Dye printing treatment liquid composition, ink set, and recording method

Abstract

To provide a printed material which has excellent fixability and color development, suppresses color unevenness, and reduces the total nitride content when drained. SOLUTION: A dye printing treatment liquid composition containing ε-caprolactam and a dyeing assistant containing one or more selected from benzenesulfonate, sodium sulfate, sodium carbonate, and sodium hydrogencarbonate, and having a pH of 4.0 to 12.

Description

[Technical Field]

[0001] The present invention relates to a dye textile printing treatment liquid composition, an ink set, and a recording method. [Background technology]

[0002] Inkjet recording methods are capable of recording high-resolution images with relatively simple equipment and have been rapidly developing in various fields. For example, Patent Document 1 discloses a water-based functional ink for inkjet textile printing to be used in combination with a recording ink containing a reactive dye, the ink containing a humectant and an alkali agent, a sizing agent content of 0% by mass or more and 1% by mass or less, and a hydrogen ion concentration index (pH) of 10 or less, with the aim of providing a functional ink for inkjet textile printing that can improve the durability of the inkjet head while ensuring the color development of the recording ink. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2024-25269 Summary of the Invention [Problem to be solved by the invention]

[0004] In textile printing technology, pretreatment is carried out to prevent bleeding of recording ink that has landed on a recording medium such as fabric and to improve fixation. Urea is used in such pretreatment solutions to improve fixation and color development, but environmental compatibility is a concern because waste liquid containing urea is generated when the printed material is washed. [Means for solving the problem]

[0005] The dye printing treatment liquid composition of the present invention contains ε-caprolactam and a dyeing assistant containing one or more selected from benzenesulfonate, sodium sulfate, sodium carbonate, and sodium hydrogencarbonate, and has a pH of 4.0 to 12.

[0006] The ink set of the present invention comprises a textile printing ink containing a reactive dye and water, and the above-described dye textile printing treatment liquid composition.

[0007] The recording method of the present invention comprises a treatment liquid application step of applying the dye textile printing treatment liquid composition to a fabric, and an ink application step of applying a textile printing ink containing a reactive dye and water to the fabric. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 2 is a diagram illustrating an example of a recording apparatus used in the recording method of the present embodiment. [Figure 2] 1 is a table showing examples and comparative examples using a rotary screen system. [Figure 3] 1 is a table showing examples and comparative examples using an inkjet method. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail with reference to the drawings as necessary, but the present invention is not limited to this, and various modifications are possible without departing from the spirit of the present invention. In the drawings, the same elements are given the same reference numerals, and redundant explanations will be omitted. Furthermore, positional relationships such as up, down, left, and right will be based on the positional relationships shown in the drawings unless otherwise specified. Furthermore, the dimensional ratios of the drawings are not limited to those shown in the drawings.

[0010] 1. Dye printing treatment liquid composition The dye printing treatment liquid composition according to this embodiment (hereinafter also simply referred to as "treatment liquid composition") contains ε-caprolactam and a dyeing assistant containing one or more selected from benzenesulfonate, sodium sulfate, sodium carbonate, and sodium hydrogencarbonate, and has a pH of 4 to 12.

[0011] In dye printing, a treatment liquid composition is applied to a fabric before printing in order to improve the color development and other properties of the printing ink. Urea has been used in such treatment liquid compositions in the hope that it will dissolve the dye and fix it to the fabric, as well as provide effects such as uniform temperature during the steaming process. However, when a treatment liquid composition containing urea is used, a large amount of waste liquid containing nitrogen sources such as urea is generated during the washing of the printed fabric after printing, raising concerns about its environmental adaptability.

[0012] In contrast, the treatment liquid composition of this embodiment uses ε-caprolactam and a predetermined dyeing aid, which improves the fixability and color development of the textile printing ink, achieves temperature uniformity in the steaming process to suppress color unevenness, and provides a printing method that emits less nitrogen and is environmentally friendly.

[0013] The treatment liquid composition of this embodiment may be used together with either an inkjet textile printing ink or a rotary textile printing ink, and the dye contained in the textile printing ink is not particularly limited. Among these, the treatment liquid composition of this embodiment is preferably used together with a textile printing ink containing a reactive dye and water. Use of the treatment liquid composition with such a textile printing ink tends to further improve fixability and color development.

[0014] The dye printing treatment liquid composition, ink set, recording method, and the like according to this embodiment will be described in detail below.

[0015] 1.1. ε-Caprolactam Since ε-caprolactam is effective in dissolving dyes and fixing them to fabrics, its use promotes the formation of covalent bonds between the dye and fabric, further improving fixation and color development. Furthermore, the use of ε-caprolactam can also suppress in-plane color unevenness. Specifically, the formation of covalent or non-covalent bonds between the dye and fabric is promoted in the steaming step reaction described below. The use of ε-caprolactam is thought to suppress variations in in-plane temperature differences during the steaming step, thereby suppressing in-plane color unevenness.

