Treatment liquid for inkjet textile printing, ink set for inkjet textile printing, inkjet textile printing method, and inkjet textile printing device

Abstract

A treatment liquid for inkjet textile printing according to one embodiment of the present invention contains a water-soluble cationic polymer and ammonium formate.

Description

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

[0001] The present invention relates to an inkjet textile printing treatment liquid, an inkjet textile printing ink set, an inkjet textile printing method, and an inkjet textile printing apparatus.

[0002] As a method for forming images on fabric, a textile printing method using an inkjet recording system (inkjet textile printing method) has attracted attention because it can adequately accommodate high-mix, low-volume production and reduce wastewater generation. In inkjet textile printing methods, in addition to ejecting and depositing ink onto a fabric as a recording medium, a treatment liquid may also be ejected and deposited separately from the ink. Specifically, a pretreatment liquid may be ejected onto the recording medium before ejecting the ink. Examples of such treatment liquids include the treatment liquids described in Patent Documents 1 and 2. Patent Document 1 describes a pretreatment liquid for aqueous pigment textile printing that contains an aqueous nonionic polyurethane and a metal salt. Patent Document 1 discloses that the pretreatment liquid can improve the fastness of ink to be subsequently coated, prevent penetration of white ink, or increase the saturation of color ink. Patent Document 2 also describes a textile printing treatment liquid that contains an organic acid having a boiling point of 120°C or less and an organic acid having a boiling point of 140°C or more. Patent Document 2 discloses that pigment aggregation can be promoted, a coating film can be formed in a state in which the pigment has adequately penetrated into the fabric, and a printed item (textile print) can be obtained that has a good balance of set-off resistance, bleeding resistance, and washing fastness.

[0003] JP 2020-183605 A JP 2021-152091 A

[0004] The inkjet printing treatment liquid according to one aspect of the present invention contains a water-soluble cationic polymer and ammonium formate.

[0005] A treatment liquid for inkjet textile printing according to another aspect of the present invention contains a water-soluble cationic polymer and an organic acid ammonium salt, which is made of an organic acid and ammonia, and has a vapor pressure of 2 kPa or less at 20°C.

[0006] Fig. 1 is a schematic diagram partially illustrating the configuration of an inkjet textile printing device that uses a treatment liquid for inkjet textile printing according to an embodiment of the present disclosure. Fig. 2 is a perspective view illustrating the overall configuration of an inkjet printer that uses a treatment liquid for inkjet textile printing according to an embodiment of the present disclosure. Fig. 3 is a schematic cross-sectional view taken along line III-III in Fig. 2. Fig. 4 is an enlarged perspective view of the carriage shown in Fig. 2.

[0007] Hereinafter, embodiments of the present disclosure will be described, but the present disclosure is not limited to these.

[0008] [Inkjet Printing Treatment Liquid] The inkjet printing treatment liquid according to one embodiment of the present disclosure is an inkjet printing treatment liquid containing a water-soluble cationic polymer and ammonium formate. The inkjet printing treatment liquid according to this embodiment is ejected and deposited on a fabric, which is a recording medium, separately from the inkjet printing ink. In this manner, the water-soluble cationic polymer contained in the inkjet printing treatment liquid aggregates coloring materials such as pigments contained in the inkjet printing ink, thereby producing a printed item with excellent color development. Furthermore, by incorporating not only a water-soluble cationic polymer but also an organic acid salt into the inkjet printing treatment liquid, a printed item with not only excellent color development but also a good texture can be produced. Furthermore, by incorporating ammonium formate as the organic acid salt in the inkjet printing treatment liquid, a printed item with high color development and a good texture can be produced while suppressing odor generation. The inkjet textile printing treatment liquid may be a pre-treatment liquid that is ejected onto the fabric before the inkjet textile printing ink is applied to the fabric, or a post-treatment liquid that is ejected onto the fabric after the inkjet textile printing ink has been applied to the fabric. However, the inkjet textile printing treatment liquid may be a pre-treatment liquid in view of exhibiting better color development and a better texture.

[0009] When a treatment liquid containing a metal salt (e.g., the treatment liquid described in Patent Document 1) is used as the treatment liquid for inkjet textile printing, there is a concern that adding a large amount of the metal salt may deteriorate the texture of the printed textile. In contrast, when a treatment liquid containing an organic acid salt is ejected onto a fabric and adhered thereto, the treatment liquid adhered to the fabric favorably aggregates coloring materials such as pigments contained in the ink adhered to the fabric, thereby enabling the resulting printed textile to exhibit high color development and a good texture. However, some organic acid salts contained in such treatment liquids have a strong odor, and this strong odor may be perceived in the atmosphere during inkjet textile printing. Furthermore, the resulting printed textile may also have a strong odor. Furthermore, when an organic acid with a low boiling point (e.g., an organic acid having a boiling point of 120°C or less as described in Patent Document 2) is contained in the treatment liquid for inkjet textile printing, this organic acid is highly volatile and may therefore have a strong odor in the atmosphere during inkjet textile printing. The inkjet textile printing treatment liquid according to the present disclosure can suppress the occurrence of the above-mentioned concerns, suppress the generation of odor, and obtain printed textiles with high color development and good texture.

[0010] The water-soluble cationic polymer contained in the inkjet printing treatment liquid is not particularly limited, as long as it is a water-soluble cationic polymer that can aggregate the coloring material contained in the inkjet printing ink upon contact with the inkjet printing ink. Examples of the water-soluble cationic polymer include ammonium-containing polymers, amine-containing polymers, polyallylamine, polyvinylamine, polyimine, polyvinylpyrrolidone, polyethyleneimine, polyvinylpyridine, aminoacetalized polyvinyl alcohol, ionene polymers, polyvinylimidazole, polyvinylbenzylphosphonium, polyalkylallylammonium, polyamidine, and polyamine sulfone. Among these, examples of the water-soluble cationic polymer that can provide better color development include quaternary ammonium-containing polymers (quaternary ammonium salt cationic polymers), diallyldimethylammonium-sulfur dioxide copolymers, diallyldimethylammonium chloride-acrylamide copolymers, diallyldimethylammonium chloride polymers, dimethylamine-ammonia-epichlorohydrin polycondensates, and dimethylamine-ammonia-epichlorohydrin polycondensates. These may be used alone or in combination of two or more. The water-soluble cationic polymer may contain succinate anions, which can further suppress yellowing of the resulting printed textile (e.g., yellowing that may occur when the resulting printed textile is heated). That is, the water-soluble cationic polymer may contain succinic acid as a counter ion. Specifically, the water-soluble cationic polymer may form a salt with succinate anions. More specifically, at least a portion of the anions of the water-soluble cationic polymer may be ion-exchanged with succinate anions. Furthermore, when the water-soluble cationic polymer forms a salt with succinate anions, water solubility can be increased, and therefore the content of the water-soluble cationic polymer can be increased. In this way, increasing the content of the water-soluble cationic polymer can further enhance the aggregability of the inkjet printing ink with respect to coloring materials such as pigments, resulting in a printed textile with superior color development and texture.Therefore, it is possible to obtain a printed item having excellent color development and texture while suppressing yellowing.

[0011] The weight average molecular weight of the water-soluble cationic polymer is not particularly limited, but is preferably 1,000 or more and 10,000 or less in terms of improving ejection properties from an inkjet head.

[0012] The content of the water-soluble cationic polymer is not particularly limited, but from the viewpoint of further enhancing color development, the lower limit is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, relative to the inkjet textile printing treatment liquid, and the upper limit is preferably 35% by mass or less, more preferably 29.5% by mass or less, and even more preferably 20% by mass or less, relative to the inkjet textile printing treatment liquid.

[0013] As described above, the inkjet textile printing treatment liquid contains ammonium formate. Commercially available ammonium formate can be used as the ammonium formate, and there are no particular limitations on how it can be obtained. The lower limit of the ammonium formate content relative to the inkjet textile printing treatment liquid is preferably 0.1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more. The upper limit of the ammonium formate content relative to the inkjet textile printing treatment liquid is preferably 25% by mass or less, more preferably 23% by mass or less, and even more preferably 20% by mass or less. By having the ammonium formate content within the above range, it is possible to obtain a printed product with excellent color development and texture while suppressing odor generation.

[0014] As described above, the inkjet textile printing treatment liquid contains ammonium formate as an organic acid salt, and thereby it is possible to obtain a printed product having excellent color development and texture while suppressing the generation of odor, particularly odor derived from the organic acid salt.

[0015] Furthermore, the present inventors conducted a more detailed study of the odors perceived in the atmosphere during inkjet printing and the odors perceived from the resulting printed textiles, and found that in inkjet printing methods using an inkjet printing treatment liquid, an odor originating from the water-soluble cationic polymer contained in the inkjet printing treatment liquid can be detected. Specifically, when a printed textile is dried by high-temperature treatment, a strong odor can be detected from the dried printed textile. This odor is thought to be due to the alteration of the water-soluble cationic polymer caused by heating the printed textile and the compounds generated by this alteration. Specifically, when ammonium-containing polymers, amine-containing polymers, polyallylamine, polyvinylamine, quaternary ammonium salt cationic polymers, and the like are used as the water-soluble cationic polymers, high-temperature treatment of these water-soluble cationic polymers can result in a strong odor being detected from the dried printed textile due to thermal decomposition and the like. It has been found that the odor originating from the water-soluble cationic polymer (hereinafter, when a water-soluble cationic polymer that generates amines or the like upon deterioration is used, this odor may be simply referred to as "amine odor") by adding an organic acid ammonium salt, which is composed of an organic acid and ammonia and has a vapor pressure of 2 kPa or less at 20°C, to the inkjet printing treatment liquid. This is thought to be because the addition of the organic acid ammonium salt can suppress deterioration of the water-soluble cationic polymer. More specifically, it is thought that by preferentially volatilizing the base in the early stages of drying and making the inkjet printing treatment liquid acidic, deterioration of the water-soluble cationic polymer, which may proceed under basic conditions during high-temperature drying, can be suppressed.Furthermore, although it may be possible to suppress the generation of odors (e.g., amine odor) derived from the water-soluble cationic polymer by adding an organic acid to the inkjet textile printing treatment liquid instead of the organic acid ammonium salt, there is a concern that the inkjet textile printing treatment liquid may become acidic, which may corrode the inkjet textile printing device (e.g., inkjet head, flow path, etc.), but the organic acid ammonium salt can suppress the generation of such corrosion, thereby ensuring excellent compatibility with components.

[0016] The inkjet textile printing treatment liquid preferably contains the organic acid ammonium salt (an organic acid ammonium salt composed of an organic acid and ammonia, the vapor pressure of which at 20°C is 2 kPa or less). That is, the inkjet textile printing treatment liquid preferably contains the water-soluble cationic polymer and the organic acid ammonium salt. By containing the organic acid ammonium salt, it is possible to ensure excellent component compatibility while suppressing odors (e.g., amine odors) derived from the water-soluble cationic polymer. Furthermore, it is preferable that the inkjet textile printing treatment liquid contains ammonium formate and further contains the organic acid ammonium salt. That is, it is preferable that the inkjet textile printing treatment liquid contains the water-soluble cationic polymer, ammonium formate, and the organic acid ammonium salt. By doing so, it is possible to obtain a printed product that is excellent in component compatibility and that further excels in color development and texture while suppressing not only the generation of odors, particularly odors derived from organic acid salts, but also the generation of odors derived from the water-soluble cationic polymer.

[0017] The organic acid ammonium salt is not particularly limited as long as it is an organic acid ammonium salt composed of an organic acid and ammonia, and the vapor pressure at 20°C is 2 kPa or less, and examples thereof include ammonium succinate, ammonium citrate, ammonium benzoate, and ammonium acetate. Examples of the ammonium succinate include ammonium succinate and diammonium succinate. Examples of the ammonium citrate include ammonium citrate, diammonium hydrogen citrate, and triammonium citrate. The organic acid ammonium salt may be used alone or in combination of two or more. The organic acid in the organic acid ammonium salt may be an organic acid having a vapor pressure of 2 kPa or less at 20°C, or may be an organic acid that is very difficult to evaporate at 20°C and therefore does not substantially evaporate. In other words, the vapor pressure may be approximately 0 kPa, and the organic acid may be an organic acid having a vapor pressure of 0 to 2 kPa at 20°C. Examples of the organic acid include organic acids having a vapor pressure of 2 kPa or less at 20° C. according to the International Chemical Safety Cards (ICSC). This vapor pressure may be a value obtained by a general vapor pressure measurement method, and for example, a value obtained by a static method may be used, or if measurement by the static method is difficult (for example, 100 kPa or less), a value measured by a gas flow method may be used.

[0018] The content of the organic acid ammonium salt is not particularly limited, but the lower limit is preferably 10% by mass or more, and more preferably 100% by mass or more, relative to the water-soluble cationic polymer. The upper limit of the content of the organic acid ammonium salt is preferably 300% by mass or less, and more preferably 200% by mass or less, relative to the water-soluble cationic polymer. The lower limit of the content of the organic acid ammonium salt is preferably 0.5% by mass or more, and more preferably 3% by mass or more, relative to the inkjet printing treatment liquid. The upper limit of the content of the organic acid ammonium salt is preferably 10% by mass or less, more preferably 6% by mass or less, and even more preferably 5% by mass or less. By keeping the content of the organic acid ammonium salt within the above range, it is possible to obtain a printed product in which the generation of odors (e.g., amine odors) derived from the water-soluble cationic polymer is more suitably suppressed while ensuring excellent component compatibility.

[0019] The inkjet textile printing treatment liquid may contain the organic ammonium salt as long as it contains ammonium formate, and may further contain an organic acid salt (another organic acid salt) other than ammonium formate and the organic ammonium salt. The other organic acid salt is not particularly limited, but examples thereof include organic ammonium salts. Examples of the organic ammonium salt include, from the viewpoint of water solubility, ammonium propionate, ammonium oxalate, ammonium tartrate, ammonium lactate, diammonium malonate, ammonium malate, and ammonium L-glutamate. The other organic acid salts may be used alone or in combination of two or more. As described above, the inkjet textile printing treatment liquid may contain the other organic acid salt as long as it contains ammonium formate. However, the content of the other organic acid salt may be small or may not be present in order to further suppress odor. Specifically, the content of the other organic acid salt is preferably 50 parts by mass or more and 100 parts by mass or less, and may be 100 parts by mass, relative to 100 parts by mass of the total of the ammonium formate and the other organic acid salt. Furthermore, the content of the ammonium formate is preferably 50 parts by mass or more and 100 parts by mass or less, and may be 100 parts by mass, relative to 100 parts by mass of the total of the ammonium formate, the organic ammonium salt, and the other organic acid salt.

