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

Abstract

To provide a pigment textile-printing reaction liquid used by discharging by an inkjet method that is excellent in color development, friction fastness and intermittent printing stability.SOLUTION: The pigment textile-printing reaction liquid according to an embodiment of the present invention contains a polyvalent metal salt, a cationic polymer, a polyhydric alcohol with a standard boiling point of 250°C or higher, and water, and is used by being discharged by an inkjet method.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, when manufacturing printed materials by dyeing fabrics and other substrates with pigments and other colorants using an inkjet method, a technique has been known to pre-treat the substrate using a reaction solution containing cationic compounds to improve the color development of the colorants. In this context, research is being conducted on the reaction solution ejected by the inkjet method in a recording method in which the pre-treatment and ink application processes are performed in a single recording device.

[0003] For example, Patent Document 1 discloses a pretreatment solution containing a polyvalent metal compound that can be applied to a wet-on-wet recording method in which the steps from applying the pretreatment solution to applying the ink are performed without a drying step, in a printing (pigment printing) using an ink composition containing a pigment. [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 with poor color development, friction fastness, and intermittent printing stability. [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 It contains polyhydric alcohols with a standard boiling point of 250°C or higher, and water. 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 an embodiment of the present invention contains a polyvalent metal salt, a cationic polymer, a polyhydric alcohol having a standard boiling point of 250°C or higher, and water, and is discharged by an inkjet method for use.

[0012] Conventionally, when producing a printed matter by dyeing a substrate such as cloth by an inkjet method using a coloring material such as a pigment, in order to improve the color development property of the coloring material, a reaction liquid containing a cationic compound or the like is used to pretreat the substrate. Technology is known. And the pretreatment in inkjet pigment printing is usually performed by an immersion method or the like using a separate device / equipment. However, such a method not only requires the use of a separate device / equipment, but also complicates the process and requires know-how when using the separate device / equipment. In addition, there is waste liquid discharge, which is not preferable from the viewpoint of environmental load.

[0013] Therefore, in inkjet pigment printing, studies have been made on discharging 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 cloth and improve the color development property, but there is a problem that the ink stays near the surface of the cloth, making it likely 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 cloth and the rubbing fastness (especially wet rubbing fastness) can also be improved. On the other hand, when a cationic polymer is contained, even a small amount of moisture volatilized from the reaction liquid tends to have a high viscosity, and a new problem arises in that the discharge stability (intermittent printing stability) is likely to be inferior when applying the inkjet method.

[0015] As a result of further intensive studies by the present inventors, it has been found that by further containing a polyhydric alcohol having a standard boiling point of 250°C or higher, even when a cationic polymer is contained, the ejection stability (intermittent printing stability) can be improved. That is, according to the reaction liquid for pigment printing of the present embodiment, color development property, rubbing fastness, and intermittent printing stability can be improved.

[0016] 1.1 Use The reaction liquid for pigment printing according to the present embodiment is ejected by an inkjet method and used.

[0017] "For pigment printing" means, for example, that it is used in printing performed using an ink composition containing a pigment.

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

[0019] The pigment printing reaction solution according to this embodiment is dispensed by an inkjet method. Unlike conventional pretreatment, this eliminates the need for separate equipment / facilities, simplifies the process, and eliminates the discharge of waste liquid. Furthermore, by applying the reaction solution by an inkjet method, the image is less likely to bleed, even when a large amount of reaction solution is applied, compared to application by a spray or other method. This is presumed to be because, with inkjet application, the dispensing amount can be controlled to a small amount, and the ink and reaction solution can come into immediate contact in a wet-on-wet manner, thus facilitating the reaction between the reaction solution and the ink. In contrast, with application by a spray or other method, it is difficult to control the dispensing amount to a small amount, and because a drying process is usually required, the ink and reaction solution do not come into immediate contact in a wet-on-wet manner, resulting in a less effective reaction between the reaction solution and the ink. In other words, after applying a large amount of the reaction solution to the fabric by spraying or the like and allowing it to dry, 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 immediately coagulate, causing ink penetration and bleeding.

[0020] 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, the reaction solution is preferably capable of agglomerating or thickening the components of the ink composition, and more preferably contains components that agglomerate or thicken the components of the ink composition. The reaction solution may contain a colorant, but the amount is preferably 0.2% by mass or less, more preferably 0.1% by mass or less, even more preferably 0.05% by mass or less, with a lower limit of 0% by mass. It is preferable that the reaction solution does not contain a colorant.

[0021] The following describes each component contained in the pigment printing reaction solution according to this embodiment.

[0022] 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.

[0023] 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.

[0024] The anions constituting polyvalent metal salts are inorganic ions or organic ions. In other words, a polyvalent metal salt as used herein consists of an inorganic ion or organic ion and a polyvalent metal. Examples of such inorganic ions include chloride ions, bromide ions, iodide ions, nitrate ions, sulfate ions, hydroxide ions, etc. Examples of organic ions include organic acid ions, such as carboxylate ions.

[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 fabrics may be inferior. In contrast, magnesium salts, compared to other salts such as calcium salts, exhibit a milder cohesive reaction with ink, making the reaction easier to control. Therefore, This method tends to produce good color development, as well as good friction fastness and granular texture. The counterion for the polyvalent metal can be either an inorganic acid ion or an organic acid ion.

[0026] Specific examples of polyvalent metal salts are not limited to 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. These metal salts may contain hydration water in their raw material form.

[0027] 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 and friction fastness.

[0028] 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.

[0029] 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.

