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

Abstract

The present application provides a pigment printing reaction liquid, ink set, and recording method for use in inkjet printing, which have excellent color development, rubbing fastness, and intermittent printing stability. The pigment printing reaction liquid according to one embodiment of the present application is a reaction liquid for use in inkjet printing, which contains a polyvalent metal salt, a cationic polymer, a polyol having a standard boiling point of 250°C or higher, and water.

Description

Technical Field

[0001] This invention relates to a reaction solution, ink group, and recording method for pigment printing and dyeing. Background Technology

[0002] Previously, it was known that when dyeing fabrics or other substrates with pigments using inkjet printing to produce printed materials, a reaction solution containing cationic compounds was used to pretreat the substrate in order to improve the color development of the pigments. Among these methods, the reaction solution sprayed by inkjet printing was studied in a recording method that uses a recording device to perform the pretreatment and ink adhesion steps.

[0003] For example, Patent Document 1 discloses a pretreatment liquid containing a polyvalent metal compound, which can be applied to a wet-on-wet recording method in printing and dyeing (pigment printing and dyeing) using an ink composition containing pigments, to perform the step from applying the pretreatment liquid to applying the ink without a drying step.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent No. 2016-089288 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] However, the pigment printing reaction solution used by inkjet printing has problems with color development, rubbing fastness and intermittent printing stability.

[0009] means for solving problems

[0010] One embodiment of the pigment dyeing reaction solution involved in this invention is a pigment dyeing reaction solution containing a polyvalent metal salt, a cationic polymer, a polyol with a standard boiling point of 250°C or higher, and water, and is used by inkjet printing.

[0011] One aspect of the ink group involved in this invention is an ink group having a printing and dyeing inkjet ink composition containing pigments, resin particles and water, and a pigment printing and dyeing reaction solution of the above-mentioned aspect.

[0012] One aspect of the recording method involved in this invention is a recording method comprising an ink adhesion step of adhering an ink composition to a fabric using an inkjet method and a reaction liquid adhesion step of adhering a pigment printing reaction liquid of the above-mentioned method to the fabric using an inkjet method. Attached Figure Description

[0013] Figure 1This is a perspective view of an inkjet printing apparatus applicable to the recording method described in this embodiment.

[0014] Figure 2 This is a schematic diagram illustrating an example of the configuration of the inkjet printhead in an inkjet printing apparatus.

[0015] Figure 3 This is a schematic diagram illustrating an example of the configuration of the inkjet printhead in an inkjet printing apparatus.

[0016] Figure 4 This is a schematic diagram illustrating an example of the configuration of the inkjet printhead in an inkjet printing apparatus.

[0017] Figure Labels

[0018] 1...Printer; 2...Cloth; 3 (3a, 3b)...Inkjet head; 4...Carriage; 5...Main scanning mechanism; 6...Paper pressure roller; 7a, 7b, 7c, 7d, 7e, 7f...Liquid ink cartridges; 8...Synchronous belt; 9...Motor; 10...Guide shaft Detailed Implementation

[0019] The 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 to any of the following embodiments, and includes various modifications implemented without changing the spirit of the invention. It should be noted that not all of the configurations described below are necessarily essential to the present invention.

[0020] 1. Reaction solution for pigment printing and dyeing

[0021] One embodiment of the present invention relates to a pigment printing and dyeing reaction solution containing a polyvalent metal salt, a cationic polymer, a polyol with a standard boiling point of 250°C or higher, and water, and is used by inkjet printing.

[0022] Previously, it was known that when dyeing fabrics or other substrates with pigments using inkjet printing to produce printed materials, a reaction solution containing cationic compounds was used to pretreat the substrate in order to improve the color development of the pigments. Furthermore, pretreatment in inkjet pigment printing is typically performed using other equipment via methods such as immersion. However, such methods not only require the use of other equipment, but the steps become complex or require proprietary technology due to the use of such equipment. In addition, the discharge of waste liquid is undesirable from an environmental impact perspective.

[0023] Therefore, research was conducted on using inkjet printing to spray not only the ink composition but also the reaction solution in inkjet pigment printing. This approach eliminates the need for additional devices / equipment, simplifies the process, and eliminates waste liquid discharge.

[0024] However, while reaction solutions containing only polyvalent metal salts can achieve good color development by causing ink agglomeration near the fabric surface, they also suffer from poor rubbing fastness (especially wet rubbing fastness) due to the ink remaining near the fabric surface. Therefore, this study found that by further containing cationic polymers in the reaction solution, the fabric can be given water resistance and good rubbing fastness (especially wet rubbing fastness). On the other hand, the presence of cationic polymers introduces a new problem: even trace amounts of water evaporating from the reaction solution can easily result in high viscosity, leading to poor ejection stability (intermittent printing stability) when using inkjet printing.

[0025] Therefore, the inventors conducted further in-depth research and found that by further containing polyols with a standard boiling point of 250°C or higher, good ejection stability (intermittent printing stability) can be achieved even when cationic polymers are present. That is, the pigment printing reaction solution according to this embodiment can achieve good color development, rubbing fastness, and intermittent printing stability.

[0026] 1.1 Application

[0027] The pigment printing reaction solution involved in this embodiment is a reaction solution that is sprayed out using an inkjet method.

[0028] "For use in printing and dyeing with pigments" refers to use, for example, in printing and dyeing processes using ink compositions containing pigments.

[0029] "Inkjet printing" refers to a recording method in which droplets of ink, reaction liquid, etc., are ejected from the nozzle of the inkjet head of an inkjet recording device and applied to a recording medium.

[0030] The pigment printing reaction solution described in this embodiment is a reaction solution sprayed using an inkjet method. Therefore, unlike conventional pretreatment, no other devices / equipment are required, simplifying the process and eliminating waste liquid discharge. Furthermore, by using an inkjet method to coat the reaction solution, compared to coating with a non-inkjet sprayer, even with a large coating amount, the image is less prone to bleeding. This is presumably because, when using an inkjet method, the spray volume can be controlled to be small, and the ink can be brought into immediate contact in a wet-on-wet manner, thus facilitating the reaction between the reaction solution and the ink. In contrast, when using a non-inkjet sprayer, it is difficult to control the spray volume to be small, and usually, due to the drying step, the ink and reaction solution do not come into immediate contact in a wet-on-wet manner, resulting in poor reaction between the reaction solution and the ink. That is, after the reaction solution is applied to the cloth in large quantities using a sprayer and dried, the ink will not immediately agglomerate due to the reaction solution itself penetrating into the cloth, the reaction between the dried components of the reaction solution and the ink being a solid / liquid reaction, or the low agglomeration effect of the cationic polymer ink, resulting in ink penetration or bleeding.

[0031] It should be noted that the reaction solution is not an ink composition used to color fabric, but rather an auxiliary liquid used in conjunction with the ink composition. Furthermore, the reaction solution is preferably capable of causing the components of the ink composition to agglomerate or thicken, more preferably a reaction solution containing components that cause the components of the ink composition to agglomerate or thicken. The reaction solution may contain pigments, and the pigment content is preferably 0.2% by mass or less relative to the total mass of the reaction solution, more preferably 0.1% by mass or less, further preferably 0.05% by mass or less, with a lower limit of 0% by mass. The reaction solution preferably does not contain pigments.

[0032] The following describes the components contained in the pigment dyeing reaction solution involved in this embodiment.

[0033] 1.2 Polyvalent Metal Salts

[0034] The pigment printing and dyeing reaction solution involved in this embodiment contains a polyvalent metal salt. The polyvalent metal salt exhibits excellent agglomeration effect on the components of the ink composition when in contact with it, causing the ink to agglomerate near the surface of the fabric, thus resulting in good color development.

[0035] Polyvalent metal salts are compounds composed of divalent or higher metal ions and anions. Examples of divalent or higher metal ions include ions of calcium, magnesium, copper, nickel, zinc, barium, aluminum, titanium, strontium, chromium, cobalt, and iron. Among these metal ions constituting polyvalent metal salts, at least one of calcium and magnesium ions is preferred from the perspective of excellent agglomeration properties of the ink composition. Furthermore, from the viewpoint of balancing agglomeration and rubbing adhesion, magnesium ions are more preferred.

[0036] The anions constituting polyvalent metal salts are either inorganic or organic ions. That is, in this specification, polyvalent metal salts refer to substances formed by inorganic or organic ions and polyvalent metals. Examples of such inorganic ions include chloride ions, bromide ions, iodide ions, nitrate ions, sulfate ions, and hydroxide ions. Examples of such organic ions include organic acid anions, such as carboxylate ions.

[0037] Magnesium salts are preferred among polyvalent metal salts. For example, when the polyvalent metal salt is a calcium salt, it exhibits excellent agglomeration properties, but on the other hand, the agglomeration reaction is difficult to control, sometimes resulting in poor rubbing fastness and a grainy texture on the fabric. In contrast, compared to other salts such as calcium salts, magnesium salts exhibit a milder agglomeration reaction with inks, making the reaction easier to control. Therefore, it tends to produce good color development, as well as good rubbing fastness and a grainy texture. It should be noted that the counter ion of the polyvalent metal can be any of inorganic acid anions or organic acid anions.

[0038] Specific examples of polyvalent metal salts are not particularly limited, but can include: calcium carbonate (such as heavy calcium carbonate and light calcium carbonate), calcium nitrate, calcium chloride, calcium sulfate, magnesium sulfate, calcium hydroxide, magnesium chloride, magnesium carbonate, barium sulfate, barium chloride, zinc carbonate, zinc sulfide, aluminum silicate, calcium silicate, magnesium silicate, copper nitrate, calcium acetate, magnesium acetate, aluminum acetate, etc. These polyvalent metal salts can be used alone or in combination with two or more. Among them, considering the ability to produce good color development, good rubbing fastness, and good granular texture, one or more of magnesium chloride, magnesium sulfate, magnesium carbonate, magnesium silicate, and magnesium acetate are preferred. It should be noted that these metal salts may be in the form of hydrated water in the raw material.

[0039] The lower limit of the polyvalent metal salt content relative to the total mass of the reaction solution is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, further preferably 1.5% by mass or more, particularly preferably 2.0% by mass or more, and even more preferably 2.5% by mass or more. Furthermore, the upper limit of the polyvalent metal salt content relative to the total mass of the reaction solution is preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 6% by mass or less, even more preferably 5% by mass or less, particularly preferably 4% by mass or less, and even more preferably 3.5% by mass or less. When the polyvalent metal salt content is within the above range, it tends to achieve a good balance between color development and rubbing fastness.

[0040] 1.3 Cationic polymers

[0041] The pigment dyeing reaction solution according to this embodiment contains a cationic polymer. By containing a cationic polymer in the reaction solution, water resistance can be imparted to the fabric, and good rubbing fastness (especially wet rubbing fastness) can be achieved.

[0042] Cationic polymers are polymers that possess cationic properties. Examples of cationic polymers include cationic urethane resins, cationic olefin resins, and cationic amine resins. Among these, cationic amine resins are preferred.

[0043] 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 (trade name, manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.); SUPERFLEX 600, 610, 620, 630, 640, 650 (trade name, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.); Urethane Emulsion WBR-2120C, WBR-2122C (trade name, manufactured by Taisei Fine Chemicals Co., Ltd.), etc.