[0020] The inkjet printing treatment liquid may further contain a metal salt in order to further enhance the aggregating properties of the coloring material, such as the pigment, contained in the inkjet printing ink, thereby further improving, for example, washing fastness. The anions constituting the metal salt are not particularly limited, and examples thereof include organic acid anions such as acetic acid, lactic acid, and oxalic acid, carbonate ions, sulfate ions, nitrate ions, chloride ions, sulfide ions, silicate ions, and hydroxide ions. Examples of the metal ions constituting the metal salt include divalent or higher metal ions such as magnesium, calcium, copper, nickel, zinc, barium, aluminum, titanium, strontium, chromium, cobalt, and iron, and monovalent metal ions such as sodium and potassium. Among these, the metal ions constituting the metal salt may be divalent or higher metal ions in order to further enhance aggregating properties, i.e., the metal salt may be a polyvalent metal salt. Examples of the metal salt include calcium acetate, calcium carbonate, calcium nitrate, calcium chloride, calcium sulfate, calcium hydroxide, magnesium acetate, magnesium lactate, magnesium oxalate, magnesium sulfate, trimagnesium phosphate, aluminum acetate, barium sulfate, barium chloride, zinc carbonate, zinc sulfide, aluminum silicate, calcium silicate, and copper nitrate. Among these, magnesium acetate may be used as the metal salt, as it further enhances coagulation properties. The metal salts may be used alone or in combination of two or more. When the inkjet printing treatment liquid contains the metal salt, the lower limit of the content is preferably 0.1% by mass or more, and more preferably 0.3% by mass or more, relative to the inkjet printing treatment liquid. The upper limit of the content of the metal salt is preferably 3% by mass or less, and more preferably 1% by mass or less, relative to the inkjet printing treatment liquid. By having the metal salt content within the above range, the effect of improving washing fastness, which is achieved by containing the metal salt, can be suitably achieved. Therefore, it is possible to obtain a printed item that is excellent in color development, texture, and washing fastness while suppressing odor generation.

[0021] The inkjet printing treatment liquid may contain an aqueous medium as a main component (e.g., 50% by mass or more), and the balance other than the water-soluble cationic polymer and ammonium formate may be an aqueous medium. The inkjet printing treatment liquid may also contain a surfactant, etc., as necessary.

[0022] The aqueous medium contained in the inkjet textile printing treatment liquid is not particularly limited as long as it contains water. For example, it may be an aqueous medium containing water as a main component (e.g., 50% by mass or more) or an aqueous medium consisting of water. In addition, the aqueous medium may function as a solvent or a dispersion medium in the inkjet textile printing treatment liquid. The content of water relative to the aqueous medium is, for example, preferably 50% by mass or more, more preferably 90% by mass or more, and may even be 100% by mass. Furthermore, the aqueous medium may contain water and further contain an organic solvent. That is, the aqueous medium may be an aqueous medium containing water and an organic solvent. When the organic solvent is contained, the content of the organic solvent relative to the inkjet textile printing treatment liquid is preferably, for example, 3% by mass or more and 50% by mass or less, from the viewpoint of obtaining a pretreatment liquid having a viscosity that allows stable ejection and that is inhibited from drying.

[0023] Examples of the organic solvent include glycol compounds, alcohol compounds (e.g., polyhydric alcohols), ether compounds (e.g., ether compounds of polyhydric alcohols), nitrogen-containing compounds, sulfur-containing compounds, aliphatic hydrocarbons, ketone compounds, ester compounds, vegetable oils, and alkylene carbonates.

[0024] Examples of the glycol compound include ethylene glycol, 1,3-propanediol, propylene glycol, 1,2-pentanediol, 1,5-pentanediol, 1,2-octanediol, 1,8-octanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol, and tetraethylene glycol.

[0025] Examples of the polyhydric alcohol include a diol compound having 5 to 8 carbon atoms (first diol compound), a diol compound having 2 to 4 carbon atoms (second diol compound), 1,2,6-hexanetriol, glycerin, trimethylolpropane, sugar alcohols (e.g., xylitol), and sugars (e.g., xylose, glucose, and galactose).

[0026] Examples of the first diol compound include 2-methylpentane-2,4-diol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, and 1,2-hexanediol.

[0027] Examples of the second diol compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, butylene glycol, and diethylene glycol.

[0028] Examples of the alcohol compound other than the polyhydric alcohol include methanol, ethanol, isopropanol, butanol, and benzyl alcohol.

[0029] Examples of the ether compounds include ether compounds of polyhydric alcohols. Examples of the ether compounds of polyhydric alcohols include glycol ether compounds and ethylene oxide adducts of diglycerin. Examples of the glycol ether compounds include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, and dipropylene glycol monobutyl ether.

[0030] Examples of the nitrogen-containing compound include lactam compounds, 1,3-dimethylimidazolidinone, formamide, dimethylformamide, and triethanolamine. Examples of the lactam compound include pyrrolidones such as 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexylpyrrolidone, and N-methyl-2-pyrrolidone.

[0031] Examples of the sulfur-containing compound include thiodiethanol, thiodiglycerol, sulfolane, and dimethyl sulfoxide.

[0032] Examples of the aliphatic hydrocarbons include linear hydrocarbons, isoparaffinic hydrocarbons, and naphthenic hydrocarbons.

[0033] Examples of the ketone compound include methyl ethyl ketone.

[0034] Examples of the ester compounds include acetate compounds such as diethylene glycol monoethyl ether acetate.

[0035] Examples of the vegetable oil include soybean oil, linseed oil, rice bran oil, tung oil, castor oil, dehydrated castor oil, corn oil, safflower oil, South Sea tung oil, recycled vegetable oil, canola oil, rapeseed oil, tung oil, peanut oil, cottonseed oil, sesame oil, sunflower oil, olive oil, palm oil, palm kernel oil, coconut oil, and the like, as well as thermally polymerized oils and oxidatively polymerized oils thereof.

[0036] Examples of the alkylene carbonate include propylene carbonate and ethylene carbonate.

[0037] Among the above-mentioned organic solvents, glycol compounds are preferred, and 3-methyl-1,5-pentanediol is more preferred. The organic solvents may be used alone or in combination of two or more.

[0038] The content of the aqueous medium is not particularly limited and may be the remainder. Specifically, the content of the aqueous medium is, for example, preferably 5% by mass to 70% by mass, and more preferably 10% by mass to 60% by mass, based on the total mass of the inkjet textile printing treatment liquid.

[0039] The inkjet printing treatment liquid may contain a surfactant for the purpose of adjusting the surface tension, etc. Furthermore, by containing a surfactant in the inkjet printing treatment liquid, the wettability of the inkjet printing treatment liquid with respect to the fabric serving as a recording medium is improved. The surfactant is not particularly limited, and may be any of a nonionic surfactant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, etc.

[0040] Examples of the nonionic surfactant include silicone surfactants such as polyether-modified silicone, and acetylene glycol surfactants such as acetylene diol ethylene oxide adducts.

[0041] Examples of the cationic surfactant include quaternary ammonium surfactants and amine surfactants.

[0042] Examples of the anionic surfactant include carboxylic acid surfactants, carboxylate surfactants, and sulfate ester surfactants.

[0043] Examples of the amphoteric surfactant include carboxylate-type amphoteric surfactants, sulfate-type amphoteric surfactants, sulfonate-type amphoteric surfactants, and phosphate-type amphoteric surfactants.

[0044] The surfactants may be used alone or in combination of two or more.

[0045] When the inkjet textile printing treatment liquid contains the surfactant, the content thereof is not particularly limited, but is preferably 0.05% by mass or more and 5% by mass or less, and more preferably 0.1% by mass or more and 5% by mass or less, relative to the inkjet textile printing treatment liquid.

[0046] The inkjet printing treatment liquid may further contain, as necessary, known additives (more specifically, a dissolution stabilizer, a drying inhibitor, an antioxidant, a viscosity adjuster, a pH adjuster, an anti-mold agent, etc.) The pH adjuster is not particularly limited, and examples thereof include an aqueous sodium hydroxide solution.

[0047] The pH of the inkjet textile printing treatment liquid is not particularly limited, and the lower limit thereof is preferably 7 or higher from the viewpoint of suppressing corrosion of the inkjet textile printing apparatus (e.g., inkjet head, etc.). The upper limit thereof is preferably 9.5 or lower, more preferably 8 or lower, from the viewpoint of further suppressing deterioration in the texture of the resulting printed textile. The pH of the inkjet textile printing treatment liquid can be adjusted, for example, by the composition of the inkjet textile printing treatment liquid. More specifically, the pH of the inkjet textile printing treatment liquid can be adjusted by the content of sodium formate in the inkjet textile printing treatment liquid, or by the type and content of the pH adjuster added to the inkjet textile printing treatment liquid. When the inkjet textile printing treatment liquid contains the other organic acid and the metal salt, the pH of the inkjet textile printing treatment liquid can also be adjusted by the type and content of these. The pH of the inkjet printing treatment liquid can be measured using, for example, a known pH meter.

[0048] The inkjet printing treatment liquid is produced by, for example, mixing the water-soluble cationic polymer, the ammonium formate, the aqueous medium, and components added as needed (for example, metal salts, surfactants, etc.) using a mixer. The mixing time is not particularly limited, and is preferably, for example, from 1 minute to 30 minutes.

[0049] (Fabric) The fabric onto which the inkjet printing treatment liquid is ejected and deposited is the printing target (recording medium) in the inkjet printing method. Examples of the fabric include products containing fibers, and may also be products made of fibers. Examples of the fabric include woven fabrics, knitted fabrics, nonwoven fabrics, and braided fabrics. Examples of the fiber include natural fibers such as cotton, silk, wool, and linen; chemical fibers such as polyester fibers, acrylic fibers, polyurethane fibers, polyamide fibers, rayon, cupra, and acetate; and blends thereof. The fabric may contain one type of these fibers alone, or may contain two or more types in combination. More specifically, examples of the fabric include cotton fabrics, silk fabrics, linen fabrics, polyester fabrics, acetate fabrics, rayon fabrics, polyamide fabrics, and polyurethane fabrics. The fabric may be a polyester tropical fabric, which is a plain woven fabric of polyester yarn. The fabric may be used alone or in combination of two or more.

[0050] [Inkjet Printing Ink Set] As described above, the inkjet textile printing treatment liquid is used by ejecting and adhering it to a fabric, which is a recording medium, separately from the inkjet textile printing ink (hereinafter also simply referred to as ink). Therefore, the inkjet textile printing treatment liquid may be used together with the ink as an inkjet textile printing ink set. That is, the inkjet textile printing ink set includes the inkjet textile printing treatment liquid and the ink. When the inkjet textile printing treatment liquid is used, for example, as a pretreatment liquid, it is ejected and adhered to the fabric before the ink is applied to the fabric. The ink is not particularly limited as long as it is an ink used in an inkjet textile printing method, and examples thereof include inkjet textile printing inks containing anionic pigments. Furthermore, when the inkjet textile printing treatment liquid is used as, for example, a pre-treatment liquid, the ink set for inkjet textile printing may further include, as a post-treatment liquid, an inkjet textile printing treatment liquid different from the inkjet textile printing treatment liquid. That is, the ink set for inkjet textile printing may be an ink set including the inkjet textile printing treatment liquid (pre-treatment liquid), the ink, and the post-treatment liquid.

[0051] (Inkjet Textile Printing Ink) The inkjet textile printing ink is not particularly limited as long as it can be used as an ink in an inkjet textile printing method. Examples of the ink include inks containing a colorant and an aqueous medium. Furthermore, the ink may contain at least one selected from the group consisting of binder resin particles and surfactants, as necessary.

[0052] The coloring material is not particularly limited as long as it is a coloring material contained in ink in an inkjet printing method, and examples thereof include pigments such as anionic pigments. Examples of the pigment include dispersible pigments that are dispersed in an aqueous medium such as water. The volume median diameter (D ５０From the viewpoint of obtaining an ink excellent in image density, hue, and color stability, the volume median diameter (D ５０ ) is the median diameter measured using a laser diffraction / scattering particle size distribution measuring device (for example, LA-950 manufactured by Horiba, Ltd.).

[0053] The pigment is not particularly limited as long as it can form a desired image (i.e., can express the colors that constitute the desired image), and examples thereof include known organic pigments and inorganic pigments. Examples of organic pigments include azo pigments, polycyclic pigments, nitro pigments, nitroso pigments, and aniline black. Examples of azo pigments include azo lake pigments, insoluble azo pigments, condensed azo pigments, and chelate azo pigments. Examples of polycyclic pigments include phthalocyanine pigments, perylene pigments, anthraquinone pigments, quinacridone pigments, dioxandinone pigments, thioindigo pigments, isoindolinone pigments, and quinophthaloni pigments. Examples of inorganic pigments include carbon blacks such as acetylene black and lamp black.

[0054] The pigments can also be classified according to color, and examples thereof include yellow pigments, orange pigments, red pigments, blue pigments, green pigments, and black pigments.

[0055] Examples of the yellow pigment include C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 15, C.I. Pigment Yellow 17, C.I. Pigment Yellow 74, C.I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 95, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, Pigment Yellow 120, C.I. Pigment Yellow 128, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 151, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Examples of pigments that can be used include C.I. Pigment Yellow 173, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, and C.I. Pigment Yellow 193.

[0056] Examples of the orange pigment include C.I. Pigment Orange 31, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 43, C.I. Pigment Orange 61, C.I. Pigment Orange 63, and C.I. Pigment Orange 71.

[0057] Examples of the red pigment include C.I. Pigment Red 2, C.I. Pigment Red 3, C.I. Pigment Red 5, C.I. Pigment Red 6, C.I. Pigment Red 7, C.I. Pigment Red 15, C.I. Pigment Red 16, C.I. Pigment Red 48:1, C.I. Pigment Red 53:1, C.I. Pigment Red 57:1, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 139, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 150, C.I. Pigment Red 166, C.I. Examples of pigments include C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. Pigment Red 202, and C.I. Pigment Red 222.