[0016] However, in the treatment liquid composition of this embodiment, the mechanism by which fixability and color development are improved and the mechanism by which in-plane color unevenness is suppressed are not limited to those described above.

[0017] The content of ε-caprolactam is preferably 1.0 to 30% by mass relative to the total amount of the treatment liquid composition, and may be adjusted appropriately depending on the application.

[0018] Specifically, the content of ε-caprolactam in the treatment liquid composition used together with an inkjet printing ink is preferably 1.0 to 20 mass%, 2.0 to 15 mass%, 3.0 to 10 mass%, or 4.0 to 7.5 mass%, relative to the total amount of the treatment liquid composition. When the content of ε-caprolactam is within the above range, fixability and color development tend to be further improved in inkjet recording methods.

[0019] The content of ε-caprolactam in the treatment liquid composition used together with an analog textile printing ink such as a rotary screen method is preferably 2.5 to 30 mass %, 5.0 to 25 mass %, or 10 to 20 mass %, relative to the total amount of the treatment liquid composition. When the content of ε-caprolactam is within the above range, fixability and color development tend to be further improved in analog textile printing.

[0020] 1.2. Dyeing assistant The dyeing aid contains one or more selected from benzenesulfonate, sodium sulfate, sodium carbonate, and sodium bicarbonate. Among these, benzenesulfonate is preferred. The benzenesulfonate is not particularly limited, but examples thereof include metal salts of benzenesulfonic acid, nitrobenzenesulfonate, and alkylbenzenesulfonate.

[0021] Among these, benzenesulfonate is preferred, nitrobenzenesulfonate is preferred, and meta-nitrobenzenesulfonate is preferred. The metal atom constituting the benzenesulfonate is not particularly limited, but examples thereof include alkali metals such as sodium and potassium, and alkaline earth metals such as calcium and magnesium. Among these, alkali metals are preferred, and sodium is more preferred.

[0022] By using such a dyeing aid in combination with ε-caprolactam, the initial reaction of the dye is further accelerated, the color development and fixation are further improved, and printed materials with reduced color unevenness can be obtained.

[0023] The content of the dyeing assistant is preferably 0.01 to 10% by mass relative to the total amount of the treatment liquid composition, and may be adjusted appropriately depending on the application.

[0024] Specifically, the content of the dyeing aid in the treatment liquid composition used together with the inkjet printing ink is preferably 0.01 to 5.0 mass%, 0.05 to 2.5 mass%, 0.10 to 1.0 mass%, or 0.15 to 0.50 mass%, relative to the total amount of the treatment liquid composition. When the content of the dyeing aid is within the above range, fixability and color development tend to be further improved and color unevenness is further suppressed in inkjet recording methods.

[0025] The content of the dyeing auxiliary in the treatment liquid composition used together with analog textile printing ink such as that used in the rotary screen method is preferably 0.50 to 10 mass%, 0.75 to 5 mass%, or 1.0 to 2.5 mass%, relative to the total amount of the treatment liquid composition. When the content of the dyeing auxiliary is within the above range, fixation and color development in analog textile printing tend to be further improved, and color unevenness is further suppressed.

[0026] Furthermore, the ratio of the content of ε-caprolactam to the content of the dyeing assistant is preferably 2.5 to 50, and may be adjusted appropriately depending on the application.

[0027] Specifically, in a treatment liquid composition used together with an inkjet printing ink, the ratio of the content of ε-caprolactam to the content of the dyeing aid is preferably 7.5 to 50, 10 to 45, 12.5 to 40, or 15 to 35. When the ratio is within the above range, fixability and color development tend to be further improved and color unevenness is further suppressed in an inkjet recording method.

[0028] In a treatment liquid composition used together with an analog textile printing ink such as that used in a rotary screen method, the ratio of the content of ε-caprolactam to the content of the dyeing aid is preferably 2.5 to 40, 5.0 to 30, or 7.5 to 20. When the ratio is within the above range, fixability and color development are further improved in analog textile printing, and color unevenness tends to be further suppressed.

[0029] 1.3. Polymer compounds The treatment liquid composition of this embodiment may contain a polymer compound. By containing a polymer compound, the viscosity of the treatment liquid composition is further improved, and color unevenness tends to be suppressed.

[0030] The polymer compound is preferably one that has the effect of improving viscosity under alkaline conditions of pH 7 or higher. This tends to suppress color unevenness. Such polymer compounds are not particularly limited, but examples include one or more selected from the group consisting of guar gum, ethoxyguar gum, propoxyguar gum, ethoxypropoxyguar gum, tamarind gum, xanthan gum, carboxyethyl cellulose, carboxymethyl cellulose, ammonium cellulose, hydroxyethyl cellulose, sodium alginate, acrylic polymer, polyethylene glycol, polyacrylamide, acrylamide copolymer, AMPS polymer and copolymer, dextrin, carboxymethyl starch, and carbomer. Among these, hydroxyethyl cellulose and sodium alginate are more preferred.