[0044] Cationic olefin resins are resins containing olefins such as ethylene and propylene in their structural backbone, and known substances can be appropriately selected. Furthermore, cationic olefin resins can be in an emulsion state dispersed in a solvent containing water, organic solvents, etc. Commercially available products can be used as cationic olefin resins, such as ARROWBASECB-1200 and CD-1200 (trade name, manufactured by UNITIKA Co., Ltd.).

[0045] As cationic amine resins, known substances can be appropriately selected, but it is preferable that the structure has cationic functional groups selected from primary amine, secondary amine, tertiary amine, quaternary ammonium salt, imine, and amide groups, and it is particularly preferable that the structure has quaternary ammonium salt groups as cationic functional groups. When it is a cationic amine resin, it tends to have better color development. In addition, the cationic amine resin can be an amine resin having two or more of the above-mentioned cationic functional groups.

[0046] Examples of amine resins with cationic properties of primary amino groups include: polyallylamine, polyallylamine hydrochloride, polyallylamine aminosulfonate, methoxycarbonylated allylamine polymer, methylcarbonylated allylamine acetate polymer, ureylated polyallylamine polymer, carboxymethylated polyallylamine polymer, and hexamethylenediamine / epoxychloropropane resin, etc.

[0047] Commercially available amine resins with cationic properties of primary amine groups can also be used, 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 Nittobo Medical); UNISENCE KHE103L (manufactured by SENKA), etc.

[0048] As cationic amine resins with secondary amino groups, diallylamine polymers, diallylamine hydrochloride polymers, diallylamine hydrochloride-sulfur dioxide copolymers, diallylamine acetate-sulfur dioxide copolymers, diallylamine hydrochloride-acrylamide copolymers, dimethylamine / epoxychloropropane resins, dimethylamine / ammonia / epoxychloropropane resins, and dimethylamine-ethylenediamine-epoxychloropropane polymers, etc.

[0049] Cationic amine resins with secondary amino groups can also be commercially available, such as: PAS-21, PAS-21CL, PAS-92, PAS-92A, PAS-2141CL (manufactured by Nittobo Medical); UNISENCE KHE104L, UNISENCE KHE100L (manufactured by SENKA); Catiomaster PE-30 (manufactured by Yokkaichi Synthetic Co., Ltd.), etc.

[0050] Examples of amine resins with cationic tertiary amino groups include: methyl diallylamine hydrochloride polymers, methyl diallylamine aminosulfonate polymers, methyl diallylamine acetate polymers, methyl diallylamine hydrochloride-sulfur dioxide copolymers, and dicyandiamide-polyalkylene polyamine condensates.

[0051] Commercially available amine resins with tertiary amine groups can also be used, such as: PAS-M-1L, PAS-M-1; PAS-22SA-40; PAS-M-1A; PAS-2201CL (manufactured by Nittobo Medical); UNISENCEKHP10L (manufactured by SENKA), etc.

[0052] In addition, commercially available amine resins with cationic properties of primary, secondary, or tertiary amino groups include: Supramine C-305 (manufactured by Toho Chemical 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, DK6854 (manufactured by Hoshikatsu PMC Co., Ltd.), etc.

[0053] Examples of cationic amine resins with quaternary ammonium salt groups include: diallyl dimethyl ammonium chloride polymer, diallyl methyl ethyl ethanesulfonate ammonium polymer, diallyl methyl ethyl ethanesulfonate ammonium-sulfur dioxide copolymer, diallyl dimethyl ammonium chloride-sulfur dioxide copolymer, and diallyl dimethyl ammonium chloride-acrylamide copolymer.

[0054] Cationic amine resins with quaternary ammonium groups can also be used commercially available products, 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 Nittobo Medical); EP-1137 (manufactured by Takamatsu Oils & Fats); PAPYOGEN P-105, MILLIOGEN P-20, UNISENCE FPA100L, UNISENCE KHE107L (manufactured by SENKA), etc.

[0055] Examples of amine resins with cationic imino groups include: polyethyleneimine, octadecyl isocyanate-modified polyethyleneimine, and propylene oxide-modified polyethyleneimine.

[0056] Commercially available amine resins with imino cationic properties can also be used, 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.); Lupasol (manufactured by BASF Co., Ltd.), etc.

[0057] Examples of cationic amine resins with amide groups include polyamides and polyamide epoxy resins. Commercially available examples of cationic amine resins with amide groups include Sumirez Resin 633, 630(30), 675A, 6615, 6725, and SLX-1 (manufactured by Taoka Chemical Co., Ltd.).

[0058] In addition, the following substances are examples of cationic amine resins having two or more cationic functional groups.

[0059] Examples of amine resins containing cationic primary and secondary amino groups include allylamine-diallylamine copolymers and allylamine acetate-diallylamine acetate copolymers. Commercially available examples include PAA-D11 and PAA-D19A (manufactured by Nittobo Medical).

[0060] Examples of cationic amine resins containing primary amino and quaternary ammonium groups include allylamine-diallyldimethylammonium chloride copolymer, and commercially available examples include PAA-1123 (manufactured by Nittobo Medical).

[0061] Examples of cationic amine resins containing tertiary amino and quaternary ammonium groups include: methyl diallylamine-diallyldimethylammonium chloride copolymer and diallyldimethylammonium chloride-3-chloro-2-hydroxypropylated diallylamine hydrochloride copolymer. Commercially available examples include: PAA-2223 and PAS-880 (manufactured by Nittobo Medical).

[0062] Cationic polymers can be used alone or in combination of two or more.

[0063] Furthermore, the cationic polymer preferably has a structure derived from epoxy halides. Epoxy halides are monomers having epoxy groups and halogen groups. Examples of halogen groups include fluorine, chloro, bromine, iodo, and astatine groups. Epichlorohydrin, where the halogen group is chloro, is more preferably an epichlorohydrin. When the cationic polymer has a structure derived from epoxy halides, the unreacted epoxy groups and the like in the epoxy halides can act as crosslinking groups, facilitating the crosslinking reaction. That is, this tends to make the ink thicker and aggregate more easily, further improving color development, and making the ink layer stronger through crosslinking, thus achieving better rubbing fastness. In addition, when the fabric is cotton or the like, the crosslinking reaction between the crosslinking groups derived from epoxy halides and the hydroxyl groups of the cellulose in the cotton fabric tends to further improve the adhesion between the fabric and the ink layer, resulting in better rubbing fastness.

[0064] The cationic polymer having a structure derived from epoxy halides is more preferably a cationic amine resin having a structure derived from epoxy halides. Examples of such polymers include polyamine-epoxy halides copolymers, polyamide-epoxy halides copolymers, polyamide-polyamine-epoxy halides copolymers, and amine-epoxy halides copolymers.

[0065] Cationic polymers with structures derived from epichlorohydrin can be commercially available, including: Kymene 557 (manufactured by SOLENIS); MILLIOGEN P-20, UNISENCE KHE107L (manufactured by SENKA); WS-4020, 4030, 4027, TS-4070 (manufactured by Starlight PMC, polyamide-epoxychloropropane polymer); WS-4011 (manufactured by Starlight PMC, polyamine-epoxychloropropane polymer); AF-100, 251S, 255, 255LOX, 2500 (manufactured by Arakawa Industrial Chemicals, polyamide-polyamine-epoxychloropropane polymer); Catiomaster PE-30 (manufactured by Yokkaichi Synthetic Co., Ltd., dimethylamine-ethylenediamine-epoxychloropropane condensate); EPA-SK01 (manufactured by Yokkaichi Synthetic Co., Ltd., polyamide-polyamine-epoxychloropropane condensate), etc.

[0066] 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 even more particularly preferably 20,000 or less. There is no particular limitation on the lower limit of the mass-average molecular weight of the cationic polymer, but it 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, it tends to have better spray performance when coating the reaction solution using an inkjet printer. It should be noted that the mass-average molecular weight can be determined using gel permeation chromatography (GPC) with polyethylene glycol as the standard polymer.

[0067] The content of the cationic polymer relative to the total amount of the reaction solution 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. When the content of the cationic polymer is 0.5% by mass or more, good friction fastness can be achieved. On the other hand, when the content of the cationic polymer is 5.0% by mass or less, the viscosity of the reaction solution is easily made suitable for inkjet printing, and good stability of intermittent printing can be achieved.

[0068] 1,4-Polyols

[0069] Polyols are substances having one or more hydroxyl groups in their molecules, preferably having two or more hydroxyl groups, and more preferably having three or more hydroxyl groups. Examples of polyols include alcohols, alkyl glycols, polyols, and alkylene glycol monoalkyl ethers. Among these, polyols are preferably selected from one or more of polyols and alkylene glycol monoalkyl ethers, and more preferably polyols. It should be noted that polyols can be in a liquid or solid state at room temperature and pressure, but are preferably liquids.

[0070] Examples of alcohols include compounds in which one hydrogen atom of an alkane is replaced by a hydroxyl group. Alkanes can be straight-chain or branched. Examples of alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert-butanol, isobutanol, n-pentanol, 2-pentanol, 3-pentanol, and tert-pentanol.

[0071] Examples of alkyldiols include compounds in which alkanes are substituted with two hydroxyl groups. Examples of alkyldiols include: ethylene glycol (also known as ethane-1,2-diol), 1,2-propanediol (also known as propane-1,2-diol), 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, 1,3-propanediol, 1,3-butanediol (also known as 1,3-butanediol), 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, and 1,5-pentanediol. 2,4-Pentanediol, 2-Methyl-1,3-propanediol, 3-Methyl-1,3-Butanediol, 3-Methyl-1,5-Pentanediol, 2-Ethyl-1,3-Hexanediol, 2-Methyl-1,3-Pentanediol, 3-Methyl-1,5-Pentanediol, 2-Methylpentane-2,4-diol, 1,6-Hexanediol, 2-Ethyl-2-Methyl-1,3-propanediol, 2-Methyl-2-propyl-1,3-propanediol, etc.

[0072] Examples of polyols include condensates formed by the intermolecular condensation of two or more alkyl diols with hydroxyl groups, and compounds having three or more hydroxyl groups.

[0073] Examples of condensates obtained by intermolecular condensation of two or more alkyl glycol molecules through hydroxyl groups include: dialkylene glycols such as diethylene glycol and dipropylene glycol; trialkylene glycols such as triethylene glycol (standard boiling point 287°C) and tripropylene glycol.

[0074] 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: glycerol (standard boiling point 290°C), trimethylolethane, trimethylolpropane, 1,2,5-hexanetriol, 1,2,6-hexanetriol, pentaerythritol, polyoxypropylene triol, etc.

[0075] 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, tripropylene glycol monobutyl ether, etc.

[0076] 1.4.1 Polyols with a standard boiling point above 250℃

[0077] The pigment dyeing reaction solution according to this embodiment contains a polyol with a standard boiling point of 250°C or higher. This results in good moisture retention of the reaction solution, and even when containing cationic polymers, good spray stability is maintained. Furthermore, from the viewpoint of suppressing VOCs (volatile organic compounds), a polyol with a standard boiling point of 250°C or higher is preferred.

[0078] Examples of polyols with a standard boiling point of 250°C or higher include triethylene glycol (standard boiling point 287°C), trimethylolpropane (standard boiling point 295°C), and glycerol (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 polyol with a standard boiling point of 250°C or higher is preferably selected from one or more of triethylene glycol, glycerol, and triethylene glycol monobutyl ether, and more preferably glycerol. In the case of the above compounds, the moisturizing properties become better, and there is a tendency for better intermittent printing stability. Furthermore, from the same perspective, for polyols 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.