[0058] Examples of the blue pigment include C.I. Pigment Blue 15, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, and C.I. Pigment Blue 16.

[0059] Examples of the green pigment include C.I. Pigment Green 7.

[0060] Examples of the black pigment include C.I. Pigment Black 7.

[0061] As the coloring material, the pigments may be used alone or in combination of two or more.

[0062] When the ink is used together with the inkjet printing treatment liquid as in this embodiment, the pigment may be an anionic pigment for the following reasons: The anionic pigment forms an ionic bond with the water-soluble cationic polymer contained in the inkjet printing treatment liquid on the surface of the recording medium, thereby causing the anionic pigment and the water-soluble cationic polymer to aggregate. This aggregation of the anionic pigment and the water-soluble cationic polymer can prevent binder resin particles (binder resin particles described below) contained in the ink from penetrating into the recording medium. This prevents the binder resin particles from penetrating into gaps between fibers constituting the fabric and binding these fibers together. This can improve the texture (feel, etc.) of the resulting printed textile.

[0063] Examples of the anionic pigment include pigments having an anionic group such as a carboxy group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a phenylphosphonic acid group, and a phenylcarboxy group (pigments into which an anionic group has been introduced).

[0064] The content of the coloring material (pigment) is not particularly limited, but from the viewpoint of increasing image density while maintaining high ink fluidity, it is preferably 1% by mass or more and 12% by mass or less, and more preferably 1% by mass or more and 7% by mass or less, relative to the ink. A high content of the coloring material (pigment) (for example, 1% by mass or more) tends to increase image density, while a low content of the coloring material (pigment) (for example, 12% by mass or less) increases ink fluidity.

[0065] The aqueous medium contained in the ink is not particularly limited as long as it is a medium containing water, and examples thereof include the same aqueous medium as the aqueous medium contained in the inkjet textile printing treatment liquid, for example, the same organic solvent contained in the aqueous medium and its content. When the organic solvent is contained, the content of the organic solvent is preferably, for example, 3% by mass or more and 50% by mass or less relative to the ink, from the viewpoint of obtaining an ink with a viscosity that allows stable ejection and that is inhibited from drying. Furthermore, the aqueous medium may function as a solvent or a dispersion medium in the ink. The content of the aqueous medium is not particularly limited and may be the remainder. Specifically, the content of the aqueous medium is, for example, preferably 5% by mass or more and 70% by mass or less, and more preferably 10% by mass or more and 60% by mass or less, relative to the ink.

[0066] The ink may contain binder resin particles for the purpose of improving image fixation. The binder resin particles may be present in a dispersed state in an aqueous medium. The binder resin particles can function as a binder that binds the fabric, which is the object of textile printing, to a coloring material such as a pigment. Therefore, by including the binder resin particles in the ink, a printed product with excellent image fixation can be obtained.

[0067] The resin contained in the binder resin particles is not particularly limited, and examples thereof include urethane resin, acrylic resin, methacrylic resin, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-maleic acid copolymer, vinylnaphthalene-acrylic acid copolymer, vinylnaphthalene-methacrylic acid copolymer, and vinylnaphthalene-maleic acid copolymer. Among these, urethane resin is preferred as the resin contained in the binder resin particles. The content of urethane resin in the binder resin particles is preferably 80% by mass or more, and may be 100% by mass. In other words, the binder resin particles may be particles made of urethane resin.

[0068] The content of the binder resin particles is not particularly limited, but from the viewpoint of improving image fixation and maintaining stable ink ejection, it is preferably 1% by mass or more and 20% by mass or less, and more preferably 2% by mass or more and 10% by mass or less, relative to the ink. A high content of the binder resin particles (for example, 1% by mass or more) tends to improve image fixation, while a low content of the binder resin particles (for example, 20% by mass or less) allows stable ink ejection.

[0069] The ink may contain a surfactant for the purpose of adjusting the surface tension, etc. Furthermore, by containing a surfactant in the ink, the wettability of the ink to the fabric to be recorded is also improved. The surfactant is not particularly limited, and may be any of a nonionic surfactant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, etc. Furthermore, examples of the surfactant include the same surfactants as those contained in the inkjet textile printing treatment liquid.

[0070] The content of the surfactant is not particularly limited, but is preferably 0.06% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 5% by mass or less, and more preferably 0.5% by mass or more and 2% by mass or less, relative to the ink.

[0071] The inkjet textile printing ink may further contain known additives (more specifically, a dissolution stabilizer, a drying inhibitor, an antioxidant, a viscosity adjuster, a pH adjuster, an anti-mold agent, etc.) as needed.

[0072] The ink is produced by, for example, using a mixer to mix the colorant (pigment), the aqueous medium, and optional components (for example, binder resin particles, surfactants, etc.) The mixing time is not particularly limited, and is preferably, for example, from 1 minute to 30 minutes.

[0073] (Post-treatment liquid) The post-treatment liquid is not particularly limited as long as it is a treatment liquid that can be used as a post-treatment liquid in an inkjet textile printing method. Examples of the post-treatment liquid include a post-treatment liquid containing a silicone oil emulsion. By including the silicone oil emulsion in the post-treatment liquid, the slipperiness of the fabric surface can be improved and the friction fastness can be improved. Furthermore, the post-treatment liquid may contain an aqueous medium as a main component (for example, 50% by mass or more), and may contain a surfactant as necessary.

[0074] The silicone oil is not particularly limited, and can be exemplified by dimethylsilicone oil, amino group-containing silicone oil, carboxy group-containing silicone oil, phenolic hydroxy group-containing silicone oil, silanol group-containing silicone oil, epoxy group-containing silicone oil, mercapto group-containing silicone oil, phenyl group-containing silicone oil, long-chain alkyl group-containing silicone oil etc.The silicone oil emulsion can be the emulsion that contains one of these silicone oils alone, or can be the emulsion that contains two or more of them in combination.In addition, the silicone oil emulsion itself can be used alone, or can be used in combination of two or more.

[0075] The content of the silicone oil emulsion is not particularly limited, but from the viewpoint of improving the friction resistance, it is preferably, for example, from 1% by mass to 35% by mass relative to the post-treatment liquid.

[0076] The aqueous medium contained in the post-treatment liquid is not particularly limited as long as it contains water, and may be, for example, the same as the aqueous medium contained in the inkjet textile printing treatment liquid (or the aqueous medium contained in the ink), for example, the same organic solvent contained in the aqueous medium and its content. When the organic solvent is contained, the content of the organic solvent may be, for example, 3% by mass or more and 50% by mass or less relative to the post-treatment liquid, from the viewpoint of obtaining a post-treatment liquid having a viscosity that allows stable ejection and that is inhibited from drying. Furthermore, the aqueous medium may function as a solvent or a dispersion medium in the post-treatment liquid. The content of the aqueous medium is not particularly limited and may be the remainder of the silicone oil emulsion, etc., and is preferably, for example, 50% by mass or more and 90% by mass or less, and more preferably 55% by mass or more and 70% by mass or less, relative to the post-treatment liquid.

[0077] The post-treatment liquid may contain a surfactant for the purpose of adjusting the surface tension, etc. Furthermore, by containing a surfactant in the post-treatment liquid, the wettability of the post-treatment liquid with respect to the fabric to be recorded is also improved. The surfactant is not particularly limited, and may be any of a nonionic surfactant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, etc.

[0078] The content of the surfactant is not particularly limited, but is preferably 0% by mass or more and 5% by mass or less, and more preferably 0.1% by mass to 5% by mass, relative to the post-treatment liquid.

[0079] The post-treatment liquid may further contain known additives (more specifically, a dissolution stabilizer, a drying inhibitor, an antioxidant, a viscosity adjuster, a pH adjuster, an anti-mold agent, etc.) as needed.

[0080] The post-treatment liquid is produced by, for example, using a stirrer to mix the silicone oil emulsion, the aqueous medium, and optional components. The mixing time is not particularly limited, but is preferably, for example, from 1 minute to 30 minutes.

[0081] [Inkjet Printing Method] The inkjet printing method using the inkjet textile printing treatment liquid is not particularly limited as long as it is a method of forming an image on a fabric by ejecting (inkjet ejecting) the inkjet textile printing treatment liquid and the ink onto the fabric. Specific examples of the inkjet textile printing method include a method of sequentially ejecting the inkjet textile printing treatment liquid and the inkjet textile printing ink onto the fabric. That is, in an inkjet textile printing method according to another embodiment of the present disclosure, first, the inkjet textile printing treatment liquid is ejected onto the fabric to adhere thereto (pretreatment liquid ejecting step). Next, the ink is ejected onto the fabric to which the inkjet textile printing treatment liquid has been applied to adhere thereto (ink ejecting step). In this way, by sequentially ejecting the inkjet textile printing treatment liquid and the ink onto the fabric, a printed product having high color development and a good texture can be obtained while suppressing odor generation. In addition, in the inkjet textile printing method, the post-treatment liquid may be ejected onto the fabric to which the ink has been applied (post-treatment liquid ejection step). The inkjet textile printing method can be performed, for example, by an inkjet textile printing apparatus described below.

[0082] [Inkjet Textile Printing Apparatus] The inkjet textile printing apparatus is not particularly limited as long as it is an apparatus that performs the inkjet textile printing method and can perform the pretreatment liquid ejection step and the ink ejection step. That is, an inkjet textile printing apparatus according to another embodiment of the present disclosure includes a pretreatment liquid head that ejects and deposits the inkjet textile printing treatment liquid onto a fabric, and an ink head that ejects and deposits the ink onto the fabric to which the pretreatment liquid has been deposited. As described above, the inkjet coating apparatus can sequentially eject the inkjet textile printing treatment liquid and the ink onto the fabric, thereby suppressing odor generation and producing a printed product with high color development and a good texture. The inkjet textile printing apparatus may further include a posttreatment liquid head that ejects and deposits the posttreatment liquid onto the fabric to which the ink has been deposited. Examples of the inkjet textile printing apparatus include the inkjet textile printing apparatus shown in FIG. 1 . 1 is a schematic diagram partially illustrating the configuration of an inkjet textile printing apparatus 10 using the inkjet textile printing treatment liquid according to one embodiment of the present disclosure (an inkjet textile printing apparatus 10 according to another embodiment of the present disclosure). Also, Fig. 1 shows each component diagrammatically, and the size, number, etc. of each component may be changed as appropriate.

[0083] The inkjet printing apparatus 10 ejects (inkjet ejects) the inkjet printing treatment liquid (pre-treatment liquid), the ink, and the post-treatment liquid onto an object (fabric) P to be printed.

[0084] 1, the inkjet printing apparatus 10 includes a pretreatment liquid head 5, an ink head 4, a posttreatment liquid head 6, and a mounting table 3. The ink head 4 may include a first ink head 4a, a second ink head 4b, a third ink head 4c, and a fourth ink head 4d. The pretreatment liquid head 5, the ink head 4, and the posttreatment liquid head 6 are inkjet heads.

[0085] The pretreatment liquid head 5 ejects the pretreatment liquid onto at least an image formation area of ​​the printing object P. The pretreatment liquid head 5 is not particularly limited, and examples thereof include a piezo type head and a thermal inkjet type head. The inkjet printing apparatus 10 may include one or more pretreatment liquid tanks (not shown) that contain the inkjet printing treatment liquid. In this case, the inkjet printing treatment liquid is supplied from the pretreatment liquid tank to the pretreatment liquid head 5.

[0086] The ink heads 4 eject the ink onto an image formation area of ​​the printing object P. The first ink head 4a, second ink head 4b, third ink head 4c, and fourth ink head 4d of the ink heads 4 eject ink of different colors (e.g., yellow ink, magenta ink, cyan ink, and black ink), respectively. The number of ink heads 4 is not limited to four, and the number of ink heads 4 may be one to three, or five or more. The ink heads 4 are not particularly limited, but examples thereof include piezo-type heads and thermal inkjet-type heads. The inkjet printing device 10 may include one or more ink tanks (not shown) that contain the ink, and in this case, a treatment liquid is supplied to the ink heads 4 from the ink tanks.

[0087] The post-treatment liquid head 6 ejects the post-treatment liquid onto at least an image formation area of ​​the printing object P. The post-treatment liquid head 6 is not particularly limited, but examples thereof include a piezo type head and a thermal inkjet type head. The inkjet printing apparatus 10 may include one or more post-treatment liquid tanks (not shown) that contain the post-treatment liquid. In this case, the post-treatment liquid is supplied from the post-treatment liquid tank to the post-treatment liquid head 6.

[0088] A printing object P is placed on the placement table 3. The pretreatment liquid head 5, the ink head 4, and the posttreatment liquid head 6 are disposed above the placement table 3 so that the inkjet printing treatment liquid (pretreatment liquid), the ink, and the posttreatment liquid can be ejected onto the printing object P. By driving a motor (not shown), the placement table 3 moves horizontally in a direction from the pretreatment liquid head 5 toward the posttreatment liquid head 6 (for example, to the right in FIG. 1 ). The placement table 3 moves horizontally, thereby transporting the printing object P on the placement table 3.

[0089] In the inkjet printing method (production of a printed item), first, a mounting table 3 on which an object to be printed P is placed moves horizontally, and the object to be printed P is transported to a position facing the pretreatment liquid head 5. The pretreatment liquid head 5 ejects the pretreatment liquid onto the object to be printed P. The pretreatment liquid head 5 may eject the pretreatment liquid only onto an image formation area of ​​the object to be printed P, or may eject the inkjet printing treatment liquid (pretreatment liquid) onto an area wider than the image formation area of ​​the object to be printed P, or may eject the pretreatment liquid onto the entire surface of the object to be printed P. The pretreatment liquid head 5 may eject the pretreatment liquid only onto the image formation area of ​​the object to be printed P, in order to reduce the amount of pretreatment liquid used and prevent deterioration in the feel of the printed item.

[0090] After the pretreatment liquid is ejected from the pretreatment liquid head 5, the mounting table 3 on which the object to be printed P is placed further moves horizontally, and the object to be printed P is transported to a position facing the ink head 4. Then, the ink is ejected from the ink head 4 onto an image formation area of ​​the object to be printed P. In this way, an image is formed with the inkjet printing ink in the image formation area of ​​the object to be printed P.