[0030] As cationic urethane resins, commercially available products can be used, such as Hydran 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.).

[0031] 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.).

[0032] As cationic amine resins, known ones can be appropriately selected and used. Preferably, 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, cationic amine resins may also contain two or more of the above-mentioned cationic functional groups.

[0033] 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.

[0034] 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.).

[0035] 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.

[0036] 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.).

[0037] Cationic amine resins having a tertiary amine group include methyldiallylamine hydrochloride polymers, methyldiallylamine amide sulfate polymers, methyldiallylamine acetate polymers, methyldiallylamine hydrochloride-sulfur dioxide copolymers, and dicyandiamide-polyalkylene polyamine polycondensates.

[0038] 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.).

[0039] 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.).

[0040] Cationic amine resins containing a quaternary ammonium base include diallyl dimethyl Examples include ammonium chloride polymers, diallylmethylethylammonium ethyl sulfate polymers, diallylmethylethylammonium ethyl sulfate / sulfur dioxide copolymers, diallyldimethylammonium chloride / sulfur dioxide copolymers, and diallyldimethylammonium chloride / acrylamide copolymers.

[0041] 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.).

[0042] Cationic amine resins having an imino group include polyethyleneimine, octadecyl isocyanate-modified polyethyleneimine, and propylene oxide-modified polyethyleneimine.

[0043] 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).

[0044] 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.).

[0045] Furthermore, the following are examples of cationic amine resins having two or more cationic functional groups.

[0046] 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.).

[0047] Cationic amine resins having a primary amine group and a quaternary ammonium base include allylamine-diallyldimethylammonium chloride copolymers, and commercially available examples include PAA-1123 (manufactured by Nitto Boseki Medical Co., Ltd.).

[0048] 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.).

[0049] Cationic polymers may be used individually or in combination of two or more types.

[0050] Furthermore, it is preferable that the cationic polymer has a structure derived from an epihalohydrin. An epihalohydrin is a monomer having an epoxy group and a halogeno group. Examples of such groups include fluoro groups, chloro groups, bromo groups, iodine groups, and astat groups. It is more preferable that the epihalohydrin is an epichlorohydrin, where the halogeno group is a chloro group. When the cationic polymer has a structure derived from epihalohydrin, unreacted epoxy groups and other components of the epihalohydrin can contribute to the crosslinking reaction as crosslinking groups. This allows the ink to thicken and aggregate more easily, improving color development, and the crosslinking strengthens the ink layer, resulting in better friction fastness. Furthermore, when the fabric is cotton, a crosslinking reaction occurs between the crosslinking groups derived from the epihalohydrin and the hydroxyl groups of the cotton cellulose, improving adhesion between the fabric and the ink layer and resulting in better friction fastness.

[0051] 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.

[0052] Cationic polymers having a structure derived from epihalohydrins may be commercially available products, including Kymene557 (manufactured by SOLENIS), Myriogen P-20, Unisense KHE107L (manufactured by Senka), 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), Catiomaster 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).

[0053] 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.

[0054] 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, and particularly preferably 2.0 to 3.5% by mass, relative to the total amount of the reaction solution. When the cationic polymer content is 0.5% by mass or more, good friction fastness can be achieved. On the other hand, when the cationic polymer content is 5.0% by mass or less, the viscosity of the reaction solution can be made suitable for the inkjet method, and good intermittent printing stability can be achieved.

[0055] 1.4 Polyhydric alcohols A polyhydric alcohol is a substance having one or more hydroxyl groups in its molecule, preferably two or more hydroxyl groups, and more preferably three or more hydroxyl groups. Examples of polyhydric alcohols include alcohols, alkanediols, polyols, and alkylene glycol monoalkyl ethers. Among these, the polyhydric alcohol is preferably one or more selected from polyols and alkylene glycol monoalkyl ethers, and more preferably polyols. The state of a polyhydric alcohol at room temperature and pressure may be a liquid or a solid. It may be any other form, but it is preferable that it be a liquid.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] Examples of alkylene glycol monoalkyl ethers 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, and tripropylene glycol monobutyl ether.

[0062] 1.4.1 Polyhydric alcohols with a standard boiling point of 250°C or higher The pigment printing reaction solution according to this embodiment contains a polyhydric alcohol with a standard boiling point of 250°C or higher. This ensures good moisture retention of the reaction solution and allows for good discharge stability, even when a cationic polymer is included. Furthermore, from the viewpoint of suppressing VOC (volatile organic compound) issues, it is preferable that the polyhydric alcohol has a standard boiling point of 250°C or higher.

[0063] 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). Examples of alkylene glycol monoalkyl ethers with a standard boiling point of 250°C or higher include triethylene glycol monobutyl ether (BTG, standard boiling point 278°C), triethylene glycol monoethyl ether (standard boiling point 255°C), and tetraethylene glycol monobutyl ether (standard boiling point 290°C or higher). Among these, the polyhydric alcohol with a standard boiling point of 250°C or higher is preferably one or more selected from triethylene glycol, glycerin, and triethylene glycol monobutyl ether, and more preferably glycerin. When the above compounds are used, the moisture retention is better and the intermittent printing stability tends to be superior. Furthermore, from a similar viewpoint, of the polyhydric alcohols with a standard boiling point of 250°C or higher, a standard boiling point of 260°C or higher is preferred, a standard boiling point of 270°C or higher is more preferred, a standard boiling point of 280°C or higher is even more preferred, and a standard boiling point of 285°C or higher is particularly preferred.