[0079] The content of polyols with a standard boiling point of 250°C or higher is not particularly limited, but relative to the total amount of the reaction solution, it is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, further 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. There is no particular upper limit, but it is preferably 30% by mass or less, more preferably 25% by mass or less, further 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 polyols with a standard boiling point of 250°C or higher is within the above range, the balance between moisturizing and drying properties is excellent, and it tends to produce good intermittent printing stability and rubbing fastness.

[0080] 1.4.2 Polyols with a standard boiling point below 230℃

[0081] The pigment printing reaction solution described in this embodiment preferably further contains a polyol with a standard boiling point of 230°C or lower. Polyols with a standard boiling point of 250°C or higher have excellent moisturizing properties, making it difficult for the solvent to dry and leaving residue on the fabric. This can sometimes inhibit the reaction of cationic polymers, leading to poor rub fastness. To address this, further containing a polyol with a standard boiling point of 230°C or lower mitigates the above problem, improves the reactivity of the cationic polymer, and thus enables good rub fastness. It should be noted that when only a polyol with a standard boiling point of 230°C or lower is contained, the moisturizing properties are poor, and good intermittent printing stability cannot be obtained.

[0082] Polyols with a standard boiling point below 230°C, such as alkyldiols, include: ethylene glycol (standard boiling point 197°C), 1,2-propanediol (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), and 1,3-butanediol (standard boiling point 207°C). 1,4-Butanediol (standard boiling point 230℃), 2-ethyl-2-methyl-1,3-propanediol (standard boiling point 226℃), 2-methyl-1,3-propanediol (standard boiling point 214℃), 2,2-dimethyl-1,3-propanediol (standard boiling point 210℃), 3-methyl-1,3-butanediol (standard boiling point 203℃), 2-methylpentane-2,4-diol (standard boiling point 197℃), etc. Examples of alkylene glycol monoalkyl ethers with a standard boiling point below 230°C 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, polyols with a standard boiling point of 230°C or lower are preferably selected from one or more of 1,2-propanediol and 1,3-butanediol, more preferably 1,2-propanediol. With the above-mentioned compounds, there is a tendency to further reduce the inhibition of cationic polymer reactions and to achieve better friction fastness. Furthermore, from the same viewpoint, polyols with a standard boiling point of 230°C or lower preferably have a standard boiling point of 220°C or lower, more preferably 210°C or lower, even more preferably 200°C or lower, and particularly preferably 190°C or lower.

[0083] The content of polyols with a standard boiling point below 230°C is not particularly limited, but relative to the total amount of the reaction solution, it is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, further 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. There is no particular upper limit, but it is preferably 30% by mass or less, more preferably 25% by mass or less, further 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 polyols with a standard boiling point below 230°C is within the above range, the balance between moisturizing and drying properties is excellent, and it tends to produce good intermittent printing stability and rubbing fastness.

[0084] 1.5 content ratio

[0085] In the pigment printing reaction solution according to this embodiment, when the content of polyols with a standard boiling point of 250°C or higher relative to the total amount of the reaction solution is defined as M1, and the content of polyols with a standard boiling point of 230°C or lower relative to the total amount of the reaction solution is defined as M2, 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, further 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, further preferably 0.6 or more, and especially preferably 0.8 or more. When the content ratio (M2 / M1) is within the above range, the balance between moisturizing and drying properties is excellent, and it tends to have good intermittent printing stability and rubbing fastness.

[0086] In the pigment printing reaction solution according to this embodiment, when the content of polyols with a standard boiling point of 250°C or higher relative to the total amount of the reaction solution is defined as M1, and the content of cationic polymers relative to the total amount of the reaction solution is defined as M3, 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, further preferably 25 or less, even more preferably 20 or less, particularly preferably 15 or less, even more 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, further preferably 3 or more, even more preferably 4 or more, particularly preferably 5 or more, and even more preferably 6 or more. When the content ratio (M1 / M3) is within the above range, the cationic polymer exhibits an excellent balance between reactivity and moisture retention, tending to provide good intermittent printing stability and rubbing fastness.

[0087] 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 set as M3 and the content of the polyvalent metal salt relative to the total amount of the reaction solution is set as 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, further preferably 1.7 or less, even more preferably 1.4 or less, particularly preferably 1.1 or less, and even more 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, further preferably 0.4 or more, particularly preferably 0.5 or more, and even more preferably 0.6 or more. When the content ratio (M3 / M4) is within the above range, it is sometimes possible to achieve a good balance of color development, rubbing fastness, and intermittent printing stability.

[0088] 1.6 water

[0089] The pigment dyeing reaction solution described in this embodiment may contain water. Examples of water include pure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water; and water with reduced ionic impurities such as ultrapure water. In addition, when water that has been sterilized by ultraviolet irradiation or the addition of hydrogen peroxide is used, the growth of bacteria and fungi can be inhibited during long-term storage of the reaction solution.

[0090] The water content relative to the total amount of the reaction solution 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 even more particularly preferably 60% by mass or more. By keeping the water content within the above range, the viscosity of the reaction solution for pigment printing and dyeing can be kept low. Furthermore, the upper limit of the water content relative to the total amount of the reaction solution is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0091] 1.7 Organic solvents

[0092] The pigment dyeing reaction solution according to this embodiment may contain organic solvents other than the polyols 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 non-cyclic amides. Examples of non-cyclic amides include alkoxyalkylamides.

[0093] Examples of esters include: ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, methoxybutyl acetate, and other diol monoacetates; and ethylene glycol diacetates, diethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, ethylene glycol acetate propionate, ethylene glycol acetate butyrate, diethylene glycol acetate butyrate, diethylene glycol acetate propionate, diethylene glycol acetate butyrate, dipropylene glycol acetate propionate, propylene glycol acetate butyrate, dipropylene glycol acetate butyrate, dipropylene glycol acetate propionate, and other diol diesters.

[0094] 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, tripropylene glycol dimethyl ether, etc.

[0095] Examples of cyclic esters include: β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, β-butyrolactone, β-valerolactone, γ-valerolactone, β-caprolactone, γ-caprolactone, δ-caprolactone, β-heptanelactone, γ-heptanelactone, δ-heptanelactone, ε-heptanelactone, γ-octanelactone, δ-octanelactone, ε-octanelactone, δ-nonanolactone, ε-nonanolactone, ε-decanolactone, etc.; and compounds in which the hydrogen atom of the methylene group adjacent to their carboxyl group is replaced by an alkyl group having 1 to 4 carbon atoms.

[0096] 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-methyl... Ethylpropionamide, 3-n-propoxy-N,N-dimethylpropionamide, 3-n-propoxy-N,N-diethylpropionamide, 3-n-propoxy-N,N-methylethylpropionamide, 3-isopropoxy-N,N-dimethylpropionamide, 3-isopropoxy-N,N-diethylpropionamide, 3-isopropoxy-N,N-methylethylpropionamide, 3-tert-butoxy-N,N-dimethylpropionamide, 3-tert-butoxy-N,N-diethylpropionamide, 3-tert-butoxy-N,N-methylethylpropionamide, etc.

[0097] As cyclic amides, examples include lactams, such as 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, and other pyrrolidones.

[0098] Organic solvents can be used alone or in combination with two or more.

[0099] 1.8 Alkali compounds

[0100] The pigment printing reaction solution according to this embodiment may contain an alkaline compound. By containing an alkaline compound, the reaction solution can be easily adjusted to a preferred pH (described later). This tends to reduce inkjet head corrosion. Examples of alkaline compounds include inorganic and organic alkaline compounds.

[0101] Examples of inorganic alkali compounds include: hydroxides of alkali metals or alkaline earth metals, carbonates of alkali metals or alkaline earth metals, phosphates of alkali metals or alkaline earth metals, etc.

[0102] 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.

[0103] Examples of organic base compounds include: ammonia, aliphatic amines, aromatic amines, aliphatic ammonium compounds, aromatic ammonium compounds, heterocyclic compounds and their hydroxides, carbonates, phosphates, etc. Examples of organic base 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 their modified products.

[0104] When an alkaline compound is present, the upper limit of the alkaline compound content relative to the total amount of the reaction solution is preferably 5% by mass or less, more preferably 4% by mass or less, further preferably 3% by mass or less, particularly preferably 2% by mass or less, and even more preferably 1.5% by mass or less. Furthermore, the lower limit of the alkaline compound content relative to the total amount of the reaction solution is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, further preferably 0.5% by mass or more, particularly preferably 0.7% by mass or more, and even more preferably 0.9% by mass or more. When the alkaline compound content is below the above-mentioned upper limit, it can effectively reduce inkjet head corrosion, while also reducing the reactivity of cations, and tends to provide good friction fastness. Furthermore, when the alkaline compound content is above the above-mentioned lower limit, it tends to sufficiently reduce inkjet head corrosion.

[0105] In the pigment printing and dyeing reaction solution according to this embodiment, when the content of the alkali compound relative to the total amount of the reaction solution is set as M5 and the content of the cationic polymer relative to the total amount of the reaction solution is set as 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, further 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 further preferably 0.4 or more. When the content ratio (M5 / M3) is within the above range, it tends to achieve a good balance between friction resistance and inkjet head corrosion reduction.

[0106] 1.9 Surfactants

[0107] The pigment dyeing reaction solution according to this embodiment may contain a surfactant. There are no particular limitations on the surfactant; examples include acetylenic diol surfactants, fluorinated surfactants, and organosilicon surfactants. It is preferred to contain at least one of these, with acetylenic diol surfactants being more preferred.

[0108] As a type of acetylenic diol surfactant, there are no particular limitations. Examples include: Sufynol 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 trade names, manufactured by Air Products, Japan Co., Ltd.); OLFINE 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 trade names, manufactured by Nissin Chemical Industry Co., Ltd.); ACETYLENOL E00, E00P, E40, E100 (all trade names, manufactured by Kawaken Fine Chemicals Co., Ltd.).

[0109] There are no particular limitations on the type of organosilicon surfactant, but polysiloxane compounds are preferred. Furthermore, there are no particular limitations on the type of polysiloxane compound, but examples include polyether-modified organosilicon compounds. Commercially available examples of this polyether-modified organosiloxane include: BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-348 (trade names, manufactured by BYK Chemicals 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, and KF-6017 (trade names, manufactured by Shin-Etsu Chemical Industry Co., Ltd.).

[0110] As a fluorinated surfactant, fluorinated modified polymers are preferred. For example, BYK-340 (trade name, manufactured by BYK Chemicals Japan Co., Ltd.) can be cited.

[0111] When a surfactant is present, the surfactant content can be set to 0.1% by mass or more and 1.5% by mass or less relative to the total amount of the reaction solution, preferably 0.5% by mass or more and 1% by mass or less.

[0112] 1.10 Metal sealant

[0113] The pigment printing and dyeing reaction solution described in this embodiment may contain a metal blocking agent. The metal blocking agent is capable of removing specified ions from the reaction solution.