[0091] After ink is ejected from the ink head 4, the mounting table 3 on which the object to be printed P is placed further moves horizontally, and the object to be printed P is transported to a position facing the posttreatment liquid head 6. The posttreatment liquid head 6 ejects the posttreatment liquid onto at least the image formation area of ​​the object to be printed P. The posttreatment liquid head 6 may eject the posttreatment liquid only onto the image formation area of ​​the object to be printed P, or may eject the posttreatment liquid onto an area wider than the image formation area of ​​the object to be printed P, or may eject the posttreatment liquid onto the entire surface of the object to be printed P. The posttreatment liquid head 6 may eject the posttreatment liquid only onto the image formation area of ​​the object to be printed P, in order to reduce the amount of posttreatment liquid used and prevent a deterioration in the feel of the printed object. In this way, a treatment film is formed by the posttreatment liquid on the image formed in the image formation area of ​​the object to be printed P.

[0092] After the post-treatment liquid is ejected from the post-treatment liquid head 6, the mounting table 3 on which the object to be printed P is placed further moves horizontally, and the object to be printed P is transported to a position facing a heating unit (not shown) that heats the object to be printed P. The heating unit heats the object to be printed P, thereby drying the pre-treatment liquid, the ink, and the post-treatment liquid. The heating temperature is not particularly limited and may be, for example, 120°C or higher and 180°C or lower, so as to be able to suitably dry the pre-treatment liquid, the ink, and the post-treatment liquid. The heating time is not particularly limited and may be, for example, 1 minute or longer and 10 minutes or shorter, so as to be able to suitably dry the pre-treatment liquid, the ink, and the post-treatment liquid. The volatile components contained in the pre-treatment liquid, the ink, and the post-treatment liquid that have been attached to the object to be printed P are dried by the heating, thereby facilitating the fixation of the pre-treatment liquid, the ink, and the post-treatment liquid to the object to be printed P. As a result, an image is formed with the ink, and a printing object P (printed item) is formed that has been treated with the pre-treatment liquid and the post-treatment liquid.

[0093] In the inkjet printing apparatus 10, for example, instead of the stage 3 moving horizontally as described above, the stage 3 may be fixed and the pretreatment liquid head 5, the ink head 4, and the posttreatment liquid head 6 may move horizontally.

[0094] Next, an inkjet recording apparatus that can use the inkjet textile printing treatment liquid (pretreatment liquid) will be described in detail as an inkjet textile printing apparatus. Hereinafter, an inkjet printer equipped with an ink head that ejects ink onto a wide, long recording medium will be exemplified as a specific example of the inkjet recording apparatus. Here, this inkjet printer will be described with reference to FIGS. 2 to 4.

[0095] FIG. 2 is a perspective view showing the overall configuration of an inkjet printer 100 that uses an inkjet textile printing treatment liquid according to an embodiment of the present disclosure. The inkjet printer 100 is a device that prints images such as letters and patterns on a fabric, which is the object of textile printing, using an inkjet method, and may be, for example, a device that performs digital textile printing. The inkjet printer may also be a device that can print various images on recording media other than the fabric, which is the object of textile printing, such as paper sheets and resin sheets. FIG. 3 is a schematic cross-sectional view taken along line III-III in FIG. 2. FIG. 4 is an enlarged perspective view of the carriage shown in FIG. 2.

[0096] The inkjet printer 100 is a printer that prints images on a wide and long workpiece W (recording medium) using an inkjet system. The inkjet printer 100 can also be used as a printer that forms an image on a fabric, which is the workpiece W to be printed. That is, in this embodiment, the inkjet printer 100 is used as an inkjet textile printing device. Note that in the inkjet textile printing device according to this embodiment, the recording medium is fabric, but here the recording medium is also referred to as the workpiece W. The width of the workpiece W is, for example, several meters. As shown in FIG. 2 , the inkjet printer 100 includes an apparatus frame 11 and a work transport unit 20 and a carriage 300 incorporated into this apparatus frame 11. Note that in this embodiment, the left-to-right direction is the main scanning direction S ( FIG. 4 ) when printing on the workpiece W, and the direction from rear to front is the sub-scanning direction (the transport direction F of the workpiece W, which intersects with the main scanning direction S).

[0097] The device frame 11 forms a framework for mounting various components of the inkjet printer 100. The work transport unit 20 is a mechanism that intermittently feeds (transports) the workpiece W so that the workpiece W progresses in a transport direction F from rear to front in a printing area where inkjet printing processing is performed. The carriage 300 is equipped with an ink head 4, a pre-treatment liquid head 5, a post-treatment liquid head 6, and a sub-tank 7, and moves back and forth in a main scanning direction S (left and right direction) that intersects with the transport direction F of the workpiece W during the inkjet printing processing.

[0098] The device frame 11 includes a central frame 111, a right frame 112, and a left frame 113. The central frame 111 forms a framework for mounting various components of the inkjet printer 100, and has a left-to-right width corresponding to the work transport unit 20. The right frame 112 and the left frame 113 are erected to the right and left of the central frame 111, respectively. Between the right frame 112 and the left frame 113 is the printing area 12 where printing processing is performed on the workpiece W.

[0099] The right frame 112 forms a maintenance area 13. The maintenance area 13 is an area where the carriage 300 is retracted when the printing process is not being performed. In the maintenance area 13, cleaning processes, purging processes, etc. are performed on the nozzles (ejection holes) of the ink heads 4, pre-treatment liquid heads 5, and post-treatment liquid heads 6, and caps are also fitted. The left frame 113 forms a turn-back area 14 for the carriage 300. The turn-back area 14 is an area where the carriage 300 temporarily enters when it performs a main scan in the opposite direction after performing a main scan in the opposite direction across the printing area 12 from right to left during the printing process.

[0100] A carriage guide 15 for reciprocating the carriage 300 in the left-right direction is attached to the upper side of the device frame 11. The carriage guide 15 is a flat plate-shaped member that is long in the left-right direction, and is disposed above the work transport unit 20. A timing belt 16 is attached to the carriage guide 15 so as to be able to move in a circular motion in the left-right direction (main scanning direction). The timing belt 16 is an endless belt that is driven to move in a circular motion in the left or right direction.

[0101] The carriage guide 15 is equipped with a pair of upper and lower guide rails 17 that extend parallel to the left and right and that hold the carriage 300 in a state that allows it to move back and forth in the main scanning direction S. The carriage 300 is engaged with the guide rails 17. The carriage 300 is also fixed to the timing belt 16. As the timing belt 16 moves orbitally leftward or rightward, the carriage 300 moves leftward or rightward along the carriage guide 15 while being guided by the guide rails 17.

[0102] Next, explanation will be made mainly with reference to Figure 3. The work transport unit 20 includes a feed roller 21 that pays out the work W before printing, and a take-up roller 22 that takes up the work W after printing. The feed roller 21 is located at the rear lower part of the device frame 11, and is a take-up shaft for a feed roll WA that is a roll of the work W before printing. The take-up roller 22 is located at the front lower part of the device frame 11, and is a take-up shaft for a take-up roll WB that is a roll of the work W after the printing process. A first motor M1 is attached to the take-up roller 22, which rotates the take-up roller 22 about its axis and performs the operation of winding up the work W.

[0103] The path between the delivery roller 21 and the take-up roller 22 and passing through the printing area 12 is the transport path for the workpiece W. Arranged on this transport path, in order from upstream, are a first tension roller 23, a work guide 24, a transport roller 25 and a pinch roller 26, a turn-back roller 27, and a second tension roller 28. The first tension roller 23 applies a predetermined tension to the workpiece W on the upstream side of the transport roller 25. The work guide 24 changes the transport direction of the workpiece W from upward to forward, allowing the workpiece W to enter the printing area 12.

[0104] The transport roller 25 is a roller that generates a transport force that intermittently feeds the workpiece W in the printing area 12. The transport roller 25 is driven to rotate around its axis by the second motor M2, and intermittently transports the workpiece W forward (in a predetermined transport direction F) so that the workpiece W passes through the printing area 12 (image forming position) facing the carriage 300. The pinch roller 26 is disposed opposite the transport roller 25 from above, and forms a transport nip portion with the transport roller 25.

[0105] The turn-back roller 27 changes the transport direction of the workpiece W that has passed through the printing area 12 from forward to downward, and guides the workpiece W after printing processing to the take-up roller 22. The second tension roller 28 applies a predetermined tension to the workpiece W downstream of the transport roller 25. A platen 29 is disposed below the transport path of the workpiece W in the printing area 12.

[0106] The carriage 300 is cantilevered on the guide rail 17 and moves back and forth in a main scanning direction S (left and right direction in FIGS. 2 and 3 ) that intersects with the transport direction F (orthogonal in FIGS. 2 and 3 ). The carriage 300 includes a carriage frame 30, and an ink head 4, a pre-treatment liquid head 5, a post-treatment liquid head 6, and a sub-tank 7 ( FIG. 4 ) that are mounted on the carriage frame 30. The carriage frame 30 includes a head support frame 31 and a back frame 32.

[0107] The head support frame 31 is a horizontal plate that holds the ink heads 4, the pre-treatment liquid heads 5, and the post-treatment liquid heads 6. The back frame 32 is a vertical plate that extends upward from the rear end edge of the head support frame 31. As described above, the timing belt 16 is fixed to the back frame 32. Furthermore, the guide rails 17 are engaged with the back frame 32. That is, in the example shown in Fig. 3, the back frame 32 is an engaging portion that holds the back frame 32 in a cantilevered state on the guide rails 17. The head support frame 31 is a horizontal plate whose rear end side is supported in a cantilevered state on the guide rails 17 by the engaging portion.

[0108] The cantilevered state refers to a state in which the engagement portion (back frame 32), which is a portion of the carriage 300 that is held by the guide rail 17, which is a holding member, is present only on one side, either upstream or downstream, from the center of the carriage 300 in the transport direction F, and no other engagement portion is present on the side opposite to the side where the engagement portion is present. The engagement portion may also be located outside the range in which the ink heads 4, pretreatment liquid heads 5, and posttreatment liquid heads 6 are arranged in the transport direction F. In other words, the engagement portion may be located only on the upstream side or only on the downstream side of the range in which the ink heads 4, pretreatment liquid heads 5, and posttreatment liquid heads 6 are arranged in the transport direction F.

[0109] The carriage 300 will now be further described. Fig. 4 is an enlarged perspective view of the carriage 300 shown in Fig. 2. Fig. 4 shows the transport direction F (sub-scanning direction) of the workpiece W and the main scanning direction S, which is the direction of movement of the carriage 300. Fig. 4 shows an example in which the carriage 300 is equipped with a plurality of ink heads 4 that eject ink for image formation onto the workpiece W, a pre-treatment liquid head 5 and a post-treatment liquid head 6 that eject non-color-forming treatment liquid, and a plurality of sub-tanks 7 that supply the ink, treatment liquid, and post-treatment liquid to these heads 4 to 6.

[0110] Each ink head 4 has a number of nozzles (ink ejection holes) that eject ink droplets using an ejection method such as a piezoelectric method using a piezoelectric element or a thermal method using a heating element, and ink passages that guide ink to the nozzles. For example, the inks described above can be used. In the example shown in FIG. 4, the multiple ink heads 4 are capable of ejecting eight colors of ink. The ink heads 4 are mounted on the head support frame 31 of the carriage 300 so as to be aligned in two rows in the main scanning direction S. Each color ink head 4 has two heads.

[0111] In the example shown in FIG. 4 , the ink heads 4 specifically include a first upstream ink head 41A and a first downstream ink head 41B. These ink heads 4 eject, for example, yellow ink. The ink heads 4 also include a second upstream ink head 42A and a second downstream ink head 42B. These ink heads 4 eject, for example, magenta ink. Similarly, as shown in FIG. 4 , two ink heads 4 ejecting the same color ink are arranged at positions offset from each other in the transport direction F and the main scanning direction S. These two ink heads 4 form a set, making a total of eight sets of ink heads 4 (the first upstream ink head 41A to the eighth upstream ink head 48A, and the first downstream ink head 41B to the eighth downstream ink head 48B) that eject inks of different colors. The inks described above can be used.

[0112] The pre-treatment liquid head 5 and the post-treatment liquid head 6 are disposed at positions different from the ink heads 4 in the transport direction F. The pre-treatment liquid head 5 is disposed upstream of the ink heads 4 in the transport direction F. FIG. 4 shows an example in which one pre-treatment liquid head 5 is disposed near the left end of the array of ink heads 4. Similarly, the post-treatment liquid head 6 is disposed downstream of the ink heads 4 in the transport direction F. FIG. 4 shows an example in which one post-treatment liquid head 6 is disposed at the right end of the array of ink heads 4. In other examples of inkjet recording devices, for example, a plurality of pre-treatment liquid heads 5 or a plurality of post-treatment liquid heads 6 may be disposed.

[0113] A series of heads along the main scanning direction S, which are made up of the ink heads 4, pretreatment liquid heads 5, and posttreatment liquid heads 6, will be referred to as a row of heads, or simply as a row. Also, a series of heads along the transport direction F, which are made up of the ink heads 4, pretreatment liquid heads 5, and posttreatment liquid heads 6, will be referred to as a row of heads, or simply as a row.

[0114] The pretreatment liquid head 5 ejects a pretreatment liquid for performing a predetermined pretreatment on the workpiece W. The pretreatment liquid is ejected from the pretreatment liquid head 5 onto a position on the workpiece W where ink has not yet been ejected from the ink head 4. The inkjet printing treatment liquid can be used as the pretreatment liquid. The inkjet printing treatment liquid is a non-color-forming treatment liquid.

[0115] The post-treatment liquid head 6 ejects a post-treatment liquid for performing a predetermined post-treatment on the workpiece W to which ink has adhered. The post-treatment liquid is ejected from the post-treatment liquid head 6 onto the position of the workpiece W after the ink has been ejected from the ink head 4. The post-treatment liquid can be the same as above. The post-treatment liquid is a non-color-forming treatment liquid.

[0116] Here, a non-color-forming treatment liquid refers to a treatment liquid that, when printed alone on a recording medium, is not perceived as having a color by the naked eye. Colors here include colors with a saturation of zero, such as black, white, and gray. A non-color-forming treatment liquid is essentially a transparent liquid; however, when viewed in its liquid state, for example, 1 liter of treatment liquid may not be completely transparent, but may appear slightly white. Such colors are so faint that, when printed alone on a recording medium, they are not perceived as having a color by the naked eye. Note that, depending on the type of treatment liquid, when printed alone on a recording medium, changes such as gloss may appear on the recording medium, but such a state is not considered color-forming.