[0064] 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, particularly preferably 10% by mass or more, and even more preferably 12% 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 16% 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.

[0065] 1.4.2 Polyhydric alcohols with a standard boiling point of 230°C or less The pigment printing reaction solution according to this embodiment preferably further contains 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 the solvent difficult to dry and causing it to remain on the fabric. This can inhibit the reaction of the cationic polymer, potentially leading to poor friction fastness. In contrast, the inclusion of a polyhydric alcohol with a standard boiling point of 230°C or lower mitigates this problem, improving the reactivity of the cationic polymer and thus achieving good friction fastness. However, if only a polyhydric alcohol with a standard boiling point of 230°C or lower is included, the moisturizing properties are poor, and good intermittent printing stability cannot be obtained.

[0066] 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), 1,4-butanediol (standard boiling point 230°C), 2-ethyl-2-methyl-1,3-propanediol (standard boiling point 226°C), 2-methyl-1,3-propanediol (standard boiling point 214°C), and 2,2-dimethyl-1,3 Examples include 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). Examples of alkylene glycol monoalkyl ethers with a standard boiling point of 230°C or lower include ethylene glycol monomethyl ether (standard boiling point 124°C), ethylene glycol monoethyl ether (standard boiling point 135°C), ethylene glycol monoisopropyl ether (standard boiling point 141°C), ethylene glycol monobutyl ether (standard boiling point 171°C), diethylene glycol monomethyl ether (standard boiling point 194°C), diethylene glycol monoethyl ether (standard boiling point 196°C), propylene glycol monomethyl ether (standard boiling point 121°C), propylene glycol monoethyl ether (standard boiling point 132°C), propylene glycol monopropyl ether (standard boiling point 149°C), propylene glycol monobutyl ether (standard boiling point 170°C), dipropylene glycol monomethyl ether (standard boiling point 188°C), and dipropylene glycol monopropyl ether (standard boiling point 210°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 compound is used, the inhibition of the reaction of the cationic polymer is further reduced and the frictional fastness tends to be superior. Also, from a similar viewpoint, the polyhydric alcohol with a standard boiling point of 230°C or lower is preferably 220°C or lower, more preferably 210°C or lower, even more preferably 200°C or lower, and particularly preferably 190°C or lower.

[0067] 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, particularly preferably 10% by mass or more, and even more preferably 12% 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 16% 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.

[0068] 1.5 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 30.0. The upper limit of the content ratio (M2 / M1) is more preferably 25 or less, even more preferably 20 or less, even more preferably 15 or less, particularly preferably 10 or less, even more preferably 5 or less, and especially preferably 3 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.

[0069] 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 50.0. The upper limit of the content ratio (M1 / M3) is preferably 40 or less, more preferably 30 or less, even more preferably 25 or less, and even more preferably 20 or less. More preferably, the ratio is 15 or less, most preferably 12 or less, and especially preferably 9 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, most preferably 5 or more, and most preferably 6 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.

[0070] 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 4.0. The upper limit of the content ratio (M3 / M4) is preferably 3.0 or less, more preferably 2.0 or less, even more preferably 1.7 or less, even more preferably 1.4 or less, particularly preferably 1.1 or less, and most particularly preferably 0.9 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 most 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.

[0071] 1.6 Water The pigment printing reaction solution according to this embodiment may contain 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.

[0072] The water content is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 45% by mass or more, even more preferably 50% by mass or more, particularly preferably 55% by mass or more, and most particularly preferably 60% by mass or more, based on the total amount of the reaction solution. By keeping the water content within the above range, the reaction solution for pigment printing can be made relatively low viscosity. Furthermore, the upper limit of the water content is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, based on the total amount of the reaction solution.

[0073] 1.7 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 esters, alkylene glycol dialkyl ethers, cyclic esters, and nitrogen-containing solvents. Examples of nitrogen-containing solvents include cyclic amides and acyclic amides. Examples of acyclic amides include alkoxyalkyl amides.

[0074] Esters include glycol monoacetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, methoxybutyl acetate, ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, ethylene glycol acetate propionate, ethylene glycol acetate butyrate, and diethylene glycol acetate. Examples of glycol diesters include tate 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.

[0075] Examples of alkylene glycol dialkyl ethers include 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] Organic solvents may be used individually or in combination of two or more types.

[0080] 1.8 Alkali Compounds The pigment printing reaction solution according to this embodiment may contain an alkaline compound. By including a compound, the reaction solution can be easily adjusted to a desirable pH (described later). This tends to reduce corrosion of the inkjet head. Examples of alkali compounds include inorganic alkali compounds and organic alkali compounds.

[0081] Examples of inorganic alkali compounds include alkali metal hydroxides or alkaline earth metal hydroxides, alkali metal carbonates or alkaline earth metal carbonates, alkali metal phosphates or alkaline earth metal phosphates, and the like.

[0082] Examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, and potassium hydroxide. Examples of alkaline earth metal hydroxides include calcium hydroxide and magnesium hydroxide. Examples of alkali metal carbonates include lithium carbonate, lithium bicarbonate, potassium carbonate, potassium bicarbonate, sodium carbonate, and sodium bicarbonate. Examples of alkaline earth metal carbonates include calcium carbonate. Examples of alkali metal phosphates include lithium phosphate, potassium phosphate, trisodium phosphate, and disodium hydrogen phosphate. Examples of alkaline earth metal phosphates include calcium phosphate and calcium hydrogen phosphate.