[0031] The content of the polymer compound is preferably 0.1 to 45% by mass relative to the total amount of the treatment liquid composition, and may be adjusted appropriately depending on the application.

[0032] Specifically, the content of the polymer compound in the treatment liquid composition used together with the inkjet textile printing ink is preferably 0.1 to 25 mass %, 0.3 to 10 mass %, 0.5 to 5.0 mass %, or 0.75 to 4.0 mass %, relative to the total amount of the treatment liquid composition. When the content of the polymer compound is within the above range, color unevenness tends to be further suppressed in inkjet recording methods.

[0033] The content of the polymer compound in the treatment liquid composition used together with the analog textile printing ink is preferably 1.0 to 45 mass %, 2.5 to 35 mass %, or 5.0 to 25 mass %, relative to the total amount of the treatment liquid composition. When the content of the polymer compound is within the above range, color unevenness tends to be further suppressed in analog textile printing.

[0034] 1.4. pH adjuster The treatment liquid composition of this embodiment may contain a pH adjuster. By containing a pH adjuster, the reaction efficiency between the fabric and the dye is further improved, the fixability and color development are further improved, and color unevenness is also suppressed.

[0035] Such pH adjusters are not particularly limited, but examples thereof include triethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, 2-isopropanolamine, sodium citrate, disodium citrate, trisodium citrate, monosodium succinate, disodium succinate, sodium acetate, sodium lactate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, trisodium phosphate, tripotassium phosphate, glutamic acid ... Examples of the surfactant include one or more selected from the group consisting of sodium conate, potassium gluconate, sodium tartrate, sodium hydrogen tartrate, potassium hydrogen tartrate, sodium fumarate, sodium malate, dipotassium hydrogen malate, disodium hydrogen malate, sodium dihydrogen pyrophosphate, citric acid, ammonium phosphate, ammonium sulfate, boric acid, lactic acid, boronic acid, maleic acid, malic acid, polyacrylic acid, tartaric acid, ammonium tartrate, ammonium lactate, acetic acid, ammonium acetate, ammonium nitrate, oxalic acid, ammonium oxalate, thiosulfate, ammonium thiosulfate, and formic acid.

[0036] Note that sodium sulfate, sodium carbonate, and sodium bicarbonate, which are exemplified as dyeing assistants, also function as pH adjusters. For example, when a processing liquid composition contains sodium sulfate, it can be considered to contain both a dyeing assistant and a pH adjuster. Furthermore, when sodium sulfate is contained in an amount of 1% by mass, it can be considered to contain both a dyeing assistant and a pH adjuster in an amount of 1% by mass each.

[0037] The content of the pH adjuster is preferably 0.01 to 3.0% by mass relative to the total amount of the treatment liquid composition, and may be adjusted appropriately depending on the application.

[0038] Specifically, the content of the pH adjuster in the treatment liquid composition used together with the inkjet printing ink is preferably 0.01 to 2.0 mass%, 0.03 to 1.0 mass%, or 0.05 to 0.5 mass%, relative to the total amount of the treatment liquid composition. When the content of the pH adjuster is within the above range, fixability and color development tend to be further improved in inkjet recording methods.

[0039] The content of the pH adjuster in the treatment liquid composition used together with the analog textile printing ink is preferably 0.10 to 3.0 mass%, 0.20 to 2.0 mass%, or 0.30 to 1.5 mass%, relative to the total amount of the treatment liquid composition. When the content of the pH adjuster is within the above range, fixability and color development tend to be further improved in analog textile printing.

[0040] 1.5.pH If the pH is too high or too low, the reaction efficiency between the fabric and the dye may decrease. Therefore, in the treatment liquid composition of this embodiment, which uses ε-caprolactam and a dyeing auxiliary in combination, the pH is 4.0 to 12, preferably 5.0 to 11.5, 6.0 to 11, 7.0 to 10.5, 7.5 to 10, or 8.0 to 9.5. A pH of 12 or less improves the reaction efficiency between the fabric and the dye, thereby further improving fixability and color development, and also tends to suppress color unevenness. A pH of 4.0 or higher tends to provide excellent handleability and reduce damage to fabrics, etc., caused by acid.

[0041] 1.6.Viscosity The viscosity of the treatment liquid composition is 2.0 mPa·s or more and 20,000 mPa·s or less, and may be adjusted appropriately depending on the application. In this specification, viscosity refers to a value measured at 20°C using a Brookfield viscometer at 20 rpm for 60 seconds.