[0117] In the inkjet printer 100, by using the ink, the inkjet textile printing treatment liquid (pretreatment liquid), and the posttreatment liquid as the ink, pretreatment liquid, and posttreatment liquid, it is possible to form an image on the fabric that has high color development and a good texture while suppressing the generation of odor.

[0118] 2 to 4, the pretreatment liquid and the posttreatment liquid may be ejected onto substantially the entire surface of the workpiece W, or the pretreatment liquid and the posttreatment liquid may be selectively ejected in accordance with the image to be printed, similar to ink. Furthermore, the pretreatment liquid, the ink, and the posttreatment liquid are ejected in this order onto the portion of the workpiece W where a color is to be printed in accordance with the image. In this case, the ink may be of one color or multiple colors. Basically, the pretreatment liquid and the posttreatment liquid are not ejected onto the portion where no color is to be printed, i.e., the portion where no ink is ejected.

[0119] 4, openings 31H are provided in the head support frame 31 at positions where the heads are arranged. The ink heads 4, the pre-treatment liquid heads 5, and the post-treatment liquid heads 6 are attached to the head support frame 31 so as to be fitted into the respective openings 31H. Nozzles arranged on the lower end surfaces of the heads (ink heads 4, pre-treatment liquid heads 5, and post-treatment liquid heads 6) are exposed from the respective openings 31H.

[0120] The plurality of sub-tanks 7 are supported by the carriage 300 above the respective heads (ink head 4, pre-treatment liquid head 5, and post-treatment liquid head 6) via a holding frame (not shown). The plurality of sub-tanks 7 are provided corresponding to each of the ink heads 4, pre-treatment liquid heads 5, and post-treatment liquid heads 6. The ink, pre-treatment liquid, or post-treatment liquid is supplied to each sub-tank 7 from a main tank 90 (described below) that contains the ink, pre-treatment liquid, or post-treatment liquid, and these are supplied to each of the heads 4, 5, and 6. The sub-tanks 7 and the respective heads 4, 5, and 6 are connected by conduits (not shown in FIG. 4 ).

[0121] 4, the subtanks 7 specifically include a first supply subtank 71A to an eighth supply subtank 78A, a pre-processing supply subtank 7FA, and a post-processing supply subtank 7RA, which are arranged on the rear side along the main scanning direction S. Furthermore, the subtanks 7 further include a first recovery subtank 71B to an eighth recovery subtank 78B, a pre-processing recovery subtank 7FB, and a post-processing recovery subtank 7RB, which are arranged on the front side along the main scanning direction S.

[0122] The first supply subtank 71A and the first recovery subtank 71B located at the leftmost side of the carriage 300 store, for example, yellow ink containing a pigment. In this case, the first supply subtank 71A supplies yellow ink to the first upstream ink head 41A and the first downstream ink head 41B (both referred to as supply destinations). Meanwhile, the first recovery subtank 71B stores yellow ink recovered from the first upstream ink head 41A and the first downstream ink head 41B. As described above, a portion of the yellow ink is ejected toward the workpiece W from the first upstream ink head 41A and the first downstream ink head 41B. Similarly, the second supply subtank 72A supplies magenta ink to, for example, the second upstream ink head 42A and the second downstream ink head 42B. Meanwhile, the second recovery subtank 72B stores magenta ink recovered from the second upstream ink head 42A and the second downstream ink head 42B. The other sub-tanks, from the third sub-tank to the eighth sub-tank, also have the same structure and function as those described above.

[0123] The pre-treatment supply sub-tank 7FA supplies the pre-treatment liquid to the pre-treatment liquid head 5, and the pre-treatment recovery sub-tank 7FB recovers the pre-treatment liquid from the pre-treatment liquid head 5. The post-treatment supply sub-tank 7RA supplies the post-treatment liquid to the post-treatment liquid head 6, and the post-treatment recovery sub-tank 7RB recovers the post-treatment liquid from the post-treatment liquid head 6.

[0124] As described above, the inkjet printer 100 is an all-in-one printer in which three types of heads - the ink head 4, the pre-treatment liquid head 5, and the post-treatment liquid head 6 - are mounted on a single carriage 300. With this inkjet printer 100, for example, in the printing process of performing inkjet printing on fabric in digital textile printing, the pre-treatment liquid ejection process and the post-treatment liquid ejection process can be executed integrally. This makes it possible to simplify the textile printing process and make the textile printing device more compact.

[0125] The inkjet printer 100 uses a serial printing method to perform printing on the workpiece W. Specifically, if the workpiece W is wide, it is not possible to print while continuously feeding the workpiece W. The serial printing method is a printing method in which a carriage 300 carrying ink heads 4 of each color moves back and forth in the main scanning direction S, and the workpiece W is intermittently fed in the transport direction F, repeatedly.

[0126] In the inkjet printer 100, a band-shaped image is printed while the carriage 300 moves in the forward direction, which is one of the main scanning directions S. During this main scanning in the forward direction, the feeding of the workpiece W is stopped. After printing the band-shaped image, the workpiece W is sent out in the transport direction F by a predetermined pitch. At this time, the carriage 300 waits in the turn-back area 14 on the left end side. After sending out the workpiece W, the carriage 300 turns back in the return direction, which is opposite to the forward direction, as the timing belt 16 moves in reverse. The workpiece W is in a stationary state. Then, while moving in the return direction, the carriage 300 prints the next band-shaped image upstream of the previous band-shaped image. Similar operations are repeated thereafter.

[0127] As described above, this specification discloses various aspects of the technology, the main technologies of which are summarized below.

[0128] The inkjet printing treatment liquid according to the first aspect is an inkjet printing treatment liquid containing a water-soluble cationic polymer and ammonium formate.

[0129] The inkjet printing treatment liquid according to a second aspect is the inkjet printing treatment liquid according to the first aspect, wherein the content of the ammonium formate in the inkjet printing treatment liquid is 0.1% by mass or more and 25% by mass or less, based on the inkjet printing treatment liquid.

[0130] The inkjet printing treatment liquid according to a third aspect is the inkjet printing treatment liquid according to the first or second aspect, wherein the water-soluble cationic polymer forms a salt with succinic acid anions.

[0131] A treatment liquid for inkjet printing according to a fourth aspect is the treatment liquid for inkjet printing according to any one of the first to third aspects, wherein the content of the water-soluble cationic polymer is 0.3% by mass or more and 35% by mass or less with respect to the treatment liquid for inkjet printing.

[0132] The inkjet printing treatment liquid according to a fifth aspect is the inkjet printing treatment liquid according to any one of the first to fourth aspects, wherein the pH is from 7 to 9.5.

[0133] The inkjet printing treatment liquid according to a sixth aspect is the inkjet printing treatment liquid according to any one of the first to fifth aspects, further comprising a metal salt.

[0134] The inkjet printing treatment liquid according to the seventh aspect is the inkjet printing treatment liquid according to any one of the first to sixth aspects, which is a pretreatment liquid.

[0135] The treatment liquid for inkjet printing according to an eighth aspect is the treatment liquid for inkjet printing according to any one of the first to seventh aspects, further comprising an organic acid ammonium salt formed from an organic acid having a vapor pressure of 2 kPa or less at 20°C and ammonia.

[0136] A treatment liquid for inkjet printing according to a ninth aspect is the treatment liquid for inkjet printing according to the eighth aspect, in which the content of the organic acid ammonium salt is 10% by mass or more with respect to the water-soluble cationic polymer.

[0137] A treatment liquid for inkjet printing according to a tenth aspect is a treatment liquid for inkjet printing, comprising a water-soluble cationic polymer and an organic acid ammonium salt, which is made of an organic acid and ammonia and has a vapor pressure of 2 kPa or less at 20°C.

[0138] An inkjet printing ink set according to an eleventh aspect is an inkjet printing ink set having the inkjet printing treatment liquid according to any one of the first to tenth aspects and an inkjet printing ink containing a pigment.

[0139] An inkjet textile printing method according to a twelfth aspect is an inkjet textile printing method comprising ejecting and adhering the inkjet textile printing treatment liquid according to any one of the first to tenth aspects onto a fabric, and ejecting and adhering an inkjet textile printing ink containing a pigment onto the fabric to which the inkjet textile printing treatment liquid has been adhered.

[0140] An inkjet textile printing apparatus according to a thirteenth aspect is an inkjet textile printing apparatus including: a treatment liquid head that ejects and deposits the inkjet textile printing treatment liquid according to any one of the first to tenth aspects onto a fabric; and an ink head that ejects and deposits an inkjet textile printing ink containing a pigment onto the fabric to which the inkjet textile printing treatment liquid has been deposited.

[0141] According to the present invention, it is possible to provide an inkjet textile printing treatment liquid, an inkjet textile printing ink set, an inkjet textile printing method, and an inkjet textile printing apparatus that can produce printed textiles with high color development and good texture while suppressing odor generation.

[0142] The present disclosure will be explained in more detail below using examples, but the present disclosure is not limited to these examples in any way.

[0143] [Example 1] As a water-soluble cationic polymer, 3.0 parts by mass (solid content) of a copolymer of diallyldimethylammonium chloride and sulfur dioxide (PAS-A5 manufactured by Nittobo Medical Co., Ltd., weight average molecular weight Mw 4000) in which at least a part of the chloride ions have been ion-exchanged with succinate anions, 8.2 parts by mass of ammonium formate (manufactured by Yoneyama Chemical Industry Co., Ltd.), 0.5 parts by mass of magnesium acetate (manufactured by Yoneyama Chemical Industry Co., Ltd.) as a metal salt, and 0.5 parts by mass of a nonionic surfactant (manufactured by Yoneyama Chemical Industry Co., Ltd.) as a surfactant. 0.02 parts by mass of a surfactant (silicone-based surfactant, Silface SAG503A manufactured by Nissin Chemical Industry Co., Ltd.), 37 parts by mass of 3-methyl-1,5-pentanediol (MPD manufactured by Kuraray Co., Ltd.) as an organic solvent, 1.0 part by mass of a 1 mol / L sodium hydroxide solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a pH adjuster, and the balance (50.28 parts by mass) of water were mixed and then filtered through a 5 μm filter to obtain an inkjet printing treatment liquid (pretreatment liquid 1) according to Example 1. The formulation of pretreatment liquid 1 was 3.0% by mass of the water-soluble cationic polymer, 8.2% by mass (1.30 mol / L) of ammonium formate, 0.5% by mass of the metal salt, 0.02% by mass of the surfactant, 37% by mass of the organic solvent, 1.0% by mass of the pH adjuster, and the balance (50.28% by mass) of water. The pH of the resulting pretreatment solution 1 was measured using a pH meter (D-71 manufactured by Horiba Ltd.) and found to be 7.21.

[0144] Example 2 3.0 parts by mass (solids content) of the water-soluble cationic polymer, 4.0 parts by mass of the ammonium formate, 0.5 parts by mass of the metal salt (magnesium acetate), 0.02 parts by mass of the surfactant (nonionic surfactant), 40 parts by mass of the organic solvent (3-methyl-1,5-pentanediol), 1.0 part by mass of the pH adjuster, and the balance (51.48 parts by mass) of water were mixed and then filtered through a 5 μm filter to obtain an inkjet printing treatment liquid (pre-treatment liquid 2) according to Example 2. The formulation of pre-treatment liquid 2 was 3.0% by mass of the water-soluble cationic polymer, 4.0% by mass (0.63 mol / L) of the ammonium formate, 0.5% by mass of the metal salt, 0.02% by mass of the surfactant, 40% by mass of the organic solvent, 1.0% by mass of the pH adjuster, and the balance (51.48% by mass) of water. The pH of the obtained pretreatment solution 2 was measured with the pH meter and found to be 7.15.

[0145] Example 3 3.0 parts by mass (solids content) of the water-soluble cationic polymer, 10 parts by mass of the ammonium formate, 0.5 parts by mass of the metal salt (magnesium acetate), 0.02 parts by mass of the surfactant (nonionic surfactant), 35 parts by mass of the organic solvent (3-methyl-1,5-pentanediol), 1.0 part by mass of the pH adjuster, and the balance (50.48 parts by mass) of water were mixed and then filtered through a 5 μm filter to obtain an inkjet printing treatment liquid (pre-treatment liquid 3) according to Example 3. The formulation of pre-treatment liquid 3 was 3.0% by mass of the water-soluble cationic polymer, 10% by mass (1.59 mol / L) of the ammonium formate, 0.5% by mass of the metal salt, 0.02% by mass of the surfactant, 35% by mass of the organic solvent, 1.0% by mass of the pH adjuster, and the balance (50.48% by mass) of water. The pH of the obtained pretreatment solution 3 was measured with the pH meter and found to be 7.22.

[0146] Example 4 3.0 parts by mass (solids content) of the water-soluble cationic polymer, 20 parts by mass of the ammonium formate, 0.5 parts by mass of the metal salt (magnesium acetate), 0.02 parts by mass of the surfactant (nonionic surfactant), 25 parts by mass of the organic solvent (3-methyl-1,5-pentanediol), 1.0 part by mass of the pH adjuster, and the balance (50.48 parts by mass) of water were mixed and then filtered through a 5 μm filter to obtain an inkjet printing treatment liquid (pre-treatment liquid 4) according to Example 4. The formulation of pre-treatment liquid 4 was 3.0% by mass of the water-soluble cationic polymer, 20% by mass (3.17 mol / L) of the ammonium formate, 0.5% by mass of the metal salt, 0.02% by mass of the surfactant, 25% by mass of the organic solvent, 1.0% by mass of the pH adjuster, and the balance (50.48% by mass) of water. The pH of the obtained pretreatment solution 4 was measured with the pH meter and found to be 7.25.