[0114] Examples of metal blocking agents include: EDTA, EDTA-2Na (disodium dihydrogen ethylenediaminetetraacetate), EDTA-3Na (trisodium monohydrogen ethylenediaminetetraacetate), EDTA-4Na (tetrasodium dihydrogen ethylenediaminetetraacetate), and EDTA-3K (tripotassium monohydrogen ethylenediaminetetraacetate), and other ethylenediaminetetraacetic acid and its salts; DTPA, DTPA-2Na (disodium diethylenetriaminepentaacetate), and DTPA-5Na (disodium diethylenetriaminepentaacetate). Diethylenetriaminepentaacetic acid (PTA) and its salts, including PTA-2Na (disodium PTA-2Na) and PTA-3Na (trisodium PTA-3Na); ethylenediamine-N,N'-disuccinic acid and its salts; 3-hydroxy-2,2'-iminodisuccinic acid and its salts; L-aspartic-N,N'-diacetic acid and its salts; and N-(2-hydroxyethyl)iminodiacetic acid and its salts.

[0115] In addition to acetic acid analogues, other metal blocking agents include: ethylenediaminetetramethylenesulfonic acid and its salts; ethylenediaminetetramethoxylic acid and its salts; ethylenediamine pyrophosphate and its salts; and ethylenediamine metaphosphate and its salts, etc.

[0116] Metal sealants can be used alone or in combination with two or more.

[0117] When a metal blocking agent is present, the content of the metal blocking agent relative to the total amount of the reaction solution 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.

[0118] 1.11 Antibacterial agent

[0119] The pigment dyeing reaction solution involved in this embodiment may contain an antibacterial agent. Examples of antibacterial agents include: sodium benzoate, sodium pentachlorophenolate, sodium 2-pyridinium-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), 4-chloro-3-methylphenol (Preventol CMK from Bayer, etc.), etc.

[0120] When an antimicrobial agent is present, the content of the antimicrobial agent relative to the total amount of the reaction solution can 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.

[0121] 1.12 Other ingredients

[0122] The pigment dyeing reaction solution described in this embodiment may also contain various additives such as softeners, solubilizers, viscosity modifiers, ultraviolet absorbers, antioxidants, and corrosion inhibitors as components other than those mentioned above.

[0123] 1.13 Manufacturing method and physical properties of reaction solution for pigment printing and dyeing

[0124] The pigment dyeing reaction solution according to this embodiment is obtained by mixing the above-mentioned components in any order and removing impurities by filtration or other methods as needed. As a method for mixing the components, it is preferable to use a method in which the materials are added sequentially to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and then stirred and mixed.

[0125] From the viewpoint of reliability when using inkjet printing, the surface tension of the pigment printing reaction solution according to this embodiment at 20°C is preferably 20–40 mN / m, more preferably 22–35 mN / m. Similarly, from the same viewpoint, the viscosity of the reaction solution at 20°C is preferably 2–10 mPa·s, more preferably 2.5–8 mPa·s, further preferably 3–6 mPa·s, and particularly preferably 3.5–5 mPa·s. It should be noted that, in order to adjust the surface tension and viscosity to the above ranges, the types of polyols or surfactants and their amounts with water can be appropriately adjusted.

[0126] It should be noted that surface tension can be measured using the Wilhelmie method. Surface tension can be measured using a surface tension meter such as the CBVP-7 manufactured by Kyowa Interface Science Co., Ltd. Furthermore, viscosity can be measured by adjusting the shear rate from 10 [s] at 20°C using a viscoelastic testing apparatus such as the MCR-300 manufactured by Pysica Co., Ltd. -1 Increased to 1000 [s] -1 And read the shear rate as 200 [s] -1 The viscosity was determined by measuring the viscosity at that time.

[0127] The pH of the pigment printing reaction solution according to this embodiment at 20°C is preferably 4.5 or higher, 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. The pigment printing reaction solution according to this embodiment contains cationic components, therefore the pH is prone to decrease, which can sometimes corrode the stainless steel of the inkjet head. Therefore, when the pH of the reaction solution is within the above-mentioned range, it tends to reduce inkjet head corrosion. It should be noted that adjusting the pH to the above-mentioned range is preferably done using the aforementioned alkaline compound.

[0128] 2. Ink group

[0129] One embodiment of the present invention relates to an ink group comprising a printing and dyeing inkjet ink composition containing pigments, resin particles and water, and the above-mentioned pigment printing and dyeing reaction solution.

[0130] According to the ink group involved in this embodiment, since it is an ink group having the above-mentioned pigment printing reaction solution, it can achieve good color development, rubbing fastness and intermittent printing stability.

[0131] It should be noted that, in this invention, the ink set refers to a package of ink and reaction solution that combines at least a printing and dyeing inkjet ink composition and a pigment printing and dyeing reaction solution. The printing and dyeing inkjet ink composition in the ink set may be a single type or two or more types. The same applies to the pigment printing and dyeing reaction solution in the ink set.

[0132] 2.1 Reaction solution for pigment printing and dyeing

[0133] The ink group involved in this embodiment is an ink group having the above-described pigment dyeing reaction solution. Regarding the pigment dyeing reaction solution, as described above, the explanation is omitted.

[0134] 2.2 Printing and Dyeing Inkjet Ink Composition

[0135] The ink group involved in this embodiment is an ink group having a printing and dyeing inkjet ink composition containing pigments, resin particles and water.

[0136] The following describes each component contained in the ink group of the printing and dyeing inkjet ink composition according to this embodiment. It should be noted that the printing and dyeing inkjet ink composition can be prepared independently of the aforementioned pigment printing and dyeing reaction solution.

[0137] Additionally, in the following description, "printing inkjet ink composition" will sometimes be referred to as "inkjet ink composition", "ink composition" or "ink".

[0138] 2.2.1 Pigments

[0139] The ink group according to this embodiment contains a printing and dyeing inkjet ink composition containing pigments. As pigments, such as inorganic pigments and organic pigments can be used. It should be noted that pigments are one type of colorant. Examples of colorants include pigments and dyes.

[0140] As inorganic pigments, there are no particular restrictions, and examples include: furnace black, lamp black, acetylene black, channel black and other carbon blacks; white inorganic oxides such as iron oxide, titanium oxide, zinc oxide, and silicon oxide.

[0141] Examples of carbon blacks include CI (Color Index Common Name) Pigment Black 1, 7, and 11. Commercially available carbon blacks are also available, 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; Monarch (registered trademark) 700, 800, 880, 900, 1000, 1100, 1300, and 1400; and Degussa's ColorBlack. FW1, FW2, FW2V, FW18, FW200, S150, S160, S170; Printex (registered trademark) 35, U, V, 140U; Special Black 6, 5, 4A, 4, etc.

[0142] Examples of organic pigments include: quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthraquinone pigments, anthraquinone pigments, indigoanthrone pigments, yellow anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments, violet ketone pigments, quinacridone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, isoindolinone pigments, azomethyl alkaloid pigments, or azo pigments, etc.

[0143] The following substances can be listed as specific examples of organic pigments.

[0144] Examples of cyan pigments include: CI Pigment Blue 1, 2, 3, 15:3, 15:4, 15:34, 16, 22, 60, etc.; CI Vat Blue 4, 60, etc., preferably a mixture of one or more of the group consisting of CI Pigment Blue 15:3, 15:4 and 60.

[0145] 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; CI Pigment Violet 19, etc., preferably including one or more mixtures selected from the group consisting of CI Pigment Red 122, 202 and 209, and CI Pigment Violet 19.

[0146] 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., and 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.

[0147] Other colors of pigment can also be used. Examples include orange pigment and green pigment.

[0148] Pigments can be used alone or in combination of two or more.

[0149] It should be noted that, in order to improve the dispersibility of pigments in ink compositions, it is preferable to perform surface treatment on the pigments or to add dispersants, etc.

[0150] Surface treatment of pigments refers to the process of directly or indirectly bonding functional groups such as carbonyl groups, carboxyl groups, aldehyde groups, hydroxyl groups, sulfonyl groups, ammonium groups, and their salts onto the surface of the pigment through physical or chemical treatment.

[0151] When a dispersant is incorporated into the ink composition, it is preferable to use a dispersant having both a hydrophobic portion (hydrophobic group) and a hydrophilic portion (hydrophilic group) in its molecular structure. Such a dispersant has the effect of adsorbing the hydrophobic portion onto the surface of the pigment particles and orienting the hydrophilic portion toward the aqueous medium side of the ink composition. Through this effect, it tends to contain the pigment more stably in the ink composition in the form of a dispersion.

[0152] There are no particular limitations on such dispersants, and examples include: acrylic resins; styrene-(meth)acrylic acid copolymers, styrene-(meth)acrylic acid-(meth)acrylate copolymers, and other styrene-acrylic acid resins; styrene-maleic acid resins; and their salts, aromatic sulfonates, and formaldehyde condensates, etc., and one or more of these substances can be used. It should be noted that commercially available products can also be used as dispersants.

[0153] Alternatively, methods that impart dispersibility by coating pigment particles with resins or similar materials can be used. Methods for coating pigment particles include acid precipitation, phase inversion emulsification, and microemulsion polymerization.

[0154] The pigment content can be appropriately adjusted according to the application. Relative to the total amount of the ink composition, the pigment content is preferably 0.1% by mass or more and 17.0% by mass or less, more preferably 0.2% by mass or more and 15.0% by mass or less, even more preferably 1.0% by mass or more and 10.0% by mass or less, and particularly preferably 2.0% by mass or more and 5.0% by mass or less. When the pigment content is within the above range, it tends to further improve the ejection performance when ejected using inkjet technology.

[0155] It should be noted that 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.

[0156] 2.2.2 Resin particles

[0157] The ink group involved in this embodiment has a printing and dyeing inkjet ink composition containing resin particles. Resin particles are particles containing resin, also referred to as "resin dispersion" or "resin emulsion".

[0158] Examples of resins include: polyurethane resins, polycarbonate resins, (meth)acrylic resins, styrene resins, silicone resins, styrene-acrylic resins, fluorene resins, polyolefin resins, rosin-modified resins, terpene resins, polyester resins, polyamide resins, epoxy resins, vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, and ethylene-vinyl acetate resins. These resins can be used alone or in combination of two or more.

[0159] Among these, the resin particles are preferably polyurethane resin, polycarbonate resin, (meth)acrylic resin, or styrene resin, more preferably polyurethane resin and (meth)acrylic resin, and even more preferably polyurethane resin. In particular, by using polyurethane resin as the resin particles, the cationic polymer contained in the aforementioned reaction solution can react with the polyurethane resin, sometimes resulting in improved color development, rubbing fastness, and bleeding properties.

[0160] Polyurethane resin is a resin containing urethane bonds within its molecule. From the viewpoint of ink preservation stability, polyurethane resin is preferably anionic polyurethane resin having anionic functional groups such as carboxyl, sulfonyl, and hydroxyl groups.

[0161] Examples of polyurethane resins include: polyether-type polyurethane resins containing ether bonds in the main chain (in addition to urethane bonds), polyester-type polyurethane resins containing ester bonds in the main chain, and polycarbonate-type polyurethane resins containing carbonate bonds in the main chain. These polyurethane resins can be used in various combinations.