[0083] Examples of organic alkali compounds include ammonia, aliphatic amines, aromatic amines, aliphatic ammonium compounds, aromatic ammonium compounds, heterocyclic compounds and their hydroxides, carbonates, phosphates, etc. Examples of organic alkali compounds include ammonia, hydrazine, methylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, butylamine, diaminoethane, diaminopropane, diaminobutane, diaminopentane, diaminohexane, cyclohexylamine, aniline, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, pyridine, N,N-dimethyl-4-aminopyridine, ammonium carbonate, ammonium bicarbonate, diammonium hydrogen phosphate, piperidine, diethanolamine, triethanolamine, triisopropanolamine, morpholine, etc., and modified products thereof.

[0084] When an alkali compound is included, the upper limit of its content is preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less, particularly preferably 2% by mass or less, and most preferably 1.5% by mass or less, relative to the total amount of the reaction solution. The lower limit of the alkali compound content is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, particularly preferably 0.7% by mass or more, and most preferably 0.9% by mass or more, relative to the total amount of the reaction solution. When the alkali compound content is below the aforementioned upper limit, corrosion of the inkjet head can be effectively reduced, the reactivity of the cation is less likely to be inhibited, and frictional fastness tends to be good. Furthermore, when the alkali compound content is above the aforementioned lower limit, corrosion of the inkjet head tends to be sufficiently reduced.

[0085] In the pigment printing reaction solution according to this embodiment, when the content of the alkaline compound relative to the total amount of the reaction solution is M5 and the content of the cationic polymer relative to the total amount of the reaction solution is M3, the content ratio (M5 / M3) is preferably 0.1 to 1.0. The upper limit of the content ratio (M5 / M3) is preferably 0.9 or less, more preferably 0.8 or less, even more preferably 0.7 or less, and particularly preferably 0.6 or less. The lower limit of the content ratio (M5 / M3) is preferably 0.2 or more, more preferably 0.3 or more, and even more preferably 0.4 or more. When the content ratio (M5 / M3) is within the above range, a good balance is achieved between friction fastness and reduction of inkjet head corrosion. It tends to be possible.

[0086] 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.

[0087] 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, DF110D (all of the above are brand names, manufactured by Air Products Japan Co., Ltd.), O Examples include Rufin 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 brand names, manufactured by Nisshin Chemical Industry Co., Ltd.), and Acetyleneol E00, E00P, E40, E100 (all brand names, manufactured by Kawaken Fine Chemical Co., Ltd.).

[0088] 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.).

[0089] 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.).

[0090] If a surfactant is included, its content can be 0.1% by mass or more and 1.5% by mass or less relative to the total amount of the reaction solution, and is preferably 0.5% by mass or more and 1% by mass or less.

[0091] 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.

[0092] 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); diethylenetriaminepentaacetic acid and its salts such as DTPA, DTPA-2Na (diethylenetriaminepentaacetic acid disodium salt), and DTPA-5Na (diethylenetriaminepentaacetic acid pentasodium salt); and nitrilotriacetic acid such as NTA, NTA-2Na (nitrilotriacetic acid disodium salt), and NTA-3Na (nitrilotriacetic acid trisodium salt). Examples include 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.

[0093] 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.

[0094] Metal sealants may be used individually or in combination of two or more types.

[0095] If a metal sealant is included, its content can be, for example, 0.005% 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, relative to the total amount of the reaction solution.

[0096] 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).

[0097] 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.

[0098] 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.

[0099] 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.

[0100] From the viewpoint of reliability when ejected by the inkjet method, the pigment printing reaction solution 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 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 ranges, the types of polyhydric alcohols and surfactants mentioned above, and the amounts of these and water added can be adjusted as appropriate.

[0101] Furthermore, the surface tension can be measured using the Wilhelmy method. Surface tension can be measured using a surface tension meter such as the CBVP-7 manufactured by Kyowa Interface Science Co., Ltd. This can be done. Furthermore, 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].

[0102] The pH of the pigment printing reaction solution according to this embodiment is preferably 4.5 or higher at 20°C, more preferably 5.0 or higher, even more preferably 5.5 or higher, even more preferably 6.0 or higher, particularly preferably 6.5 or higher, even more preferably 7.0 or higher, and especially preferably 7.5 or higher. Because the pigment printing reaction solution according to this embodiment contains cationic components, its pH tends to be low, which may corrode the stainless steel of the inkjet head. In contrast, if the pH of the reaction solution is within the above range, corrosion of the inkjet head tends to be reduced. The pH can preferably be adjusted to the above range using the aforementioned alkaline compound.

[0103] 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.

[0104] According to the ink set of this embodiment, since it is equipped with the above-mentioned pigment printing reaction solution, it is possible to achieve good color development, friction fastness, and intermittent printing stability.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] Furthermore, in the following explanation, "printing inkjet ink composition" may also be referred to as "inkjet ink composition," "ink composition," or "ink."

[0110] 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. A pigment is a type of colorant. Examples of colorants include pigments and dyes.

[0111] 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.

[0112] 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 (registered trademark) 5750, 5250, 5000, 3500, 1255, and 700; CABOT's Rega1 (registered trademark) 400R, 330R, and 660R; Mogul (registered trademark) L; and Monarch (registered trademark) 700, 800, 880, 900, 1000, 1100, 1300, and 1400; and Degussa's Color Black. Examples include FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Printex® 35, U, V, 140U, and SpecialBlack 6, 5, 4A, 4.

[0113] 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.

[0114] Specific examples of organic pigments include the following:

[0115] 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.

[0116] 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.

[0117] 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.