[0147] Example 5 3.0 parts by mass (solids content) of the water-soluble cationic polymer, 8.2 parts by mass of the ammonium formate, 0.02 parts by mass of the surfactant (nonionic surfactant), 37 parts by mass of the organic solvent (3-methyl-1,5-pentanediol), 1.0 part by mass of the pH adjuster, and the balance (50.78 parts by mass) of water were mixed and then filtered through a 5 μm filter to obtain an inkjet printing treatment liquid (pre-treatment liquid 5) according to Example 5. The formulation of pre-treatment liquid 5 was 3.0% by mass of the water-soluble cationic polymer, 8.2% by mass (1.30 mol / L) of the ammonium formate, 0.02% by mass of the surfactant, 37% by mass of the organic solvent, 1.0% by mass of the pH adjuster, and the balance (50.78% by mass) of water. The pH of the obtained pre-treatment liquid 5 was measured with the pH meter and found to be 7.20.

[0148] Comparative Example 1 3.0 parts by mass (solids content) of the water-soluble cationic polymer, 10 parts by mass of ammonium acetate (manufactured by Yoneyama Chemical Co., Ltd.), 0.5 parts by mass of the metal salt (magnesium acetate), 0.02 parts by mass of the surfactant (nonionic surfactant), 31 parts by mass of the organic solvent (3-methyl-1,5-pentanediol), and the balance (55.48 parts by mass) of water were mixed and then filtered through a 5 μm filter to obtain an inkjet printing treatment liquid (pretreatment liquid 6) according to Comparative Example 1. The formulation of pretreatment liquid 6 was 3.0% by mass of the water-soluble cationic polymer, 10% by mass (1.30 mol / L) of ammonium acetate, 0.5% by mass of the metal salt, 0.02% by mass of the surfactant, 31% by mass of the organic solvent, and the balance (55.48% by mass) of water. The pH of the obtained pretreatment liquid 6 was measured using the pH meter and found to be 7.05.

[0149] Comparative Example 2 3.0 parts by mass (solids content) of the water-soluble cationic polymer, 14 parts by mass of ammonium lactate (manufactured by Yoneyama Chemical Co., Ltd.), 0.5 parts by mass of the metal salt (magnesium acetate), 0.02 parts by mass of the surfactant (nonionic surfactant), 26 parts by mass of the organic solvent (3-methyl-1,5-pentanediol), 8.0 parts by mass of the pH adjuster, and the balance (48.48 parts by mass) of water were mixed and then filtered through a 5 μm filter to obtain an inkjet printing treatment liquid (pretreatment liquid 7) according to Comparative Example 2. The formulation of pretreatment liquid 7 was 3.0% by mass of the water-soluble cationic polymer, 14% by mass (1.31 mol / L) of the ammonium lactate, 0.5% by mass of the metal salt, 0.02% by mass of the surfactant, 26% by mass of the organic solvent, 8.0% by mass of the pH adjuster, and the balance (48.48% by mass) of water. The pH of the resulting pretreatment solution 7 was measured with the pH meter and found to be 7.30.

[0150] Comparative Example 3 3.0 parts by mass (solids content) of the water-soluble cationic polymer, 18 parts by mass of ammonium benzoate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 0.5 parts by mass of the metal salt (magnesium acetate), 0.02 parts by mass of the surfactant (nonionic surfactant), 25 parts by mass of the organic solvent (3-methyl-1,5-pentanediol), and the balance (53.48 parts by mass) of water were mixed and then filtered through a 5 μm filter to obtain an inkjet printing treatment liquid (pretreatment liquid 8) according to Comparative Example 3. The formulation of pretreatment liquid 8 was 3.0% by mass of the water-soluble cationic polymer, 18% by mass (1.29 mol / L) of the ammonium benzoate, 0.5% by mass of the metal salt, 0.02% by mass of the surfactant, 25% by mass of the organic solvent, and the balance (53.48% by mass) of water. The pH of the obtained pretreatment liquid 8 was measured using the pH meter and found to be 7.01.

[0151] Comparative Example 4 3.0 parts by mass (solids content) of the water-soluble cationic polymer, 15 parts by mass of ammonium succinate (manufactured by Kanto Chemical Co., Inc.), 0.5 parts by mass of the metal salt (magnesium acetate), 0.02 parts by mass of the surfactant (nonionic surfactant), 26 parts by mass of the organic solvent (3-methyl-1,5-pentanediol), and the balance (55.48 parts by mass) of water were mixed and then filtered through a 5 μm filter to obtain an inkjet printing treatment liquid (pretreatment liquid 9) according to Comparative Example 4. The formulation of pretreatment liquid 9 was 3.0% by mass of the water-soluble cationic polymer, 15% by mass (0.99 mol / L) of ammonium succinate, 0.5% by mass of the metal salt, 0.02% by mass of the surfactant, 26% by mass of the organic solvent, and the balance (55.48% by mass) of water. The pH of the obtained pretreatment liquid 9 was measured using the pH meter and found to be 7.23.

[0152] Comparative Example 5 3.0 parts by mass (solids content) of the water-soluble cationic polymer, 9.0 parts by mass of triammonium citrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 0.5 parts by mass of the metal salt (magnesium acetate), 0.02 parts by mass of the surfactant (nonionic surfactant), 31 parts by mass of the organic solvent (3-methyl-1,5-pentanediol), and the balance (56.48 parts by mass) of water were mixed and then filtered through a 5 μm filter to obtain an inkjet printing treatment liquid (pretreatment liquid 10) according to Comparative Example 5. The formulation of the pretreatment liquid 9 was 3.0% by mass of the water-soluble cationic polymer, 9.0% by mass (0.37 mol / L) of triammonium citrate, 0.5% by mass of the metal salt, 0.02% by mass of the surfactant, 31% by mass of the organic solvent, and the balance (56.48% by mass) of water. The pH of the obtained pretreatment liquid 10 was measured with the pH meter and found to be 7.11.

[0153] The inkjet printing treatment liquid according to Example 1 was prepared so that the content of ammonium formate was 1.30 mol / L, and the inkjet printing treatment liquids according to Comparative Examples 1 to 3 were prepared so that the content of organic acid ammonium salt was 1.30 mol / L. Since the organic acid ammonium salt contained in the inkjet printing treatment liquids according to Comparative Examples 4 and 5 cannot be dissolved up to 1.30 mol / L, the inkjet printing treatment liquids according to Comparative Examples 4 and 5 were prepared so that the organic acid ammonium salt was in the maximum amount that could be dissolved.

[0154] The ink-jet printing treatment liquid prepared as above was evaluated by the following methods.

[0155] The inkjet printing treatment liquid was ejected onto and adhered to a fabric to be printed, thereby obtaining a printed item. Specifically, the printed item was obtained as follows. First, a polyester tropical fabric (manufactured by Toray Industries, Inc.) was used as the fabric to be printed in the inkjet printing process. To produce the printed item, a flatbed printing jig (a flatbed inkjet recording device corresponding to FIG. 1 , equipped with the inkjet heads, a prototype manufactured by Kyocera Corporation) was used, in which inkjet heads (KJ4B manufactured by Kyocera Corporation) were arranged in the conveyance direction. The first inkjet head (downstream in the conveyance direction) was filled with the inkjet printing treatment liquid. The second inkjet head was filled with the inkjet printing ink described below. The third inkjet head (upstream in the conveyance direction) was filled with the post-treatment liquid described below. Using this flatbed printing jig, the inkjet textile printing treatment liquid, the inkjet textile printing ink, and the post-treatment liquid were each ejected at a rate of 10 g / m ２ , 20 g / m ２ , and 5 g / m ２ The ink was ejected from each head onto the polyester tropical fabric so that the ink was uniformly distributed over the entire surface of the fabric. The inkjet printing conditions were a distance of 3 mm between the fabric and the inkjet head, and an inkjet head temperature of 25°C. Next, the object to be printed onto which the inkjet printing treatment liquid, the inkjet printing ink, and the post-treatment liquid had been ejected was heated in an oven at 160°C for 3 minutes. By doing so, the inkjet printing treatment liquid, the inkjet printing ink, and the post-treatment liquid ejected onto the object to be printed were dried, and a printed item was obtained.

[0156] (Inkjet Textile Printing Ink) An ink was obtained by mixing 4 parts by mass (solids content) of an anionic pigment dispersion (AE-2078F, C.I. Pigment Black manufactured by Sanyo Dish Co., Ltd.) having a pigment concentration of 20% by mass, 8 parts by mass (solids content) of a urethane dispersion (Superflex 470 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) having a solids content of 38% by mass, 1 part by mass of a nonionic surfactant (acetylene glycol ethylene oxide adduct, Surfynol 440 manufactured by Nissin Chemical Industry Co., Ltd.), 30 parts by mass of propylene glycol, and the balance being water, and then filtering the mixture through a 5 μm filter. That is, the formulation of the ink was 4% by mass of pigment, 8% by mass of binder resin particles, 1% by mass of nonionic surfactant, 30% by mass of propylene glycol, and the balance being water.

[0157] (Post-treatment liquid) 10 parts by mass (solids) of a silicone oil emulsion (POLON-MF-51 manufactured by Shin-Etsu Chemical Co., Ltd.) with a silicone oil content of 39% by mass, 30 parts by mass of propylene glycol, and the remainder of water were mixed, and then filtered through a 5 μm filter to obtain a post-treatment liquid. That is, the formulation of the post-treatment liquid was 10% by mass of silicone oil emulsion, 30% by mass of propylene glycol, and the remainder of water.

[0158] [Color development] The L value of the image formed on the obtained printed textile (the L value when the color tone of the image is expressed in Lab system) was measured with a spectrophotometer (FD-5 manufactured by Konica Minolta, Inc.) If the obtained L value was less than 26.5, it was judged that the color development was good and was evaluated as "Good", and even if the obtained L value was 26.5 or more, although the color development was at a predetermined level, it was not as good as that evaluated as "Good", and was evaluated as "Good".

[0159] [Texture] First, an unused fabric to be printed was folded in half along the warp (longitudinal direction of the fabric), and the distance (loop height) between the lower and upper fabrics at the fold was measured. The measured loop height of the unused fabric to be printed was taken as the loop height before printing.

[0160] Next, the area of ​​the printed textile where the image was formed was folded in half along the warp (longitudinal direction of the fabric), and the loop height was measured. The measured loop height of the printed textile was defined as the loop height after printing.

[0161] The ratio of the loop height after printing to the loop height before printing was calculated according to the following formula: This ratio was defined as the rate of change in loop height.

[0162] Loop height change rate (%) = loop height after printing / loop height before printing × 100 The lower the loop height change rate, the more suppressed the deterioration of texture due to printing. Specifically, the lower the loop height change rate, the more suppressed the increase in swelling (the distance between the lower fabric and the upper fabric) when the printed item obtained after printing is folded in half, and it can be seen that even if the object to be printed is printed, it can be suppressed from becoming hard. Therefore, it indicates that the deterioration of the texture of the printed item is suppressed.

[0163] From these facts, if the obtained rate of change in loop height was less than 130%, it was judged that the texture was good and was rated as "Good". On the other hand, even if the obtained rate of change in loop height was 130% or more, although the texture was of a predetermined level, it was not as good as that rated as "Good", and was rated as "Good".

[0164] [Odor: aqueous solution]

[0165] (Sensory test) Aqueous solutions were prepared in which the concentrations of the organic acid ammonium salt and magnesium acetate were the same as those of the inkjet textile printing treatment liquids of each example (Examples 1 to 5 and Comparative Examples 1 to 5). If less than two of the five testers detected an odor in the aqueous solution, it was determined that the inkjet textile printing treatment liquid obtained had a sufficiently low odor, and the odor was rated as "absent." Furthermore, if two or more of the five testers detected an odor in the aqueous solution, it was determined that the inkjet textile printing treatment liquid obtained did not have a sufficiently low odor, and the odor was rated as "present."

[0166] (Odor concentration) The odor concentration of the aqueous solution evaluated as having an odor in the sensory test was obtained by converting the sensor value obtained by measurement with an odor sensor (manufactured by Calmor Co., Ltd.) using a calibration curve prepared by an odor judge.

[0167] (Evaluation) If the result of the sensory test was "absent" or the odor intensity was less than 100, it was determined that the odor of the inkjet printing treatment liquid obtained was sufficiently low, and the liquid was evaluated as "Good." Also, even if the odor intensity was 100 or more, the odor of the inkjet printing treatment liquid was low to a certain extent, but it could not be said that the odor was less than that of a liquid evaluated as "Good," and therefore the liquid was evaluated as "Good."

[0168] [Odor: during printing]

[0169] (Sensory Test) Five testers judged the odor when obtaining printed textiles (i.e., during textile printing) as described above using the inkjet textile printing treatment solutions according to Examples 1 to 5 and Comparative Example 1, which were evaluated as having an odor in the sensory test regarding the odor of the aqueous solution. Specifically, the testers were positioned 1 m away from (1 m forward of) the flatbed printing jig and measured the odor intensity of the atmosphere after three minutes of continuous textile printing processing, based on a six-level odor intensity rating method, and the arithmetic mean value of the obtained odor intensities was calculated.

[0170] (Odor concentration) The odor sensor (manufactured by Calmor Co., Ltd.) was positioned in the same position as the tester in the sensory test, with the suction port facing the flatbed printing jig. Of the sensor values ​​obtained, the maximum value obtained when the printing process was carried out continuously for 3 minutes was converted using a calibration curve prepared by an odor judge to obtain the odor concentration.

[0171] (Evaluation) If the sensory test for the odor of the aqueous solution resulted in a judgment of "no odor" or if the odor concentration was less than 2000, it was judged that the odor during printing was sufficiently low and was evaluated as "Good." Also, even if the odor concentration was 2000 or more, although the odor during printing was low to a predetermined extent, it could not be said that the odor was less than that of the sample evaluated as "Good," and therefore it was evaluated as "Good."

[0172] [Washing Fastness] The printed fabric was treated using a washing tester in accordance with the A-1 test described in JIS L 0844:2005 (Testing method for color fastness to washing). After rinsing, spin-drying, and drying, the printed fabric was evaluated for the degree of discoloration and fading in accordance with the "Criteria for Determining Discoloration and Fading." The closer the washing fastness was to grade 5, the better it was; grades 4-5 or higher were evaluated as "◎", and grades below 4-5 were evaluated as "◯".

[0173] The types of organic acid ammonium salts, their contents, magnesium acetate contents, and pH in Examples 1 to 5 and Comparative Examples 1 to 5 are shown in Table 1, and the results are shown in Table 2.