[0162] Commercially available polyurethane resins include: ETERNACOLL UW-1501F, UW-1527F, UW-5002 (manufactured by Ube Industries, Inc., trade name); TAKELAC WS-5000, W-6061, W-6110, WS-5984, WS-5100 (manufactured by Mitsui Chemicals, Inc., trade name); PERMARIN UA-150, UA-200; UCOAT UX-390 (manufactured by Sanyo Chemical Industries, Inc., trade name); HYDRAN WLS-210 (manufactured by DIC Corporation, trade name).

[0163] Polycarbonate resin refers to resins that have polycarbonate bonds within their molecules. When polyurethane resin is not used, polycarbonate resin is preferred as a substitute.

[0164] Commercially available (meth)acrylic resins include: Mowinyl 966A and 6760 (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name), which are acrylic resins.

[0165] (Meth)acrylic resins refer to resins having a (meth)acrylic backbone. There are no particular limitations on the definition of (meth)acrylic resins; examples include polymers of (meth)acrylic acid, (meth)acrylates, and other (meth)acrylic acid monomers; and copolymers of (meth)acrylic acid monomers with other monomers. Examples of other monomers include vinyl monomers such as styrene. It should be noted that in this specification, "(meth)acrylic acid" encompasses both "methacrylic acid" and "acrylic acid."

[0166] Commercially available silicone resins include: POLON-MF014, POLON-MF-18T, POLON-MF-33, and KM-2002-T (manufactured by Shin-Etsu Silicone Co., Ltd., trade names); WACKER FINISH WR1100, NP2406, POWERSOFT FE 55, and TS2406 (manufactured by Asahi Kasei Corporation, trade names).

[0167] There is no particular limitation on the acid value of the resin contained in the resin particles, but it is preferably 1 to 300 mg / g of KOH, more preferably 10 to 200 mg / g of KOH, and even more preferably 20 to 100 mg / g of KOH.

[0168] The content of resin particles relative to the total amount of the ink composition 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. With the content of resin particles within the above range, it is likely to obtain a recording material with excellent color development and excellent rubbing fastness.

[0169] 2.2.3 Water

[0170] The ink group according to this embodiment contains a printing and dyeing inkjet ink composition containing water. The same water as that contained in the aforementioned pigment printing and dyeing reaction solution can be used, and the content can also be the same.

[0171] 2.2.4 Polyols with a standard boiling point above 250℃

[0172] The ink group according to this embodiment may contain a polyol with a standard boiling point of 250°C or higher. The type and content of such polyols with a standard boiling point of 250°C or higher can be the same as those in the aforementioned pigment printing reaction solution. Furthermore, it may contain polyols and organic solvents with a standard boiling point of 230°C or lower, similar to those in the aforementioned pigment printing reaction solution.

[0173] 2.2.5 Surfactants

[0174] The ink composition of the ink group involved in this embodiment may contain a surfactant. As such a surfactant, the same surfactant that may be contained in the aforementioned pigment printing and dyeing reaction solution can be used, and the content can also be the same.

[0175] 2.2.6 pH adjuster

[0176] The ink group according to this embodiment may contain a pH adjuster in its inkjet ink composition. There are no particular limitations on the pH adjuster; suitable combinations of acids, bases, weak acids, and weak bases can be listed. 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, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium carbonate, sodium carbonate, sodium bicarbonate, ammonia, etc.; as organic bases, triethanolamine, diethanolamine, monoethanolamine, tripropanolamine, triisopropanolamine, diisopropanolamine, tris(hydroxymethyl)aminomethane (THAM), etc.; and as organic acids, adipic acid, citric acid, succinic acid, lactic acid, N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES), 4- Good's buffer, phosphate buffer, citrate buffer, Tris buffer, etc. contain (2-hydroxyethyl)-1-piperazine ethanesulfonic acid (HEPES), morpholine ethanesulfonic acid (MES), carbamoyl methyl iminodiacetic acid (ADA), piperazine-1,4-bis(2-ethanesulfonic acid) (PIPES), N-(2-acetamido)-2-aminoethanesulfonic acid (ACES), ethanolamine hydrochloride, N-tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid (TES), acetamyl glycine, tris(hydroxymethyl)methylglycine, glycine amide, N,N-di(hydroxyethyl)glycine, etc.

[0177] The ink composition may use a single pH adjuster or two or more in combination. Furthermore, when using a pH adjuster, the total content of the pH adjuster 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, more preferably 0.1% by mass or more and 1.0% by mass or less.

[0178] 2.2.7 Other components

[0179] The ink group involved in this embodiment may also contain various additives such as lubricants, softeners, cosolvents, viscosity modifiers, antioxidants, antibacterial agents such as Proxel XL2 (manufactured by Arch Chemicals, trade name), corrosion inhibitors, and metal blocking agents (such as sodium ethylenediaminetetraacetate) for capturing metal ions that affect dispersion as components other than those mentioned above.

[0180] 2.2.8 Manufacturing and physical properties of ink compositions

[0181] The ink group according to this embodiment contains a printing and dyeing inkjet ink composition obtained by mixing the above-mentioned components in any order and removing impurities by filtration or other methods as needed. As a method for mixing the components, it is preferable to use a method of sequentially adding the materials to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stirring and mixing them.

[0182] From the viewpoint of reliability when using inkjet printing, the surface tension of the ink composition of the printing inkjet ink group according to this embodiment at 20°C is preferably 20 to 40 mN / m, more preferably 22 to 35 mN / m. Furthermore, 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 adjust the surface tension and viscosity to the above ranges, the types of organic solvents and surfactants, as well as the amounts of water added, can be appropriately adjusted.

[0183] 3. Recording Method

[0184] One embodiment of the present invention relates to a recording method comprising an ink adhesion step of adhering an ink composition to a fabric using an inkjet method and a reaction liquid adhesion step of adhering the aforementioned pigment printing and dyeing reaction liquid to the fabric using an inkjet method.

[0185] According to the recording method of this embodiment, since there is a reaction liquid adhesion step that allows the above-mentioned pigment printing reaction liquid to adhere, the color development, rubbing fastness and intermittent printing stability are good.

[0186] The recording method described in this embodiment is applied to a fabric. There are no particular limitations on the materials constituting the fabric; examples include natural fibers such as cotton, linen, wool, and silk; synthetic fibers such as polypropylene, polyester, acetate fiber, triacetate fiber, polyamide, and polyurethane; biodegradable fibers such as polylactic acid; and blends of these materials.

[0187] The fabric is preferably a hydroxyl-containing fabric. Examples of such fabrics include cellulose-containing fabrics such as cotton and linen, or fabrics containing polyurethane. When the fabric is a hydroxyl-containing fabric, a cross-linking reaction can occur between the cationic polymer contained in the aforementioned reaction solution and the hydroxyl groups of the fabric, sometimes resulting in improved color development due to thickening and aggregation, and improved rubbing fastness due to improved adhesion between the fabric and the ink.

[0188] The fabric can be any type of fabric made from the aforementioned fibers, such as woven fabric, braided fabric, or nonwoven fabric. Furthermore, there are no particular limitations on the basis weight of the fabric used in this embodiment; it can be 1.0 oz or more and 10.0 oz or less, preferably 2.0 oz or more and 9.0 oz or less, more preferably 3.0 oz or more and 8.0 oz or less, and even more preferably 4.0 oz or more and 7.0 oz or less. If the basis weight of the fabric is within this range, good recording is possible. Moreover, the recording method described in this embodiment is applicable to various fabrics with different basis weights and allows for good printing and dyeing.

[0189] In this embodiment, examples of "fabric" include: cloth, clothing, or other apparel items. Cloth includes textiles, woven fabrics, non-woven fabrics, etc. Clothing or other apparel items include: sewn T-shirts, handkerchiefs, scarves, towels, tote bags, cloth bags, curtains, bed sheets, bedspreads, wallpaper, and other household items; as well as fabric before and after cutting, which are components before sewing. Examples of their forms include: long forms rolled into a roll, forms cut into a specified size, and forms in the shape of a finished product.

[0190] As the fabric, cotton fabric that has been pre-dyed with dyes can also be used. Examples of dyes used for pre-dyeing the fabric include water-soluble dyes such as acid dyes and basic dyes; disperse dyes with dispersants; and reactive dyes. When using cotton fabric, it is preferable to use reactive dyes that are suitable for dyeing cotton fabric.

[0191] The following describes each step of the recording method described in this embodiment.

[0192] 3.1 Ink Adhesion Steps

[0193] The recording method involved in this embodiment is a method having an ink adhesion step that uses inkjet technology to adhere an ink composition to a cloth.

[0194] The above-described inkjet ink composition is preferred as an ink composition.

[0195] It should be noted that inkjet printing refers to a recording method in which droplets of ink or the like are ejected from the nozzles of an inkjet printing head and applied to a recording medium.

[0196] The preferred amount of ink composition adhering to each unit area of ​​the recording area of ​​the cloth is 10–21 mg / inch. 2 More preferably 12–20 mg / inch 2 More preferably 14–19 mg / inch 2 The preferred concentration is 15–18 mg / inch. 2 .

[0197] 3.1.1 Step Interval

[0198] In the recording method of this embodiment, the time difference between the ink adhesion step and the reaction liquid adhesion step (described later) is preferably within 5 seconds. When the ink adhesion step and the reaction liquid adhesion step are performed with such a time difference, a wet-on-wet method can be achieved where the second droplet is adhered before the first droplet dries. It should be noted that when the first droplet is an ink composition, the second droplet is a reaction liquid; conversely, when the first droplet is a reaction liquid, the second droplet is an ink composition. While the wet-on-wet method has advantages in terms of device miniaturization and high speed, it also suffers from problems such as bleeding, poor color development, and reduced rubbing fastness. However, according to the recording method of this embodiment, even with this wet-on-wet method, color development and rubbing fastness are excellent, and bleeding is suppressed. Furthermore, in the recording method of this embodiment, when the time difference between the above steps is within 5 seconds, the reaction between the ink and the reaction liquid is easier to occur, tending to result in even better color development and rubbing fastness.

[0199] In this invention, the time difference between the ink adhesion step and the reaction liquid adhesion step refers to the time difference from the last spraying of the reaction liquid to the initial spraying of the ink composition.

[0200] Furthermore, in the following description, "alternating spraying" refers to applying the ink composition and reaction liquid to the same scanning area of ​​the fabric using the same main scan (moving the inkjet head in a direction perpendicular to the fabric's transport direction), forming a layer containing both the ink composition and the reaction liquid. "First spraying" refers to applying the ink composition and reaction liquid to the same scanning area of ​​the fabric using different main scans, layering a layer containing the reaction liquid and a layer containing the ink composition. In particular, the case where the layer containing the reaction liquid is formed first, followed by the layer containing the ink composition, is called "reaction liquid first spraying."

[0201] In the case of alternating spraying, the time difference between the ink adhesion step and the reaction solution adhesion step 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. There is no particular limitation on the lower limit, but it is preferably 0.1 seconds or more, more preferably 0.2 seconds or more. In the case of alternating spraying, the time difference between the ink adhesion step and the reaction solution adhesion step is particularly preferably 0.3 seconds. With such a time difference, the reaction between the ink and the reaction solution is easier to occur, tending to result in better color development and rubbing fastness.

[0202] When the reaction liquid is sprayed first, the time difference between the ink adhesion step and the reaction liquid adhesion step 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. There is no particular limitation on the lower limit, but it 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. When the reaction liquid is sprayed first, the time difference between the ink adhesion step and the reaction liquid adhesion step is particularly preferably 4.5 seconds. With such a time difference, the reaction between the ink and the reaction liquid is easier to carry out, tending to result in better color development and rubbing fastness.