[0118] Other colored pigments can also be used. For example, orange pigment and green pigment can be used.

[0119] Pigments may be used individually or in combination of two or more types.

[0120] 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.

[0121] Pigment surface treatment refers to the process of adding carbonyl groups, carboxyl groups, aldehyde groups, hydroxyl groups, sulfone groups, ammonium groups, and other components to the surface of the pigment through physical or chemical treatment. This refers to the process of directly or indirectly attaching functional groups, such as salts of these compounds.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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."

[0127] 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.

[0128] 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.

[0129] 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.

[0130] In addition to urethane bonds, urethane resins also include polyethers that contain ether bonds in their main chain. Examples include urethane resins, 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.

[0131] Commercially available urethane resins include ETERNACOLL UW-1501F, UW-1527F, UW-5002 (all product names from Ube Industries), Takelac WS-5000, W-6061, W-6110, WS-5984, WS-5100 (all product names from Mitsui Chemicals), Permarin UA-150, UA-200, U-Coat UX-390 (all product names from Sanyo Chemical Industries), and Hydran WLS-210 (product name from DIC).

[0132] 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.

[0133] Examples of commercially available (meth)acrylic resins include Movinyl 966A and 6760 (product names of Nippon Synthetic Chemical Co., Ltd.), which are acrylic resins.

[0134] (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" is a concept that includes both "methacrylic" and "acrylic."

[0135] 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).

[0136] 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.

[0137] 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.

[0138] 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.

[0139] 2.2.4 Polyhydric alcohols with a standard boiling point of 250°C or higher The inkjet ink composition for textile printing provided in the ink set according to this embodiment may contain polyhydric alcohols with a standard boiling point of 250°C or higher. The type and content of such polyhydric alcohols with a standard boiling point of 250°C or higher can be the same as those of the pigment textile printing reaction solution described above. Furthermore, it may also contain polyhydric alcohols or organic solvents with a standard boiling point of 230°C or lower, and can be the same as those of the pigment textile printing reaction solution described above.

[0140] 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.

[0141] 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 buffer, phosphate buffer, citrate buffer, Tris buffer, etc., containing ethyl (C)-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. may also be used.

[0142] 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.

[0143] 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.

[0144] 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. 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.

[0145] 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.

[0146] 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.

[0147] According to the recording method of this embodiment, since it includes a reaction solution application step in which the above-mentioned pigment printing reaction solution is applied, good color development, friction fastness, and intermittent printing stability can be achieved.

[0148] 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.

[0149] 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.

[0150] 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.

[0151] In this embodiment, examples of fabrics include cloth, clothing, and other fashion accessories. Cloths include woven fabrics, knitted fabrics, nonwoven fabrics, etc. Clothing and other fashion accessories include sewn T-shirts, handkerchiefs, scarves, towels, tote bags, cloth bags, curtains, sheets, bedspreads, wallpaper and other furniture, as well as fabrics before and after cutting as parts before sewing. These forms include long rolls, cut to predetermined sizes, and product shapes.

[0152] As the fabric, cotton fabric that has been pre-colored with dye may be used. Examples of dyes used to pre-color the fabric include water-soluble dyes such as acid dyes and basic dyes, disperse dyes used in combination with dispersants, and reactive dyes. When using cotton fabric, it is preferable to use a reactive dye suitable for dyeing cotton.

[0153] The following describes each step of the recording method according to this embodiment.

[0154] 3.1 Ink application process The recording method according to this embodiment includes an ink application step in which an ink composition is applied to a fabric by an inkjet method.

[0155] As the ink composition, the above-mentioned textile inkjet ink composition can preferably be used.

[0156] The inkjet method refers to the inkjet head used in inkjet recording devices, etc. This recording method involves ejecting droplets of liquid, such as ink, from a nozzle and applying them to a recording medium.

[0157] The amount of ink composition applied is 10-21 mg / inch per unit area of ​​the recording area of ​​the fabric. 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 / inch2 It is particularly preferable that this be the case.

[0158] 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.

[0159] 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.

[0160] 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."

[0161] 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.

[0162] The time difference between the ink application process and the reaction solution application process is preferably 4.9 seconds or less, more preferably 4.8 seconds or less, even more preferably 4.7 seconds or less, and particularly preferably 4.6 seconds or less, in the case of reaction solution pre-application. The lower limit is not particularly limited, but is preferably 3.0 seconds or more, more preferably 3.5 seconds or more, even more preferably 4.0 seconds or more, particularly preferably 4.2 seconds or more, and even more preferably 4.4 seconds or more. In the case of reaction solution pre-application, 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 tends to result in better color development and friction fastness.

[0163] 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.

[0164] 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.

[0165] 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.

[0166] 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.

[0167] 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.

[0168] 3.1.2.2 Pre-emptive strike 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 in which the inkjet head is moved perpendicular to the transport direction of the fabric to perform recording, and the reaction solution and the ink composition may be attached to the same scanning area of ​​the fabric by different main scans.

[0169] 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.

[0170] Furthermore, in the pre-printing process, the ink composition and reaction solution are applied by different main scans. Therefore, the order is not restricted, but it is more preferable to apply the reaction solution first and then apply the ink composition on top of it.

[0171] 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.

[0172] 3.1.2.3 Other attachment methods The above alternating printing and pre-printing use a serial inkjet head, but may use a line inkjet head to perform the ink attachment step and the reaction liquid attachment step.