[0174]

[0175]

[0176] Tables 1 and 2 show that when an inkjet printing treatment liquid containing a water-soluble cationic polymer and ammonium formate is used (Examples 1 to 5), odor generation can be suppressed compared to when ammonium acetate is used instead of ammonium formate (Comparative Example 1). It was also found that when ammonium formate is used (Examples 1 to 5), printed items with higher color development can be obtained compared to when ammonium lactate, ammonium succinate, and triammonium citrate, which are thought to suppress odor generation, are used instead of ammonium formate (Comparative Examples 2, 4, and 5). It was also found that when ammonium formate is used (Examples 1 to 5), printed items with better texture can be obtained compared to when ammonium benzoate, ammonium succinate, and triammonium citrate, which are thought to suppress odor generation, are used instead of ammonium formate (Comparative Examples 3 to 5). From these findings, it was found that when the inkjet printing treatment liquid containing a water-soluble cationic polymer and ammonium formate was used (Examples 1 to 5), it was possible to obtain printed products having high color development and good texture while suppressing the generation of odor.

[0177] Next, we investigated whether the amine odor can be suppressed by adding the organic acid ammonium salt to the inkjet printing treatment liquid. Here, the organic acid ammonium salts used were ammonium succinate (organic acid: succinic acid, vapor pressure at 20°C: approximately 0 kPa), ammonium citrate (organic acid: citric acid, vapor pressure at 20°C: approximately 0 kPa), ammonium benzoate (organic acid: benzoic acid, vapor pressure at 20°C: 0.13 kPa), and ammonium acetate (organic acid: acetic acid, vapor pressure at 20°C: 1.5 kPa). The vapor pressure of formic acid at 20°C is 4.6 kPa.

[0178] Reference Example 1 As a water-soluble cationic polymer, 3.0 parts by mass (solid content) of a copolymer of diallyldimethylammonium chloride and sulfur dioxide (PAS-A5 manufactured by Nittobo Medical Co., Ltd., weight average molecular weight Mw 4000) in which at least a portion of the chloride ions have been ion-exchanged with succinate anions, 1.0 part by mass of ammonium succinate (manufactured by Yoneyama Chemical Industry Co., Ltd.), 0.5 part by mass of magnesium acetate (manufactured by Yoneyama Chemical Industry Co., Ltd.) as a metal salt, and 0.5 part by mass of a nonionic surfactant (manufactured by Yoneyama Chemical Industry Co., Ltd.) as a surfactant. 0.02 parts by mass of a surfactant (silicone surfactant, Silface SAG503A manufactured by Nissin Chemical Industry Co., Ltd.), 40 parts by mass of 3-methyl-1,5-pentanediol (MPD manufactured by Kuraray Co., Ltd.) as an organic solvent, 1.0 part by mass of a 1 mol / L sodium hydroxide solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a pH adjuster, and the remainder (54.48 parts by mass) of water were mixed and then filtered through a 5 μm filter to obtain an inkjet printing treatment liquid according to Reference Example 1 (Reference Pretreatment Liquid 1). The formulation of Reference Pretreatment Liquid 1 was 3.0% by mass of the water-soluble cationic polymer and 1.0% by mass of ammonium succinate. The pH of the obtained Reference Pretreatment Liquid 1 was measured using a pH meter (D-71 manufactured by Horiba, Ltd.), and the result was 7.06.

[0179] Reference Example 2 A treatment liquid for inkjet printing according to Reference Example 2 (reference pretreatment liquid 2) was obtained by mixing 3.0 parts by mass (solid content) of a water-soluble cationic polymer in which at least a portion of the chloride ions of a copolymer of diallyldimethylammonium chloride and sulfur dioxide (PAS-A5 manufactured by Nittobo Medical Co., Ltd., weight-average molecular weight Mw 4000) had been ion-exchanged with succinate anions, 3.0 parts by mass of ammonium succinate (manufactured by Yoneyama Chemical Co., Ltd.), 0.5 parts by mass of magnesium acetate (manufactured by Yoneyama Chemical Co., Ltd.) as a metal salt, 0.02 parts by mass of a nonionic surfactant (silicone-based surfactant, Silface SAG503A manufactured by Nissin Chemical Industry Co., Ltd.) as a surfactant, 38 parts by mass of 3-methyl-1,5-pentanediol (MPD manufactured by Kuraray Co., Ltd.) as an organic solvent, and the balance (55.48 parts by mass) of water, and then filtering the mixture through a 5 μm filter. The formulation of the reference pretreatment solution 2 was 3.0% by mass of the water-soluble cationic polymer and 3.0% by mass of ammonium succinate. The pH of the reference pretreatment solution 2 was measured using a pH meter (D-71 manufactured by Horiba, Ltd.) and found to be 7.15.

[0180] Reference Example 3 As a water-soluble cationic polymer, 10.0 parts by mass (solid content) of a copolymer of diallyldimethylammonium chloride and sulfur dioxide (PAS-A5 manufactured by Nittobo Medical Co., Ltd., weight average molecular weight Mw 4000) in which at least a portion of the chloride ions have been ion-exchanged with succinate anions, 10.0 parts by mass of ammonium succinate (manufactured by Yoneyama Chemical Industry Co., Ltd.), 0.5 parts by mass of magnesium acetate (manufactured by Yoneyama Chemical Industry Co., Ltd.) as a metal salt, and 0.5 parts by mass of a nonionic surfactant. An inkjet printing treatment liquid according to Reference Example 3 (Reference Pretreatment Liquid 3) was obtained by mixing 0.02 parts by mass of an activator (silicone surfactant, Silface SAG503A manufactured by Nissin Chemical Industry Co., Ltd.), 25 parts by mass of 3-methyl-1,5-pentanediol (MPD manufactured by Kuraray Co., Ltd.) as an organic solvent, 3.0 parts by mass of a 1 mol / L sodium hydroxide solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a pH adjuster, and the remainder (51.48 parts by mass) of water, and then filtering the mixture through a 5 μm filter. The formulation of Reference Pretreatment Liquid 3 was 10.0% by mass of the water-soluble cationic polymer and 10.0% by mass of ammonium succinate. The pH of the obtained Reference Pretreatment Liquid 3 was measured using a pH meter (D-71 manufactured by Horiba, Ltd.), and the result was 7.25.

[0181] Reference Example 4 A treatment liquid for inkjet printing according to Reference Example 4 (reference pretreatment liquid 4) was obtained by mixing 3.0 parts by mass (solid content) of a water-soluble cationic polymer in which at least a portion of the chloride ions of a copolymer of diallyldimethylammonium chloride and sulfur dioxide (PAS-A5 manufactured by Nittobo Medical Co., Ltd., weight-average molecular weight Mw 4000) had been ion-exchanged with succinate anions, 3.0 parts by mass of ammonium citrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 0.5 parts by mass of magnesium acetate (manufactured by Yoneyama Chemical Co., Ltd.) as a metal salt, 0.02 parts by mass of a nonionic surfactant (silicone-based surfactant, Silface SAG503A manufactured by Nissin Chemical Industry Co., Ltd.) as a surfactant, 38 parts by mass of 3-methyl-1,5-pentanediol (MPD manufactured by Kuraray Co., Ltd.) as an organic solvent, and the balance (55.48 parts by mass) of water, and then filtering the mixture through a 5 μm filter. The formulation of the reference pretreatment liquid 4 was 3.0% by mass of the water-soluble cationic polymer and 3.0% by mass of ammonium citrate. The pH of the reference pretreatment liquid 4 was measured using a pH meter (D-71 manufactured by Horiba, Ltd.) and found to be 7.28.

[0182] Reference Example 5 A treatment liquid for inkjet printing according to Reference Example 5 (reference pretreatment liquid 5) was obtained by mixing 3.0 parts by mass (solid content) of a water-soluble cationic polymer in which at least a portion of the chloride ions of a copolymer of diallyldimethylammonium chloride and sulfur dioxide (PAS-A5 manufactured by Nittobo Medical Co., Ltd., weight-average molecular weight Mw 4000) had been ion-exchanged with succinate anions, 10.0 parts by mass of ammonium citrate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 0.5 parts by mass of magnesium acetate (manufactured by Yoneyama Chemical Co., Ltd.) as a metal salt, 0.02 parts by mass of a nonionic surfactant (silicone-based surfactant, Silface SAG503A manufactured by Nissin Chemical Industry Co., Ltd.) as a surfactant, 26 parts by mass of 3-methyl-1,5-pentanediol (MPD manufactured by Kuraray Co., Ltd.) as an organic solvent, and the balance (56.48 parts by mass) of water, and then filtering the mixture through a 5 μm filter. The formulation of the reference pretreatment solution 5 was 3.0% by mass of the water-soluble cationic polymer and 10.0% by mass of ammonium citrate. The pH of the reference pretreatment solution 5 was measured using a pH meter (D-71 manufactured by Horiba, Ltd.) and found to be 7.33.

[0183] Reference Example 6 A treatment liquid for inkjet printing according to Reference Example 6 (reference pretreatment liquid 6) was obtained by mixing 3.0 parts by mass (solid content) of a water-soluble cationic polymer in which at least a portion of the chloride ions of a copolymer of diallyldimethylammonium chloride and sulfur dioxide (PAS-A5 manufactured by Nittobo Medical Co., Ltd., weight average molecular weight Mw 4000) had been ion-exchanged with succinate anions, 3.0 parts by mass of ammonium benzoate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 0.5 parts by mass of magnesium acetate (manufactured by Yoneyama Chemical Co., Ltd.) as a metal salt, 0.02 parts by mass of a nonionic surfactant (silicone-based surfactant, Silface SAG503A manufactured by Nissin Chemical Industry Co., Ltd.) as a surfactant, 38 parts by mass of 3-methyl-1,5-pentanediol (MPD manufactured by Kuraray Co., Ltd.) as an organic solvent, and the balance (55.48 parts by mass) of water, and then filtering the mixture through a 5 μm filter. The formulation of the reference pretreatment solution 6 was 3.0% by mass of the water-soluble cationic polymer and 3.0% by mass of ammonium benzoate. The pH of the reference pretreatment solution 6 was measured using a pH meter (D-71 manufactured by Horiba, Ltd.) and found to be 7.03.

[0184] Reference Example 7 A treatment liquid for inkjet printing according to Reference Example 7 (reference pretreatment liquid 7) was obtained by mixing 3.0 parts by mass (solid content) of a polymer in which at least a portion of the chloride ions of a copolymer of diallyldimethylammonium chloride and sulfur dioxide (PAS-A5 manufactured by Nittobo Medical Co., Ltd., weight average molecular weight Mw 4000) as a water-soluble cationic polymer had been ion-exchanged with succinate anions, 10.0 parts by mass of ammonium acetate (manufactured by Yoneyama Chemical Co., Ltd.), 0.5 parts by mass of magnesium acetate (manufactured by Yoneyama Chemical Co., Ltd.) as a metal salt, 0.02 parts by mass of a nonionic surfactant (silicone-based surfactant, Silface SAG503A manufactured by Nissin Chemical Industry Co., Ltd.) as a surfactant, 30 parts by mass of 3-methyl-1,5-pentanediol (MPD manufactured by Kuraray Co., Ltd.) as an organic solvent, and the balance (56.48 parts by mass) of water, and then filtering the mixture through a 5 μm filter. The formulation of the reference pretreatment solution 7 was 3.0% by mass of the water-soluble cationic polymer and 10.0% by mass of ammonium acetate. The pH of the reference pretreatment solution 7 was measured using a pH meter (D-71 manufactured by Horiba, Ltd.) to find it was 7.10.

[0185] Comparative Reference Example 1 A treatment liquid for inkjet printing according to Comparative Reference Example 1 (comparative reference pretreatment liquid 1) was obtained by mixing 10.0 parts by mass (solid content) of a water-soluble cationic polymer in which at least a portion of the chloride ions of a copolymer of diallyldimethylammonium chloride and sulfur dioxide (PAS-A5 manufactured by Nittobo Medical Co., Ltd., weight-average molecular weight Mw 4000) had been ion-exchanged with succinate anions, 0.5 parts by mass of magnesium acetate (manufactured by Yoneyama Chemical Co., Ltd.) as a metal salt, 0.02 parts by mass of a nonionic surfactant (silicone-based surfactant, Silface SAG503A manufactured by Nissin Chemical Industry Co., Ltd.) as a surfactant, 31 parts by mass of 3-methyl-1,5-pentanediol (MPD manufactured by Kuraray Co., Ltd.) as an organic solvent, 3.0 parts by mass of a 1 mol / L sodium hydroxide solution (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as a pH adjuster, and the balance (55.48 parts by mass) of water, and then filtering the mixture through a 5 μm filter. The blending ratio of the water-soluble cationic polymer in the comparative pretreatment liquid 1 was 10.0% by mass. The pH of the comparative pretreatment liquid 1 was measured using a pH meter (D-71 manufactured by Horiba, Ltd.) and found to be 7.04.

[0186] Comparative Reference Example 2 As a water-soluble cationic polymer, 3.0 parts by mass (solid content) of a copolymer of diallyldimethylammonium chloride and sulfur dioxide (PAS-A5 manufactured by Nittobo Medical Co., Ltd., weight average molecular weight Mw 4000) in which at least a part of the chloride ions have been ion-exchanged with succinate anions, 10 parts by mass of ammonium formate (manufactured by Yoneyama Chemical Industry Co., Ltd.), 0.5 parts by mass of magnesium acetate (manufactured by Yoneyama Chemical Industry Co., Ltd.) as a metal salt, and 0.5 parts by mass of a nonionic surfactant (silica) as a surfactant. A ricone-based surfactant (Silface SAG503A manufactured by Nissin Chemical Industry Co., Ltd.) of 0.02 parts by mass, an organic solvent (3-methyl-1,5-pentanediol (MPD manufactured by Kuraray Co., Ltd.) of 35 parts by mass, an organic solvent (1.0 parts by mass of 1 mol / L sodium hydroxide solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) of 1.0 parts by mass, and the remainder (50.48 parts by mass) of water were mixed and then filtered through a 5 μm filter to obtain an inkjet printing treatment liquid according to Comparative Reference Example 2 (Comparative Reference Pretreatment Liquid 2). The formulation of Comparative Reference Pretreatment Liquid 2 contained 3.0% by mass of the water-soluble cationic polymer and 10.0% by mass of ammonium formate. The pH of the obtained Comparative Reference Pretreatment Liquid 2 was measured using a pH meter (D-71 manufactured by Horiba, Ltd.) to find a value of 7.21.