[0203] 3.1.2 Adhesion Method

[0204] 3.1.2.1 Alternating spray

[0205] In the recording method of this embodiment, the reaction liquid adhesion step and the ink adhesion step described later are performed using an inkjet method. The inkjet method is preferably a method of performing multiple main scans by moving the inkjet head in a direction perpendicular to the transport direction of the fabric, and adhering the reaction liquid and ink composition to the same scanning area of ​​the fabric through the same main scan, and performing the same main scan multiple times on the same scanning area.

[0206] This can be described as alternating spraying. That is, after a layer containing the ink composition and the reaction solution is adhered to a certain area of ​​the fabric through a certain main scan, another main scan is performed to overlap and adhere another layer containing the ink composition and the reaction solution. As a result, the reaction solution and the ink composition are alternately overlapped (like a layered cake), so the components are easier to mix, the reaction is easier to proceed, and there is a tendency for better color development, rubbing fastness, and inhibition of bleeding.

[0207] When the same master scan is performed multiple times on the same scanning area, the master scan that causes the ink composition and reaction solution to adhere passes through the same area multiple times. The more scans, the more times (multiple passes) the ink or reaction solution can adhere to the desired area, tending to further improve the image quality of the resulting record.

[0208] It should be noted that the number of times the inkjet head passes through an area when recording data in any given area is also called a "pass". For example, in the case of performing four main scans to adhere the ink composition and reaction solution to the same area, the number of passes is called 4 passes, etc. For example, in Figure 3When the length of one sub-scan in the sub-scanning direction SS is one-quarter of the length of the sub-scanning direction SS of the nozzle array, a rectangular scanning area extending in the main scanning direction MS and the length of one sub-scan in the sub-scanning direction SS is scanned four times. The number of scans in this case is referred to as the number of scans or the number of tracks, etc. The number of scans is 2 or more, preferably 3 or more, more preferably 4 or more. In addition, the number of scans is preferably 10 or less, more preferably 8 or less, further preferably 6 or less, and particularly preferably 4 or less. According to the recording method according to this embodiment, even if the number of scans is within the above range, it tends to have better color development, rubbing fastness, and suppression of bleeding.

[0209] Furthermore, in the aforementioned alternating spraying, a layer containing the reaction liquid can also be formed using a main scan different from the main scan used to form the layer containing the ink composition and the reaction liquid, thereby stacking the layers containing the ink composition and the reaction liquid. Thus, by forming the layer containing the reaction liquid, color development and rubbing fastness are sometimes superior. The formation of the layer containing the reaction liquid can be performed before or after the formation of the layer containing the ink composition and the reaction liquid, but it is preferable to perform it beforehand.

[0210] 3.1.2.2 Spray first

[0211] In the recording method of this embodiment, the reaction liquid adhesion step and the ink adhesion step described later are performed using an inkjet method. The inkjet method can be a method of performing multiple main scans by moving the inkjet head in a direction perpendicular to the transport direction of the fabric, and adhering the reaction liquid and ink composition to the same scan area of ​​the fabric through different main scans.

[0212] In this way, it can be recorded as a first spray, and a layer containing the reaction liquid and a layer containing the ink composition can be formed in layers. In the recording method according to this embodiment, even with such a first spray, good color development, rubbing fastness, and inhibition of bleeding are possible.

[0213] It should be noted that, in the initial spraying, if the ink composition and the reaction liquid are attached by different main scans, there is no restriction on their order, but it is more preferable to first attach the reaction liquid and then attach the ink composition on it, with the reaction liquid being sprayed first.

[0214] In the pre-jet process, multiple master scans can be performed on the same scanning area to allow the ink composition and reaction solution to adhere to the scanning area. For example, consider recording the reaction solution in 4 passes and then recording the ink composition in 4 passes. It should be noted that the number of passes in the pre-jet process can be set independently for the ink composition and the reaction solution.

[0215] 3.1.2.3 Other attachment methods

[0216] The above-mentioned alternating spraying and first spraying uses a serial inkjet head, but a row inkjet head can also be used for the ink adhesion step and the reaction liquid adhesion step.

[0217] That is, in the recording method according to this embodiment, the reaction liquid adhesion step and the ink adhesion step described later are performed by inkjet method, which can be a method of scanning the transported cloth once using an inkjet head (line head) with a length of more than the recording width of the cloth.

[0218] This line-based recording method allows the ink composition and reaction liquid to be sprayed and adhered to the cloth while the positions of the line head and the cloth are moved relative to each other in a scanning direction (the longitudinal direction of the cloth, the transport direction of the cloth) that intersects with the width direction of the cloth.

[0219] 3.2 Adhesion Steps of the Reaction Solution

[0220] The recording method involved in this embodiment is a method having a reaction liquid adhesion step of adhering the above-mentioned pigment printing and dyeing reaction liquid to the above-mentioned fabric using an inkjet method.

[0221] The preferred amount of reaction solution adhering to each unit area of ​​the recording area of ​​the cloth is 10–21 mg / inch. 2 More preferably 12–20 mg / inch 2 More preferably 14–19 mg / inch 2 The preferred concentration is 15–18 mg / inch. 2 .

[0222] 3.2.1 Step Interval

[0223] As described above, in the recording method of this embodiment, the time difference between the ink adhesion step and the reaction liquid adhesion step is preferably within 5 seconds. Regarding the preferred time difference in the case of alternating spraying with the reaction liquid sprayed first, as previously stated, further explanation is omitted.

[0224] 3.2.2 Adhesion Method

[0225] As described above, the recording method involved in this embodiment is preferably alternating spraying, but it can also be spraying first, followed by an ink adhesion step and a reaction liquid adhesion step using a line inkjet head.

[0226] 3.3 Other steps

[0227] The recording method described in this embodiment includes a step of heating the ink or the like adhered to the fabric after the ink adhesion step and the reaction solution adhesion step. There are no particular limitations on the heating method; examples include hot pressing, atmospheric pressure steam method, high pressure steam method, and heat fixation method. There are no particular limitations on the heat source; for example, an infrared lamp can be used. The heating temperature is preferably the temperature at which the resin particles of the ink fuse and the medium such as moisture evaporates. For example, it is preferably about 100°C or higher and about 200°C or lower, more preferably 170°C or lower, and even more preferably 160°C or lower. Here, the heating temperature in the heating step refers to the surface temperature of the image or the like formed on the fabric. There are no particular limitations on the heating time; for example, it is 30 seconds or more and 20 minutes or less.

[0228] After the heating step, the printed fabric can be washed and dried. During the washing process, hot soapy water or similar liquid can be used to rinse away ink and other components that are not fixed to the fabric, as a soaping treatment.

[0229] 3.4 Inkjet Printing Equipment

[0230] Reference Figure 1 An example of an inkjet printing apparatus with an inkjet head that can be applied to the recording method involved in this embodiment will be described.

[0231] It should be noted that the inkjet printing apparatus used in the following description is a serial printer that mounts a recording inkjet head on a carriage that moves in a predetermined direction, and moves the inkjet head along with the carriage to spray droplets onto the fabric. The inkjet printing apparatus applicable to the recording method described in this embodiment is not limited to a serial printer, but can also be a line printer. A line printer is a printer in which the inkjet head is formed to be wider than the width of the fabric, and sprays droplets onto the fabric without moving the inkjet head.

[0232] Inkjet printing and dyeing equipment is a device that uses an inkjet head, which ejects tiny droplets of ink composition or reaction liquid, to make the droplets fall onto the fabric for printing and dyeing. Figure 1 This is a perspective view of the inkjet printing apparatus used in the embodiment.

[0233] like Figure 1 As shown, in this embodiment, the printer 1 includes an inkjet head 3, a carriage 4, a main scanning mechanism 5, a paper pressure roller 6, and a control unit (not shown) that controls the overall operation of the printer 1. The carriage 4 carries the inkjet head 3 and is capable of detaching and attaching liquid ink cartridges 7a, 7b, 7c, 7d, 7e, and 7f that contain the ink composition and reaction liquid supplied to the inkjet head 3.

[0234] The main scanning mechanism 5 includes a timing belt 8 connected to the carriage 4, a motor 9 driving the timing belt 8, and a guide shaft 10. The guide shaft 10 serves as a support member for the carriage 4 and is mounted along the scanning direction of the carriage 4, i.e., the main scanning direction MS. The carriage 4 is driven by the motor 9 via the timing belt 8 and can reciprocate along the guide shaft 10. Thus, the main scanning mechanism 5 has the function of reciprocating the carriage 4 along the main scanning direction MS.

[0235] The pressure roller 6 has the function of transporting the fabric 2 to be printed along the secondary scanning direction SS, which is orthogonal to the main scanning direction MS, i.e., the length direction of the fabric 2. Thus, the fabric 2 is transported along the secondary scanning direction SS. The carriage 4, which carries the inkjet head 3, can reciprocate along the main scanning direction MS, which is substantially consistent with the width direction of the fabric 2. The inkjet head 3 is configured to scan the fabric 2 relative to each other in the main scanning direction MS and the secondary scanning direction SS.

[0236] Liquid ink cartridges 7a, 7b, 7c, 7d, 7e, and 7f are six independent liquid ink cartridges. Each of these cartridges can contain the ink composition and reaction solution used in the recording method of this embodiment. These cartridges contain ink compositions and reaction solutions in colors such as black, cyan, magenta, yellow, white, and orange, and can be used in any combination. Figure 1 The number of liquid ink cartridges is 6, but not limited to this. A supply port (not shown) for supplying the ink composition or reaction liquid contained in each liquid ink cartridge is provided at the bottom of the liquid ink cartridges 7a, 7b, 7c, 7d, 7e, and 7f to the ink head 3.

[0237] The inkjet head 3 is a unit that, under the control of a control unit (not shown), sprays ink compositions and reaction solutions supplied from liquid ink cartridges 7a, 7b, 7c, 7d, 7e, and 7f from multiple nozzles onto the fabric 2, causing it to adhere. The inkjet head 3 has multiple nozzles on the surface opposite the fabric 2 to which the ink compositions and reaction solutions are attached, thus adhering the ink compositions and reaction solutions to the fabric 2. These multiple nozzles are arranged in rows to form nozzle arrays, each array corresponding to a different color ink composition and reaction solution. The different color ink compositions and reaction solutions are supplied from each liquid ink cartridge to the inkjet head 3 and sprayed from the nozzles in droplet form using actuators (not shown) within the inkjet head 3. The sprayed droplets of ink compositions and reaction solutions fall onto the fabric 2, performing an adhesion process and forming images, text, patterns, and colors obtained using ink in the printing area of ​​the fabric 2. It should be noted that multiple inkjet heads 3 can be mounted on the carriage 4.

[0238] Here, the inkjet head 3 uses a piezoelectric element as the actuator of the drive unit, but is not limited to this method. For example, an electromechanical conversion element that displaces the vibrating plate that serves as the actuator by electrostatic adsorption, or a thermoelectric conversion element that uses bubbles generated by heating to eject the ink composition in the form of droplets, can also be used.