[0173] That is, in the recording method according to the present embodiment, the reaction liquid attachment step and the ink attachment step described later are performed by an inkjet method, and the inkjet method may use an inkjet head (line head) having a length equal to or greater than the recording width of the fabric, and scan the fabric to be conveyed once with the inkjet head.

[0174] In such a line recording method, the ink composition and the reaction liquid can be discharged and attached to the fabric while relatively moving the positions of the line head and the fabric in the scanning direction (the longitudinal direction of the fabric, the conveying direction) intersecting the width direction of the fabric.

[0175] 3.2 Reaction liquid attachment step The recording method according to the present embodiment has a reaction liquid attachment step of attaching the above-described reaction liquid for pigment resist printing to the fabric by an inkjet method.

[0176] The amount of the reaction liquid attached 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 still more preferably 15 - 18 mg / inch 2 particularly preferably 15 - 18 mg / inch.

[0177] 3.2.1 Process interval As described above, in the recording method according to the present embodiment, the time difference between the above-described ink attachment step and the reaction liquid attachment step is preferably within 5 seconds. The preferable time difference in the case of alternating printing or pre-printing of the reaction liquid is as described above, and the description is omitted.

[0178] 3.2.2 Attachment method As described above, the recording method according to this embodiment is preferably alternating, and may also involve pre-printing or using a line-type inkjet head to perform the ink application process and the reaction solution application process.

[0179] 3.3 Other processes The recording method according to this embodiment may include a step of heating the ink and the like attached to the fabric after the ink application step and reaction solution application 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 a 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. This is preferable. Here, the heating temperature in the heating process refers to the surface temperature of the image or the like formed on the fabric. The heating time is not particularly limited, but for example, it is 30 seconds or more and 20 minutes or less.

[0180] 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.

[0181] 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.

[0182] 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.

[0183] 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.

[0184] 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.

[0185] 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.

[0186] 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 length 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 is capable of reciprocating in the main scanning direction MS, which substantially coincides with the width direction of the fabric 2, and the inkjet head 3 is configured to scan the fabric 2 relative to the main scanning direction MS and the sub-scanning direction SS.

[0187] Liquid cartridges 7a, 7b, 7c, 7d, 7e, and 7f are six independent liquid cartridges. Liquid cartridges 7a, 7b, 7c, 7d, 7e, and 7f can contain the ink composition and reaction solution used in the recording method of this embodiment. These liquid cartridges individually contain 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 invention is not limited to this. No. 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 liquid cartridge to the inkjet head 3.

[0188] 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.

[0189] 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.

[0190] 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.

[0191] 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.

[0192] 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, it is preferable that the head that ejects the reaction solution is located at the same position as the head that ejects the ink composition in the fabric transport direction, or is located upstream of the head that ejects the ink composition in the fabric transport direction. With such a configuration, droplet adhesion becomes possible by alternating tapping or pre-tapping of the reaction solution, and the components of the ink composition and the reaction solution mix more easily and the reaction proceeds more smoothly, so the color development, friction fastness and suppression of bleeding tend to be superior.

[0193] For example, in the example shown in Figure 2, by using the inkjet head 3a as the head that ejects the reaction solution and the inkjet head 3b as the 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 in 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, and the reaction solution A layer containing [a certain substance] can be formed, and then a layer containing the ink composition can be laminated to form [another substance].

[0194] 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.

[0195] 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.

[0196] 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.

[0197] 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.

[0198] 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.

[0199] 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.

[0200] 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.

[0201] 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 and stirred with a magnetic stirrer for 2 hours. After further mixing, the mixture was dispersed in a bead mill filled with 0.3 mm diameter zirconia beads. After stirring for 1 hour, a 5 μm PTFE membrane filter was used. The pigment printing reaction solutions for each example and comparative example were obtained by filtering. The values ​​for cationic polymers in Tables 1-3 below represent the mass percentage of the solid content, which is the active ingredient.

[0202] [Table 1]

[0203] [Table 2]

[0204] [Table 3]

[0205] The following explanations will be provided regarding the descriptions in Tables 1-3 above. <Composition of reaction solution> [Cationic polymer] • Kymene 557 (product name of SOLENIS, epichlorohydrin-based resin) • Myriogen P-20 (product name manufactured by Senka Co., Ltd., quaternary salt of alkylamine epichlorohydrin adduct) • Unisense FPA 100L (Senka Co., Ltd. product name, quaternary salt of alkylamine-allylamine adduct) • Unisense KHE 107L (Senka Co., Ltd. product name, quaternary salt of alkylamine epichlorohydrin adduct) [Polyhydric alcohols] • 1,3-Butylene glycol (penetrating solvent) 〔others〕 • Orphine E1010 (product name manufactured by Nisshin Chemical Industry Co., Ltd., acetylene glycol-based surfactant) • EDTA-2Na (Ethylenediaminetetraacetate disodium salt) • Proxel XL2 (product name manufactured by Lonza Japan Co., Ltd.)

[0206] <term> "Boiling point": Indicates the standard boiling point. "bp230℃ or below / bp250℃ or above": Content of polyhydric alcohols with a standard boiling point of 230℃ or below / Content of polyhydric alcohols with a standard boiling point of 250℃ or above "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

[0207] Viscosity was measured using a viscoelasticity tester (Pysica, MCR-300). pH was measured using a benchtop pH meter (model number: F-72, manufacturer: HORIBA). The temperature for viscosity and pH measurements was 20°C.

[0208] 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.

[0209] 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.