[0187] Comparative Reference Example 3 A treatment liquid for inkjet printing according to Comparative Reference Example 3 (comparative reference pretreatment liquid 3) was obtained by mixing 3.0 parts by mass (solid content) of a water-soluble cationic polymer in which at least a portion of the chloride ions of a copolymer of diallyldimethylammonium chloride and sulfur dioxide (PAS-A5 manufactured by Nittobo Medical Co., Ltd., weight-average molecular weight Mw 4000) had been ion-exchanged with succinate anions, 3 parts by mass of succinic acid (manufactured by Nippon Shokubai Co., Ltd.), 0.5 parts by mass of magnesium acetate (manufactured by Yoneyama Chemical Co., Ltd.) as a metal salt, 0.02 parts by mass of a nonionic surfactant (silicone-based surfactant, Silface SAG503A manufactured by Nissin Chemical Industry Co., Ltd.) as a surfactant, 40 parts by mass of 3-methyl-1,5-pentanediol (MPD manufactured by Kuraray Co., Ltd.) as an organic solvent, and the balance (53.48 parts by mass) of water, and then filtering the mixture through a 5 μm filter. The formulation of the comparative reference pretreatment solution 3 was 3.0% by mass of the water-soluble cationic polymer and 3.0% by mass of succinic acid. The pH of the obtained comparative reference pretreatment solution 2 was measured using a pH meter (D-71 manufactured by Horiba, Ltd.) and was found to be 4.20.

[0188] A printed item was obtained in the same manner as in Example 1, except that the ink-jet printing treatment liquid prepared as above was used.

[0189] [Odor: Printed Fabric] The obtained printed fabric was dried at high temperature (160°C for 3 hours) and then packed in a bag. If no amine odor was detected from the printed fabric that had been dried at high temperature in this bag, it was judged that the odor of the printed fabric was sufficiently low and was rated as "Good." If an amine odor was detected but the odor of the printed fabric was less than a predetermined level but not as low as that rated as "Good," it was rated as "Good."

[0190] [Component Suitability] First, the mass of an O-ring (manufactured by Viton) used in evaluating component suitability was measured. The obtained mass was designated W0. The O-ring whose mass had been measured was then immersed in the obtained inkjet printing treatment liquid and left at 60°C for 3 months. The mass of the O-ring after this standing was measured. The obtained mass was designated W. The mass change rate R was measured from the obtained W0 and W. Specifically, the mass change rate R was calculated from R = (W - W0) / W0 × 100 (%). If the mass change rate R was within 5%, it was determined that the component suitability was excellent and was evaluated as "Good". Even if it exceeded 5%, although the component suitability was excellent to a certain extent, it could not be said that the component suitability was better than that of a sample evaluated as "Good", and therefore it was evaluated as "Good".

[0191] Table 3 shows the content of water-soluble cationic polymer, ammonium succinate, pH, and evaluation results (odor and component compatibility) for Reference Examples 1 to 7 and Comparative Reference Examples 1 to 3.

[0192]

[0193] Table 3 shows that the amine odor was suppressed when the organic acid ammonium salt was contained in the inkjet textile printing treatment liquid (Reference Examples 1 to 7) compared to when the organic acid ammonium salt was not contained (Comparative Reference Example 1) or when ammonium formate was contained instead of the organic acid ammonium salt (Comparative Reference Example 2). This indicates that the generation of amine odor can be suppressed by containing the organic acid ammonium salt in the inkjet textile printing treatment liquid. Furthermore, when succinic acid was contained in the inkjet textile printing treatment liquid instead of the organic acid ammonium salt (Comparative Reference Example 3), component compatibility was found to be inferior. On the other hand, when the organic acid ammonium salt was contained in the inkjet textile printing treatment liquid (Reference Examples 1 to 7), not only was the amine odor suppressed, but excellent component compatibility could also be ensured even when the organic acid ammonium salt was contained to suppress the amine odor. Specifically, Reference Examples 1 to 7 exhibited superior component compatibility compared to Comparative Reference Example 3. Therefore, it was found that by adding not only ammonium formate but also the organic acid ammonium salt to the inkjet textile printing treatment liquid, it is possible to obtain printed products that are excellent in compatibility with components and in color development and texture, while suppressing not only the generation of odors, particularly odors derived from organic acid salts, but also odors derived from the water-soluble cationic polymer (e.g., amine odor, etc.). To clarify this, an inkjet textile printing treatment liquid containing ammonium formate and the organic acid ammonium salt was investigated.

[0194] Example 6 A treatment liquid for inkjet printing (pre-treatment liquid 6) according to Example 6 was obtained by mixing 3.0 parts by mass (solid content) of a water-soluble cationic polymer in which at least a portion of the chloride ions of a copolymer of diallyldimethylammonium chloride and sulfur dioxide (PAS-A5 manufactured by Nittobo Medical Co., Ltd., weight-average molecular weight Mw 4000) had been ion-exchanged with succinate anions, 10 parts by mass of ammonium formate (manufactured by Yoneyama Chemical Co., Ltd.), 3.0 parts by mass of ammonium succinate (manufactured by Yoneyama Chemical Co., Ltd.), 0.5 parts by mass of magnesium acetate (manufactured by Yoneyama Chemical Co., Ltd.) as a metal salt, 0.02 parts by mass of a nonionic surfactant (silicone-based surfactant, Silface SAG503A manufactured by Nissin Chemical Industry Co., Ltd.) as a surfactant, 30 parts by mass of 3-methyl-1,5-pentanediol (MPD manufactured by Kuraray Co., Ltd.) as an organic solvent, and the balance (53.48 parts by mass) of water, followed by filtration through a 5 μm filter. The formulation of the pre-treatment liquid 6 was 3.0% by mass of the water-soluble cationic polymer, 10.0% by mass of the ammonium formate, and 3.0% by mass of the ammonium succinate. The pH of the obtained pre-treatment liquid 6 was measured using a pH meter (D-71 manufactured by Horiba, Ltd.) and was found to be 7.14.

[0195] Example 7 An inkjet printing treatment liquid (pre-treatment liquid 7) according to Example 7 was obtained by mixing 3.0 parts by mass (solid content) of a water-soluble cationic polymer in which at least a portion of the chloride ions of a copolymer of diallyldimethylammonium chloride and sulfur dioxide (PAS-A5 manufactured by Nittobo Medical Co., Ltd., weight-average molecular weight Mw 4000) had been ion-exchanged with succinate anions, 10 parts by mass of ammonium formate (manufactured by Yoneyama Chemical Co., Ltd.), 3.0 parts by mass of ammonium citrate (manufactured by Yoneyama Chemical Co., Ltd.), 0.5 parts by mass of magnesium acetate (manufactured by Yoneyama Chemical Co., Ltd.) as a metal salt, 0.02 parts by mass of a nonionic surfactant (silicone-based surfactant, Silface SAG503A manufactured by Nissin Chemical Industry Co., Ltd.) as a surfactant, 30 parts by mass of 3-methyl-1,5-pentanediol (MPD manufactured by Kuraray Co., Ltd.) as an organic solvent, and the balance (53.48 parts by mass) of water, and then filtering the mixture through a 5 μm filter. The formulation of the pretreatment liquid 7 was 3.0% by mass of the water-soluble cationic polymer, 10.0% by mass of the ammonium formate, and 3.0% by mass of the ammonium citrate. The pH of the obtained pretreatment liquid 7 was measured using a pH meter (D-71 manufactured by Horiba, Ltd.) and was found to be 7.30.

[0196] Example 8 An inkjet printing treatment liquid (pre-treatment liquid 8) according to Example 8 was obtained by mixing 3.0 parts by mass (solid content) of a water-soluble cationic polymer in which at least a portion of the chloride ions of a copolymer of diallyldimethylammonium chloride and sulfur dioxide (PAS-A5 manufactured by Nittobo Medical Co., Ltd., weight-average molecular weight Mw 4000) had been ion-exchanged with succinate anions, 10 parts by mass of ammonium formate (manufactured by Yoneyama Chemical Co., Ltd.), 3.0 parts by mass of ammonium benzoate (manufactured by Yoneyama Chemical Co., Ltd.), 0.5 parts by mass of magnesium acetate (manufactured by Yoneyama Chemical Co., Ltd.) as a metal salt, 0.02 parts by mass of a nonionic surfactant (silicone-based surfactant, Silface SAG503A manufactured by Nissin Chemical Industry Co., Ltd.) as a surfactant, 30 parts by mass of 3-methyl-1,5-pentanediol (MPD manufactured by Kuraray Co., Ltd.) as an organic solvent, and the balance (53.48 parts by mass) of water, and then filtering the mixture through a 5 μm filter. The formulation of the pre-treatment liquid 8 was 3.0% by mass of the water-soluble cationic polymer, 10.0% by mass of the ammonium formate, and 3.0% by mass of the ammonium benzoate. The pH of the obtained pre-treatment liquid 8 was measured using a pH meter (D-71 manufactured by Horiba, Ltd.) and was found to be 7.01.

[0197] The inkjet printing treatment liquid prepared as described above was evaluated by the same methods as above (color development, texture, odor: aqueous solution, odor: during printing, odor: printed material, washing fastness, and compatibility with components).

[0198] The content of the water-soluble cationic polymer, the content of ammonium formate, the type and content of the organic acid ammonium salt, and the pH in Examples 6 to 8 are shown in Table 4, and the results of the evaluation are shown in Table 5.

[0199]

[0200]

[0201] Tables 4 and 5 show that when an inkjet printing treatment liquid containing a water-soluble cationic polymer and ammonium formate and further containing the organic acid ammonium salt is used (Examples 6 to 8), not only is excellent compatibility with components achieved, but the generation of an amine odor can also be suppressed, in addition to the effects achieved in Examples 1 to 5. Therefore, it was found that by including ammonium formate and further containing the organic acid ammonium salt in an inkjet printing treatment liquid, it is possible to obtain printed products that are excellent in component compatibility and have excellent color development and texture, while not only suppressing the generation of odor, particularly odor derived from organic acid salts, but also suppressing the generation of odor derived from the water-soluble cationic polymer.

[0202] This application is based on Japanese Patent Application No. 2023-218002 filed on December 25, 2023, the contents of which are incorporated herein by reference.

[0203] In order to express the present invention, the present invention has been properly and sufficiently described through the embodiments in the above, but it should be recognized that those skilled in the art can easily change and / or improve the above-mentioned embodiments. Therefore, unless the changes or improvements made by those skilled in the art are at a level that causes departure from the scope of the claims described in the claims, such changes or improvements are interpreted as being included in the scope of the claims.

[0204] According to the present invention, there are provided an inkjet textile printing treatment liquid, an inkjet textile printing ink set, an inkjet textile printing method, and an inkjet textile printing apparatus that can produce printed textiles with high color development and good texture while suppressing odor generation.

[0205] DESCRIPTION OF SYMBOLS 3 Mounting table 4 Ink head 4a First ink head 4b Second ink head 4c Third ink head 4d Fourth ink head 5 Pre-treatment liquid head 6 Post-treatment liquid head 10 Inkjet textile printing device 11 Device frame 12 Printing area 13 Maintenance area 14 Turn-back area 15 Carriage guide 16 Timing belt 17 Guide rail 20 Work transport section 21 Feed roller 22 Take-up roller 23 First tension roller 24 Work guide 25 Transport roller 26 Pinch roller 27 Turn-back roller 28 Second tension roller 29 Platen 30 Carriage frame 31 Head support frame 32 Back frame 41A to 48A First to eighth upstream ink heads 41B to 48B First to eighth downstream ink heads 7FA Pre-treatment supply sub-tank 7FB Pre-treatment recovery sub-tank 7RA Post-treatment supply sub-tank 7RB Post-treatment recovery sub-tank 71A-78A 1st to 8th supply sub-tanks 71B-78B 1st to 8th recovery sub-tanks 90 Main tank 100 Inkjet printer 111 Center frame 112 Right frame 113 Left frame 300 Carriage F Transport direction M1 First motor M2 Second motor P Printing object S Main scanning direction W Work WA Delivery roll WB Take-up roll

Claims

1. A treatment liquid for inkjet printing, comprising a water-soluble cationic polymer and ammonium formate.

2. The treatment liquid for inkjet printing according to claim 1, wherein the content of ammonium formate is 0.1% by mass or more and 25% by mass or less with respect to the treatment liquid for inkjet printing.

3. The treatment liquid for inkjet printing according to claim 1 or 2, wherein the water-soluble cationic polymer contains a succinate anion.

4. The treatment liquid for inkjet printing according to any one of claims 1 to 3, wherein the content of the water-soluble cationic polymer is 0.3% by mass or more and 35% by mass or less with respect to the treatment liquid for inkjet printing.

5. The treatment liquid for inkjet printing according to any one of claims 1 to 4, wherein the pH is 7 or more and 9.5 or less.

6. The treatment liquid for inkjet printing according to any one of claims 1 to 5, further comprising a metal salt.

7. The treatment liquid for inkjet printing according to any one of claims 1 to 6, which is a pretreatment liquid.

8. The treatment liquid for inkjet printing according to any one of claims 1 to 7, further comprising an ammonium organic acid salt composed of an organic acid having a vapor pressure of 2 kPa or less at 20°C and ammonia.

9. The treatment liquid for inkjet printing according to claim 8, wherein the content of the ammonium organic acid salt is 10% by mass or more with respect to the water-soluble cationic polymer.

10. A treatment liquid for inkjet printing, comprising a water-soluble cationic polymer and an ammonium organic acid salt composed of an organic acid having a vapor pressure of 2 kPa or less at 20°C and ammonia.

11. An inkjet printing ink set having the treatment liquid for inkjet printing according to any one of claims 1 to 10 and an inkjet printing ink containing a pigment.

12. An inkjet printing method, comprising discharging and adhering the treatment liquid for inkjet printing according to any one of claims 1 to 10 onto a fabric, and then discharging and adhering an inkjet printing ink containing a pigment onto the fabric to which the treatment liquid for inkjet printing has been adhered.

13. An inkjet printing apparatus comprising a treatment liquid head for discharging and adhering the treatment liquid for inkjet printing according to any one of claims 1 to 10 onto a fabric, and an ink head for discharging and adhering an inkjet printing ink containing a pigment onto the fabric to which the treatment liquid for inkjet printing has been adhered.

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