[0239] The inkjet head 3 has a nozzle group for ejecting a reaction liquid and a nozzle group for ejecting an ink composition. The nozzle group for ejection refers to the nozzle group used for recording in the recording method. It refers to a group of nozzles from which ink or the like can be ejected if an image to be recorded exists in the area of ​​the fabric opposite to the nozzle group during the main scan; this group is a continuous nozzle group in the sub-scanning direction SS. Therefore, nozzle groups that are not used for recording in the recording method, even though they exist themselves, are not included in the nozzle group for ejection.

[0240] Figure 2 , Figure 3 and Figure 4 An example of the configuration of the inkjet head 3 is shown. Figure 2 In this configuration, inkjet heads 3a and 3b are arranged from the upstream side to the downstream side in the transport direction (sub-scanning direction SS). Additionally, in... Figure 3 In this configuration, inkjet heads 3a and 3b are positioned at the same location in the sub-scanning direction SS, arranged horizontally side-by-side. Additionally, in... Figure 4 In the middle, inkjet heads 3a and 3b are arranged from the upstream side to the downstream side of the transport direction (sub-scanning direction SS) in such a way that they have overlapping parts.

[0241] In the recording method according to this embodiment, the inkjet head 3 is preferably configured to have a reaction liquid nozzle group for recording on the upstream side or overlapping portion of the fabric transport direction compared to the nozzle group for recording the ink composition. Furthermore, from the same viewpoint, the head that ejects the reaction liquid is preferably located at the same position in the fabric transport direction as the head that ejects the ink composition, or located upstream of the head that ejects the ink composition in the fabric transport direction. With such a configuration, droplet adhesion can be achieved through alternating spraying, with the reaction liquid being sprayed first. The components of the ink composition and the reaction liquid mix more easily, and the reaction proceeds more readily, thus exhibiting superior color development, rubbing fastness, and inhibition of bleeding.

[0242] For example, in Figure 2In this example, inkjet head 3a is used as the head that ejects the reaction liquid, and inkjet head 3b is used as the head that ejects the ink composition. This allows the nozzle assembly for the reaction liquid to be positioned upstream of the nozzle assembly for the ink composition in the fabric transport direction (sub-scanning direction SS). In this case, the reaction liquid adheres to the fabric before the ink composition. That is, the reaction liquid can be ejected first, forming a layer containing the reaction liquid, followed by the layer containing the ink composition being formed in a stacked manner.

[0243] For example, in Figure 2 In this example, inkjet head 3a is used as the head that ejects the reaction liquid, and inkjet head 3b is used as the head that ejects the ink composition. The nozzle group for recording the reaction liquid and the nozzle group for recording the ink composition have overlapping portions. In this case, alternating ejection is possible. That is, a layer (layer cake-like layer) in which the reaction liquid and the ink composition alternately overlap can be formed.

[0244] It should be noted that the "overlapping portion" refers to the portion located at the same position in the sub-scanning direction SS within the nozzle assembly for recording the ink composition and the nozzle assembly for recording the reaction liquid. Thus, the ink composition and reaction liquid adhere to the fabric in an overlapping manner through the same main scan.

[0245] For example, in Figure 4 In one example, inkjet head 3a is used as the head for ejecting the reaction liquid, and inkjet head 3b is used as the head for ejecting the ink composition. The nozzle group for recording the reaction liquid and the nozzle group for recording the ink composition have overlapping portions, allowing for alternating ejection. Alternatively, inkjet head 3a is used as the head for ejecting the reaction liquid, and inkjet head 3b is used as the head for ejecting the ink composition. The nozzle group for recording the reaction liquid and the nozzle group for recording the ink composition do not overlap, and the nozzle group for recording the reaction liquid is located upstream of the nozzle group for recording the ink composition in the fabric transport direction (sub-scanning direction SS). In this case, the reaction liquid can be ejected first.

[0246] Printer 1 can be equipped with a drying unit and a heating unit (neither shown). The drying unit and heating unit are used to effectively dry the reaction liquid or ink adhering to the cloth 2. The location of the drying unit and heating unit is not particularly limited, as long as they are positioned where the cloth 2 can be dried and heated. To effectively dry the ink or reaction liquid adhering to the cloth 2, for example, if... Figure 1 Then the drying unit and the heating unit can be set at positions opposite to the inkjet head 3.

[0247] Examples of drying and heating units include: a printer heater mechanism that heats the cloth 2 by bringing it into contact with a heat source; a mechanism that irradiates with infrared light or microwaves, which are electromagnetic waves with a very large wavelength of approximately 2450 MHz; and a dryer mechanism that blows hot air. Heating of the cloth 2 occurs before or during the application of droplets ejected from the nozzle of the inkjet head 3 onto the cloth 2. Control of various heating conditions, such as the timing of heating, heating temperature, and heating time, is performed by a control unit.

[0248] Alternatively, the drying unit and the heating unit can be located downstream of the fabric 2 in the transport direction. In this case, the fabric 2 is heated after the ink or reaction liquid ejected from the nozzle adheres to the fabric 2 to form an image. As a result, the drying properties of the ink or reaction liquid adhering to the fabric 2 are improved.

[0249] 4. Example

[0250] The invention will now be described in more detail with reference to examples, but the invention is not limited to these examples. Unless otherwise stated, "%" refers to a mass percentage.

[0251] 4.1 Preparation of reaction solution for pigment printing and dyeing

[0252] The components were added to a container to form the compositions shown in Tables 1-3 below. Pure water was added to bring the total volume of each reaction solution to 100% by mass. The mixture was stirred and mixed using a magnetic stirrer for 2 hours, and then further dispersed using a bead mill filled with 0.3 mm diameter zirconia beads to ensure thorough mixing. After stirring for 1 hour, the mixture was filtered using a 5 μm PTFE membrane filter to obtain the pigment dyeing reaction solutions for each example and comparative example. It should be noted that the values ​​for cationic polymers in Tables 1-3 below represent the mass percentage of solids as the active ingredient.

[0253] [Table 1]

[0254]

[0255] [Table 2]

[0256]

[0257] [Table 3]

[0258]

[0259] The following supplementary explanations are provided for the records in Tables 1 to 3 above.

[0260] <Composition of the reaction solution>

[0261] [Catonic polymer]

[0262] Kymene 557 (manufactured by SOLENIS, trade name, epichlorohydrin resin)

[0263] ·MILLIOGEN P-20 (manufactured by SENKA Corporation, trade name, quaternary salt of alkylamine-epoxychloropropane adduct)

[0264] UNISENCE FPA 100L (manufactured by SENKA Corporation, trade name, quaternary salt of alkylamine-allylamine adduct)

[0265] UNISENCE KHE 107L (manufactured by SENKA Corporation, trade name, quaternary salt of alkylamine-epoxychloropropane adduct)

[0266] [Polyols]

[0267] ·1,3-Butanediol (permeation solvent)

[0268] [other]

[0269] • OLFINE E1010 (manufactured by Nissin Chemical Industry Co., Ltd., trade name, acetylenic diol surfactant)

[0270] ·EDTA-2Na (Disodium dihydrogen ethylenediaminetetraacetic acid)

[0271] • Proxel XL2 (manufactured by Lonza Japan Co., Ltd., product name)

[0272] Terminology

[0273] "Boiling point": refers to the standard boiling point.

[0274] "Below 230℃ / Above 250℃": Content of polyols with a standard boiling point below 230℃ / Content of polyols with a standard boiling point above 250℃

[0275] "Polyols with a standard boiling point above 250℃ / Catonic polymers": Content of polyols with a standard boiling point above 250℃ / content of cationic polymers.

[0276] “Bk”: The ink composition listed in Table 4 below.

[0277] "IJ": Coating using inkjet technology

[0278] Viscosity was measured using a viscoelasticity tester (Pysica MCR-300). pH was measured using a benchtop pH meter (model F-72, manufacturer: HORIBA). It should be noted that the temperature for both viscosity and pH measurements was set to 20°C.

[0279] 4.2 Preparation of Printing and Dyeing Inkjet Ink Composition

[0280] The components were added to a container to form the composition shown in Table 4 below. The mixture was stirred and mixed using a magnetic stirrer for 2 hours, and then further dispersed using a bead mill filled with 0.3 mm diameter zirconia beads to ensure thorough mixing. After stirring for 1 hour, the mixture was filtered using a 5 μm PTFE membrane filter to obtain the ink composition. Pure water was added to bring the total amount of the ink composition to 100% by mass.

[0281] It should be noted that, regarding the pigment, a pigment dispersion solution is prepared in advance by mixing and stirring a pigment dispersant (not listed in the table) used as a styrene-acrylic water-soluble resin with the pigment in a mass ratio of pigment:pigment dispersant = 2:1 in water. This pigment dispersion solution is then used in the preparation of ink.

[0282] [Table 4]

[0283] Table 4

[0284]

[0285] 4.3 Production of Printed and Dyed Materials

[0286] Using a modified PX-H8000 (manufactured by Seiko Epson Corporation) device, printing was performed on a recording medium of 100% white cotton wide-width fabric under the conditions described in Tables 1-3 above. Multiple (4) main scans were performed on the same scanning area, thereby forming a densely packed pattern image on the A4-sized fabric as the recording medium. The fabric was then dried by heat treatment at 160°C for 3 minutes in an oven, thus producing the printed and dyed products of each embodiment and comparative example. It should be noted that the inkjet head used a head unit with a nozzle spacing of 600 dpi and 600 nozzles in the width direction of the recording medium. It should also be noted that the nozzle group for the reaction liquid and the nozzle group for the ink composition have portions located at the same position in the sub-scanning direction. Figure 3 The head is configured such that the reaction solution and ink composition are adhered to the same scanning area of ​​the fabric via the same main scan. Furthermore, the time difference between ink adhesion and reaction solution adhesion is within 5 seconds.

[0287] In addition, a "close-packed pattern image" refers to an image in which all pixels of the pixel region, which is defined by the recording resolution as the smallest recording unit region, are recorded (with a duty cycle of 100%).

[0288] 4.4 Evaluation Methods

[0289] 4.4.1 Intermittent Printing Stability

[0290] The aforementioned pigment printing reaction solutions were filled into a modified PX-H8000 (manufactured by Seiko Epson Corporation). After a 3-minute no-load run, the number of missing nozzles was counted using a nozzle inspection pattern, and the intermittent printing stability was evaluated according to the following criteria. A rating of C or higher indicates good intermittent printing stability.

[0291] (Evaluation Criteria)

[0292] A: The number of non-ejecting nozzles is less than 4.

[0293] B: The number of non-ejecting nozzles is more than 4 but less than 7

[0294] C: The number of non-ejecting nozzles is 7 or more but less than 11

[0295] D: The number of non-ejecting nozzles is 11 or more.

[0296] 4.4.2 Color Developing Properties

[0297] The OD value of black in the above-obtained printed and dyed materials was measured using a fluorescence spectrophotometer ("FD-7", manufactured by Konica Minolta). The color development was evaluated according to the following criteria. A color development of B or higher indicates good color development.

[0298] (Evaluation Criteria)

[0299] A: OD value above 1.45

[0300] B: OD value above 1.40 and below 1.45

[0301] C: OD value greater than 1.35 and less than 1.40

[0302] D: OD value less than 1.35

[0303] 4.4.3 Bleeding

[0304] The same printing material used in the "Wet Rubbing Fastness" test described below was employed in the evaluation of ink bleeding. The uneven ink aggregation within the densely packed patterns of the printing material was visually observed, and the evaluation was conducted according to the following criteria.