[0210] [Table 4]

[0211] 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 (four times) on the same scanning area, a solid pattern image was formed on the A4-sized fabric recording medium. The printed materials for each example and comparative example were then prepared by heating and drying in an oven at 160°C for 3 minutes. The inkjet head used was a head unit with a nozzle distance of 600 dpi in the width direction of the recording medium and 600 nozzles. The nozzle group for the reaction solution and the nozzle group for the ink composition had parts located in the same position in the sub-scanning direction, and the head arrangement shown in Figure 3 was used. This ensured that the reaction solution and ink composition were adhered to the same scanning area of ​​the fabric by the same main scan. The time difference between ink adhesion and reaction solution adhesion was kept within 5 seconds. Furthermore, a "solid pattern image" refers to an image in which dots are recorded for all pixels of the smallest recording unit area defined by the recording resolution (Duty 100%).

[0212] 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

[0213] 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

[0214] 4.4.3 Smudging For the evaluation of bleeding, the same printed material used in the "Wet Friction Fastness" test described below was used. The unevenness of ink aggregation within the solid patterns of the printed material was observed visually and evaluated according to the evaluation criteria below. (Evaluation Criteria) A: No uneven aggregation was observed within the solid pattern. B: Some uneven aggregation was observed within the solid pattern. C: Significant unevenness in aggregation was observed throughout the solid pattern.

[0215] 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 wet friction fastness was evaluated according to the following criteria. A result of C or higher indicates good friction fastness. (Evaluation Criteria) A: Friction resistance of level 3 or higher B: Friction fastness is between grade 2 and 3 or higher, but less than grade 3. C: Friction fastness of grade 2 or higher, but less than grade 2-3. D: Friction fastness is less than grade 2.

[0216] 4.4.5 Pitting corrosion The inkjet heads were immersed in the pigment printing reaction solutions obtained above, and left to stand for two days at 60°C to check whether pitting corrosion occurred. Even in cases where pitting corrosion occurred, the printers remained usable. (Evaluation Criteria) Yes: Pittholes present None: No pitting.

[0217] 4.5 Evaluation Results The evaluation results are shown in Tables 1-3 above.

[0218] As shown in Tables 1-3 above, in each example using a pigment printing reaction solution containing a polyvalent metal salt, a cationic polymer, a polyhydric alcohol with a standard boiling point of 250°C or higher, and water, which is dispensed by an inkjet method, excellent color development, friction fastness, and intermittent printing stability were observed.

[0219] A comparison of Examples 4 and 17 with Comparative Examples 1 to 9 shows that using polyvalent metal salts in combination with cationic polymers resulted in improved friction fastness and color development.

[0220] A comparison of Example 4 and Comparative Example 10 shows that using an inkjet method to eject the reaction solution resulted in improved friction fastness and color development.

[0221] A comparison of Example 4 and Comparative Example 11 showed that including a polyhydric alcohol with a standard boiling point of 250°C or higher resulted in improved intermittent printing stability.

[0222] The results from Examples 1-6 show that polyvalent metal salts exhibited good color development, bleeding resistance, and wet friction fastness across a wide range of content.

[0223] The results from Examples 4 and 7 showed that pitting corrosion could be reduced by including an alkaline compound.

[0224] The results from Examples 4, 8-11 show that alkali compounds, across a wide range of content, were able to reduce pitting corrosion while maintaining good wet friction fastness.

[0225] The results from Examples 4, 8, 12, and 13 show that pitting corrosion could be reduced with various alkali compounds.

[0226] From the results of Examples 4 and 14, when the polyvalent metal salt is a magnesium salt, the wet friction fastness is Excellent.

[0227] The results from Examples 4, 15-21 showed that cationic polymers exhibited good intermittent printing stability and wet friction fastness across a wide content range.

[0228] The results from Examples 4 and 22-24 showed that various cationic polymers exhibited good wet friction fastness.

[0229] The results from Examples 4, 25-31 showed that when the ratio of polyhydric alcohols with a standard boiling point of 230°C or lower to polyhydric alcohols with a standard boiling point of 250°C or higher was within a predetermined range, good wet friction fastness and intermittent printing stability were achieved.

[0230] The results from Examples 4 and 32 showed that the inclusion of polyhydric alcohols with a standard boiling point of 230°C or lower resulted in better wet friction fastness.

[0231] The results from Examples 4 and 33-36 showed that polyhydric alcohols provided good intermittent printing stability, reduced bleeding, and excellent wet friction fastness over a wide range of content.

[0232] The following conclusions can be drawn from the embodiments described above.

[0233] One embodiment of a reaction solution for pigment printing is: Polyvalent metal salts, Cationic polymers and It contains polyhydric alcohols with a standard boiling point of 250°C or higher, and water. It is used by ejecting it using an inkjet method.

[0234] In one embodiment of the above-mentioned pigment printing reaction solution, The aforementioned cationic polymer may have a structure derived from an epihalohydrin.

[0235] In any aspect of the above-mentioned pigment printing reaction solution, The content of the cationic polymer may be 0.5 to 5.0% by mass relative to the total amount of the reaction solution.

[0236] In any aspect of the above reaction liquid for pigment printing, the polyvalent metal salt may be a magnesium salt.

[0237] In any aspect of the above reaction liquid for pigment printing, furthermore, it may contain a polyhydric alcohol having a standard boiling point of 230°C or lower.

[0238] In any aspect of the above reaction liquid for pigment printing, the content of the polyhydric alcohol having a standard boiling point of 250°C or higher may be 3% by mass or more based on the total amount of the reaction liquid.

