 400 hours. B: Pitting occurred between 200 hours and 400 hours later. C: Pitting occurred between 50 and 200 hours. D: Pitting occurred in less than 50 hours.

[0231] 4.5 Evaluation Results The evaluation results are shown in Tables 1 to 3 above.

[0232] From Tables 1 to 3 above, in each of the examples using a reaction liquid for pigment printing that contains a polyvalent metal salt, a cationic polymer, a polyhydric alcohol, an alkali, and water, and in which the alkali is an amine compound and is discharged by an inkjet method, all had excellent color development properties and rubbing fastness, and pitting corrosion occurring on the metal members of the recording apparatus could be suppressed.

[0233] From the comparison between Example 2 and Comparative Examples 1 and 2, pitting corrosion occurred when the alkali was not contained. Also, from the comparison between Example 2 and Comparative Examples 6 to 8, when the alkali was not an amine compound, pitting corrosion did not occur, but the wet rubbing fastness after acceleration was poor.

[0234] From the comparison between Example 2 and Comparative Examples 2 and 4, when the polyvalent metal salt was not contained, the color development property was poor.

[0235] From the comparison between Example 2 and Comparative Examples 2 and 3, when the cationic polymer was not contained, the wet rubbing fastness was poor.

[0236] From the comparison between Example 2 and Comparative Example 5, when the polyhydric alcohol was not contained, the wet rubbing fastness after acceleration was poor.

[0237] From the results of Examples 1 to 4, it was possible to achieve both suppression of pitting corrosion and wet rubbing fastness with a wide range of alkali contents.

[0238] From the results of Examples 2, 5 to 8, it was possible to achieve both suppression of pitting corrosion and wet rubbing fastness with various polyvalent metal salts.

[0239] From the results of Examples 2, 9 to 16, it was possible to achieve both suppression of pitting corrosion and wet rubbing fastness with various amine compounds. Also, when the amine compound contained a tertiary amine, the wet rubbing fastness was more excellent.

[0240] The results from Examples 2, 17, and 18 showed that including a predetermined amount of polyhydric alcohol with a relatively high standard boiling point resulted in improved intermittent printing stability.

[0241] From the results of Examples 2 and 19, it was found that when the cationic polymer content is at a predetermined level, the moisture after acceleration is reduced. The friction resistance has been improved.

[0242] The following conclusions can be drawn from the embodiments described above.

[0243] One embodiment of a reaction solution for pigment printing is: Polyvalent metal salts, Cationic polymers and Polyhydric alcohols, It contains alkali and water, The alkali is an amine compound, It is used by ejecting it using an inkjet method.

[0244] In one embodiment of the above-mentioned pigment printing reaction solution, The alkali may contain a tertiary amine.

[0245] In any aspect of the above-mentioned pigment printing reaction solution, The pH of the reaction solution may be between 5 and 10.

[0246] In any aspect of the above-mentioned pigment printing reaction solution, The pKa of the alkali may be 7.0 to 11.0.

[0247] In any aspect of the above-mentioned reaction solution for pigment printing, The alkali content may be 0.1 to 3.0% by mass relative to the total amount of the reaction solution.

[0248] In any aspect of the above-mentioned pigment printing reaction solution, The polyvalent metal salt may also be a sulfate.

[0249] In any aspect of the above-mentioned reaction solution for pigment printing, The polyhydric alcohol may be a polyhydric alcohol having a standard boiling point of 250°C or higher.

[0250] One aspect of the ink set is a printing inkjet ink composition containing a pigment, resin particles, and water, and a reaction solution for pigment printing of any of the above aspects.

[0251] One aspect of the recording method is an ink adhesion step of adhering an ink composition to a fabric by an inkjet method, and a reaction solution adhesion step of adhering the reaction solution for pigment printing of any of the above aspects to the fabric by an inkjet method.

[0252] In one aspect of the above recording method, the time difference between the ink adhesion step and the reaction solution adhesion step may be within 5 seconds.

[0253] In any aspect of the above recording method, the inkjet method performs a plurality of main scans in which an inkjet head is moved in a direction perpendicular to the conveyance direction of the fabric to perform recording, the reaction solution for pigment printing and the ink composition are adhered to the same scanning area of the fabric by the same main scan, and the same main scan may be performed a plurality of times on the same scanning area.

[0254] The present invention is not limited to the above-described embodiments, and various modifications are possible. For example, the present invention includes configurations that are substantially the same as the configurations described in the embodiments, such as configurations having the same functions, methods, and results, or configurations having the same objectives and effects. Further, the present invention includes configurations in which non-essential parts of the configurations described in the embodiments are replaced. Further, the present invention includes configurations that exhibit the same operational effects as the configurations described in the embodiments or configurations that can achieve the same objectives. Further, the present invention includes configurations in which known techniques are added to the configurations described in the embodiments. [Explanation of Symbols]

[0255] 1...Printer, 2...Fabric, 3(3a,3b)...Inkjet head, 4...Carriage, 5...Main scanning mechanism, 6...Platen roller, 7a,7b,7c,7d,7e,7f...Liquid cartridge, 8...Timing belt, 9...Motor, 10...Guide shaft

Claims

1. Polyvalent metal salts, Cationic polymers and Polyhydric alcohols, It contains alkali and water, The alkali is an amine compound, It is ejected and used by the inkjet method. The content of the aforementioned cationic polymer is 0.5% by mass or more and 5.0% by mass or less, relative to the total amount of the reaction solution. A reaction solution for pigment printing, wherein the ratio of the content of the alkali (M5) to the content of the cationic polymer (M3) (M5 / M3) is 0.1 or more and 3.0 or less.

2. The reaction solution for pigment printing according to claim 1, wherein the alkali contains a tertiary amine.

3. The reaction solution for pigment printing according to claim 1, wherein the pH of the reaction solution is 5 to 10.

4. The pigment printing reaction solution according to claim 1, wherein the pKa of the alkali is 7.0 to 11.

0.

5. The pigment printing reaction solution according to claim 1, wherein the alkali content is 0.1 to 3.0% by mass relative to the total amount of the reaction solution.

6. The pigment printing reaction solution according to claim 1, wherein the polyvalent metal salt is a sulfate.

7. The reaction solution for pigment printing according to claim 1, wherein the polyhydric alcohol is a polyhydric alcohol with a standard boiling point of 250°C or higher.

8. A textile inkjet ink composition containing pigment, resin particles, and water, An insecticide comprising a pigment printing reaction solution according to any one of claims 1 to 7, Kuset.

9. An ink application process in which an ink composition is applied to the fabric by an inkjet method, A recording method comprising a reaction solution application step of applying a pigment printing reaction solution according to any one of claims 1 to 7 to the fabric by an inkjet method.

10. The recording method according to claim 9, wherein the time difference between the ink application step and the reaction solution application step is 5 seconds or less.

11. The aforementioned inkjet method involves performing multiple main scans in which the inkjet head is moved perpendicular to the transport direction of the fabric to perform recording. The pigment printing reaction solution and the ink composition are applied to the same scanning area of ​​the fabric by the same main scan. The recording method according to claim 9, wherein the same main scan is performed multiple times on the same scanning area.

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