[0305] (Evaluation Criteria)

[0306] A: Uneven aggregation was observed within the close-packed pattern.

[0307] B: Some uneven aggregation was observed within the close-packed pattern.

[0308] C: Uneven aggregation was observed throughout the close-packed pattern.

[0309] 4.4.4 Wet Friction Resistance

[0310] The rubbing fastness of the above-obtained printed and dyed fabrics was tested according to the test method of ISO 105-X12. The wet rubbing fastness was evaluated according to the following standards. When the evaluation result is C or above, it can be said that good rubbing fastness has been obtained.

[0311] (Evaluation Criteria)

[0312] A: Friction resistance is grade 3 or above.

[0313] B: Friction fastness is grade 2-3 or higher but less than grade 3.

[0314] C: Friction fastness is grade 2 or higher but less than grade 2-3.

[0315] D: Friction fastness is less than level 2

[0316] 4.4.5 Pitting corrosion

[0317] The SUS430, a common component in inkjet heads, was immersed in the aforementioned pigment printing reaction solutions and left to stand at 60°C for 2 days to check for pitting corrosion. It should be noted that the printer can still be used even with pitting corrosion present.

[0318] (Evaluation Criteria)

[0319] Yes: Pitting corrosion

[0320] None: No pitting corrosion

[0321] 4.5 Evaluation Results

[0322] The evaluation results are shown in Tables 1-3 above.

[0323] According to Tables 1-3 above, the examples using pigment printing reaction solutions containing polyvalent metal salts, cationic polymers, polyols with a standard boiling point of 250°C or higher, and water, and which were sprayed using an inkjet method, all exhibited excellent color development, rubbing fastness, and intermittent printing stability.

[0324] Based on the comparison of Examples 4 and 17 with Comparative Examples 1 to 9, it is evident that by combining polyvalent metal salts and cationic polymers, good rubbing fastness and color development can be achieved.

[0325] Based on the comparison between Example 4 and Comparative Example 10, by using the reaction solution to spray it out by inkjet printing, good rubbing fastness and color development can be achieved.

[0326] Based on the comparison between Example 4 and Comparative Example 11, it was found that by using polyols containing a standard boiling point of 250°C or higher, good stability of intermittent printing could be achieved.

[0327] Based on the results of Examples 1-6, good color development, bleeding, and wet rubbing fastness were observed across a wide range of polyvalent metal salt contents.

[0328] According to the results of Examples 4 and 7, the presence of an alkaline compound can reduce pitting corrosion.

[0329] Based on the results of Examples 4, 8 to 11, pitting corrosion can be reduced while maintaining good wet friction fastness over a wide range of alkali compound contents.

[0330] Based on the results of Examples 4, 8, 12, and 13, various alkaline compounds can be used to reduce pitting corrosion.

[0331] According to the results of Examples 4 and 14, when the multivalent metal salt is a magnesium salt, the wet friction fastness is better.

[0332] Based on the results of Examples 4, 15-21, good intermittent printing stability and wet rubbing fastness were observed over a wide range of cationic polymer content.

[0333] Based on the results of Examples 4, 22-24, various cationic polymers showed good wet rubbing fastness.

[0334] According to the results of Examples 4, 25-31, the ratio of the content of polyols with a standard boiling point below 230°C to the content of polyols with a standard boiling point above 250°C is within the specified range, which can result in good wet rubbing adhesion and intermittent printing stability.

[0335] According to the results of Examples 4 and 32, when polyols with a standard boiling point below 230°C are included, the wet rubbing fastness becomes better.

[0336] Based on the results of Examples 4, 33-36, good intermittent printing stability, bleeding, and wet rubbing fastness can be achieved within a wide range of polyol content.

[0337] The following content is derived based on the above implementation method.

[0338] One method for preparing a reaction solution for pigment printing and dyeing is to use a reaction solution containing polyvalent metal salts, cationic polymers, polyols with a standard boiling point of 250°C or higher, and water, and to be sprayed out using an inkjet method.

[0339] In one embodiment of the above-mentioned pigment dyeing reaction solution,

[0340] The cationic polymer may have a structure derived from epoxy halogenated propane.

[0341] In any of the above-mentioned methods for preparing the reaction solution for pigment printing and dyeing,

[0342] The content of the cationic polymer can be 0.5 to 5.0% by mass relative to the total amount of the reaction solution.

[0343] In any of the above-mentioned methods for preparing the reaction solution for pigment printing and dyeing,

[0344] The polyvalent metal salt can be a magnesium salt.

[0345] In any of the above-mentioned methods for preparing the reaction solution for pigment printing and dyeing,

[0346] It may further contain polyols with a standard boiling point below 230°C.

[0347] In any of the above-mentioned methods for preparing the reaction solution for pigment printing and dyeing,

[0348] The content of the polyol with a standard boiling point of 250°C or higher can be 3% by mass or higher relative to the total amount of the reaction solution.

[0349] In any of the above-mentioned methods for preparing the reaction solution for pigment printing and dyeing,

[0350] When the content of polyols with a standard boiling point of 250°C or higher relative to the total amount of the reaction solution is set as M1, and the content of polyols with a standard boiling point of 230°C or lower relative to the total amount of the reaction solution is set as M2, the content ratio (M2 / M1) can be 0.1 to 30.0.

[0351] In any of the above-mentioned methods for preparing the reaction solution for pigment printing and dyeing,

[0352] When the content of the polyol with a standard boiling point of 250°C or higher relative to the total amount of the reaction solution is set as M1, and the content of the cationic polymer relative to the total amount of the reaction solution is set as M3, the content ratio (M1 / M3) can be 0.5 to 50.0.

[0353] In any of the above-mentioned methods for preparing the reaction solution for pigment printing and dyeing,

[0354] When the content of the cationic polymer relative to the total amount of the reaction solution is set as M3, and the content of the polyvalent metal salt relative to the total amount of the reaction solution is set as M4, the content ratio (M3 / M4) can be 0.1 to 4.0.

[0355] In any of the above-mentioned methods for preparing the reaction solution for pigment printing and dyeing,

[0356] The viscosity of the reaction solution used for pigment printing and dyeing can be 2 to 10 mPa·s.

[0357] In any of the above-mentioned methods for preparing the reaction solution for pigment printing and dyeing,

[0358] The pH of the reaction solution used for pigment printing and dyeing can be above 4.5.

[0359] In any of the above-mentioned methods for preparing the reaction solution for pigment printing and dyeing,

[0360] It may further contain alkali compounds.

[0361] When the content of the alkali compound relative to the total amount of the reaction solution is set as M5, and the content of the cationic polymer relative to the total amount of the reaction solution is set as M3, the content ratio (M5 / M3) can be 0.1 to 1.0.

[0362] One type of ink group is an ink group having a printing and dyeing inkjet ink composition containing pigments, resin particles and water, and a pigment printing and dyeing reaction solution of any of the above types.

[0363] One method of recording is an ink adhesion step that uses inkjet printing to attach an ink composition to a fabric and a reaction liquid adhesion step that uses inkjet printing to attach a pigment printing reaction liquid of either of the above methods to the fabric.

[0364] In one of the above recording methods,

[0365] The time difference between the ink adhesion step and the reaction solution adhesion step can be within 5 seconds.

[0366] In any of the above recording methods,

[0367] The inkjet method can perform multiple main scans by moving the inkjet head in a direction perpendicular to the transport direction of the fabric.

[0368] The pigment dyeing reaction solution and the ink composition are adhered to the same scanning area of ​​the fabric through the same master scan, and

[0369] The same main scan is performed multiple times on the same scanning area.

[0370] This invention is not limited to the embodiments described above and can be modified in various ways. For example, this invention includes configurations that are substantially the same as those described in the embodiments, such as configurations with the same function, method, and result, or configurations with the same purpose and effect. Furthermore, this invention includes configurations that replace non-essential parts of the configurations described in the embodiments. Additionally, this invention includes configurations that can achieve the same effect as those described in the embodiments, or configurations that can achieve the same purpose. Furthermore, this invention includes configurations that incorporate known techniques into the configurations described in the embodiments.

Claims

1. A reaction solution for pigment printing and dyeing, characterized in that, It contains polyvalent metal salts, cationic polymers, polyols with a standard boiling point above 250°C, and water. The pigment dyeing reaction solution is used by inkjet printing. It also contains polyols with a standard boiling point below 230°C. When the content of polyols with a standard boiling point of 250°C or higher relative to the total amount of the reaction solution is defined as M1, and the content of polyols with a standard boiling point of 230°C or lower relative to the total amount of the reaction solution is defined as M2, the content ratio M2 / M1 is 0.1 to 30.

0. It also contains alkali compounds. When the content of the alkali compound relative to the total amount of the reaction solution is set as M5, and the content of the cationic polymer relative to the total amount of the reaction solution is set as M3, the content ratio M5 / M3 is 0.1 to 1.

0.

2. The reaction solution for pigment printing and dyeing according to claim 1, wherein, The cationic polymer has a structure derived from epoxy halogenated propane.

3. The pigment dyeing reaction solution according to claim 1 or 2, wherein, The content of the cationic polymer is 0.5 to 5.0% by mass relative to the total amount of the reaction solution.

4. The reaction solution for pigment printing and dyeing according to claim 1, wherein, The polyvalent metal salt is a magnesium salt.

5. The reaction solution for pigment printing and dyeing according to claim 1, wherein, The content of the polyol with a standard boiling point of 250°C or higher is 3% by mass or higher relative to the total amount of the reaction solution.

6. The reaction solution for pigment printing and dyeing according to claim 1, wherein, When the content of the polyol with a standard boiling point of 250°C or higher relative to the total amount of the reaction solution is set as M1, and the content of the cationic polymer relative to the total amount of the reaction solution is set as M3, the content ratio M1 / M3 is 0.5 to 50.

0.

7. The reaction solution for pigment printing and dyeing according to claim 1, wherein, When the content of the cationic polymer relative to the total amount of the reaction solution is set as M3, and the content of the polyvalent metal salt relative to the total amount of the reaction solution is set as M4, the content ratio M3 / M4 is 0.1 to 4.

0.

8. The reaction solution for pigment printing and dyeing according to claim 1, wherein, The viscosity of the pigment printing reaction solution is 2-10 mPa s.

9. The reaction solution for pigment printing and dyeing according to claim 1, wherein, The pH of the reaction solution used for pigment printing and dyeing is above 4.

5.

10. An ink set, characterized in that, The invention comprises a printing inkjet ink composition and a pigment printing reaction solution according to any one of claims 1 to 9, wherein the printing inkjet ink composition contains pigment, resin particles and water.

11. A recording method characterized by, have: The ink adhesion step, which uses inkjet printing to adhere an ink composition to a fabric; and The reaction liquid adhesion step of applying the pigment printing reaction liquid of any one of claims 1 to 9 to the fabric using an inkjet method.

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

13. The recording method according to claim 11 or 12, wherein, The inkjet method involves multiple main scans to record data by moving the inkjet head in a direction perpendicular to the fabric's transport direction. the pigment printing reaction solution and the ink composition are attached to the same scanning region of the cloth by the same main scanning, and the same main scanning is performed a plurality of times on the same scanning region.

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