[0239] In any aspect of the above reaction liquid for pigment printing, when the content of the polyhydric alcohol having a standard boiling point of 250°C or higher with respect to the total amount of the reaction liquid is M1, and the content of the polyhydric alcohol having a standard boiling point of 230°C or lower with respect to the total amount of the reaction liquid is M2, the content ratio (M2 / M1) may be 0.1 to 30.0.

[0240] In any aspect of the above reaction liquid for pigment printing, when the content of the polyhydric alcohol having a standard boiling point of 250°C or higher with respect to the total amount of the reaction liquid is M1, and the content of the cationic polymer with respect to the total amount of the reaction liquid is M3, the content ratio (M1 / M3) may be 0.5 to 50.0.

[0241] In any aspect of the above reaction liquid for pigment printing, when the content of the cationic polymer with respect to the total amount of the reaction liquid is M3, and the content of the polyvalent metal salt with respect to the total amount of the reaction liquid is M4, the content ratio (M3 / M4) may be 0.1 to 4.0.

[0242] In any aspect of the above reaction liquid for pigment printing, the viscosity of the reaction liquid for pigment printing may be 2 to 10 mPa·s.

[0243] In any aspect of the above reaction liquid for pigment printing, The pH of the aforementioned pigment printing reaction solution may be 4.5 or higher.

[0244] In any aspect of the above-mentioned pigment printing reaction solution, Furthermore, it contains an alkali compound, When the content of the alkali compound relative to the total amount of the reaction solution is M5 and the content of the cationic polymer relative to the total amount of the reaction solution is M3, the content ratio (M5 / M3) may be 0.1 to 1.0.

[0245] One form of an ink set is, A textile inkjet ink composition containing pigment, resin particles, and water, The present invention comprises a pigment printing reaction solution according to any of the above embodiments.

[0246] One method of recording 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 of any of the above embodiments to the fabric by an inkjet method.

[0247] In one embodiment of the above recording method, The time difference between the ink application step and the reaction solution application step may be 5 seconds or less.

[0248] In any embodiment of the above recording method, 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 same main scan may be performed multiple times on the same scanning area.

[0249] The present invention is not limited to the embodiments described above, and various modifications are possible. For example, the present invention includes configurations that are substantially identical to the configurations described in the embodiments, for example, configurations that have the same function, method and result, or configurations that have the same purpose and effect. The present invention also includes configurations in which non-essential parts of the configurations described in the embodiments are replaced. Furthermore, the present invention includes configurations that produce the same effects or achieve the same purpose as the configurations described in the embodiments. Furthermore, the present invention includes configurations that add known technology to the configurations described in the embodiments. [Explanation of symbols]

[0250] 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 Body cartridge, 8...Timing belt, 9...Motor, 10...Guide shaft

Claims

1. Polyvalent metal salts, Cationic polymers and It contains a polyhydric alcohol with a standard boiling point of 250°C or higher, a polyhydric alcohol with a standard boiling point of 230°C or lower, and water. The content of the aforementioned cationic polymer is 0.5 to 5.0% by mass relative to the total amount of the reaction solution. When M1 is the content of the 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 the cationic polymer relative to the total amount of the reaction solution, the content ratio (M1 / M3) is 0.5 to 50.

0. A reaction solution for pigment printing, which is dispensed by the inkjet method.

2. The reaction solution for pigment printing according to claim 1, wherein the cationic polymer has a structure derived from an epihalohydrin.

3. The pigment printing reaction solution according to claim 1 or claim 2, wherein the polyvalent metal salt is a magnesium salt.

4. The pigment printing reaction solution according to any one of claims 1 to 3, wherein the content of the polyhydric alcohol with a standard boiling point of 250°C or higher is 3% by mass or more relative to the total amount of the reaction solution.

5. The content of the polyhydric alcohol with a standard boiling point of 250°C or higher relative to the total amount of the reaction solution is M. １ The content of the polyhydric alcohol with a standard boiling point of 230°C or lower relative to the total amount of the reaction solution is M. ２ When this is the case, the content ratio (M ２ / M １ A pigment printing reaction solution according to any one of claims 1 to 4, wherein the ratio of ) is 0.1 to 30.

0.

6. The content of the aforementioned cationic polymer relative to the total amount of the reaction solution is M. ３ The content of the polyvalent metal salt relative to the total amount of the reaction solution is M. ４ When this is the case, the content ratio (M ３ / M ４ A pigment printing reaction solution according to any one of claims 1 to 5, wherein the ratio of ) is 0.1 to 4.

0.

7. The pigment printing reaction solution according to any one of claims 1 to 6, wherein the viscosity of the pigment printing reaction solution is 2 to 10 mPa·s.

8. The pigment printing reaction solution according to any one of claims 1 to 7, wherein the pH of the pigment printing reaction solution is 4.5 or higher.

9. Furthermore, it contains an alkali compound, Let M be the content with respect to the total amount of the reaction solution of the alkali compound. ５ Let M ３ be the content with respect to the total amount of the reaction solution of the cationic polymer. ３ When the content ratio (M ５ / M ３ ) is 0.1 to 1.0, the reaction solution for pigment printing according to any one of claims 1 to 8. ５ / ３ ​

10. A textile inkjet ink composition containing pigment, resin particles, and water, An ink set comprising a pigment printing reaction solution according to any one of claims 1 to 9.

11. 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 9 to the fabric by an inkjet method.

12. The recording method according to claim 11, wherein the time difference between the ink application step and the reaction solution application step is 5 seconds or less.

13. 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 11 or claim 12, wherein the same main scan is performed multiple times on the same scanning area.

Images