[0042] Specifically, the viscosity of the pretreatment liquid composition used with the inkjet printing ink is preferably 2.0 mPa·s or more and 100 mPa·s or less, 2.1 mPa·s or more and 50 mPa·s or less, 2.2 mPa·s or more and 25 mPa·s or less, or 2.5 mPa·s or more and 10 mPa·s or less. A viscosity of 2.0 mPa·s or more tends to further improve fixability and color development, and to suppress bleeding. Furthermore, a viscosity of 100 mPa·s or less tends to further improve the ejection stability of the treatment liquid composition in the inkjet printing method.

[0043] The viscosity of the pretreatment liquid composition used with the analog textile printing ink is preferably 250 mPa·s or more and 20,000 mPa·s or less, 500 mPa·s or more and 10,000 mPa·s or less, or 750 mPa·s or more and 5,000 mPa·s or less. A viscosity of 250 mPa·s or more tends to further improve fixability and color development, and to suppress bleeding. A viscosity of 20,000 mPa·s or less tends to further improve the coatability of the treatment liquid composition in analog textile printing.

[0044] 1.7.Urea In a processing liquid composition for dye printing, urea can contribute to improving the fixability and color development of printed ink. However, a large amount of water must be used to remove urea from the printed material, which poses a problem in terms of environmental adaptability, such as wastewater treatment.

[0045] The treatment liquid composition of this embodiment contains the above-mentioned ε-caprolactam and dyeing aid as a substitute for urea. Therefore, the urea content is preferably 50 g / kg or less, 40 g / kg or less, 30 g / kg or less, 20 g / kg or less, 10 g / kg or less, 5 g / kg or less, or 1 g / kg or less, relative to the total amount of the treatment liquid composition, and it is preferable that urea is not included. By keeping the urea content at 50 g / kg or less, the amount of water used during drainage can be reduced, and environmental adaptability tends to be further improved.

[0046] 1.8. Water-soluble organic solvents The treatment liquid composition preferably contains a water-soluble organic solvent. Examples of water-soluble organic solvents include glycol-based solvents, glycol monoether-based solvents, compounds containing three hydroxyl groups such as glycerin, nitrogen-containing solvents, and alcohol-based solvents. From the viewpoint of improving penetration and color development, it is preferable to contain a glycol-based solvent among water-soluble organic solvents. The water-soluble organic solvents may be used alone or in combination of two or more.

[0047] Specific examples of glycol-based solvents include 1,3-butylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc. From the viewpoint of more effectively and reliably achieving the effects of the present invention, 1,3-butylene glycol is preferred.

[0048] The content of the glycol-based solvent is preferably 0.1 to 5.0 mass %, 0.5 to 3.0 mass %, or 0.7 to 2.0 mass %, relative to the total amount of the treatment liquid composition. By having the content of the glycol-based solvent within the above range, the effects of the present invention can be more effectively and reliably achieved.

[0049] Examples of solvents other than glycol-based solvents include glycol monoether-based solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and triethylene glycol monobutyl ether; nitrogen-containing solvents such as 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone; and alcohol-based solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, 2-butanol, tert-butanol, isobutanol, and n-pentanol.

[0050] The content of the water-soluble organic solvent is preferably 0.1 to 5.0 mass %, 0.5 to 3.0 mass %, or 0.7 to 2.0 mass %, relative to the total amount of the treatment liquid composition. By having the content of the water-soluble organic solvent within the above range, the effects of the present invention can be more effectively and reliably achieved.

[0051] 1.9.Surfactants The treatment liquid composition may further contain a surfactant. Examples of surfactants include acetylene glycol surfactants, silicone surfactants, and fluorine surfactants. The surfactants may be used alone or in combination of two or more.

[0052] From the viewpoint of more effectively and reliably achieving the effects of the present invention, the treatment liquid composition preferably contains an acetylene glycol surfactant. Examples of acetylene glycol surfactants include Olfine (registered trademark) B, Y, P, A, STG, SPC, E1004, E1010, PD-001, PD-002W, PD-003, PD-004, EXP.4001, EXP.4036, EXP.4051, AF-103, AF-104, AK-02, SK-14, and AE-3 (manufactured by Nissin Chemical Industry Co., Ltd.), Surfynol (registered trademark) 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, and 485, and Acetylenol (registered trademark) E00, E00P, E40, and E100 (manufactured by Kawaken Fine Chemicals Co., Ltd.). Among these, it is preferable to use PD-002W from the same viewpoint as above.

[0053] Examples of silicone surfactants include polysiloxane compounds such as polyether-modified organosiloxane. Commercially available polyether-modified organosiloxanes include BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, and BYK-348 (manufactured by BYK Japan Co., Ltd.), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, and KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0054] Examples of fluorine-based surfactants include fluorine-modified polymers, such as BYK-340 (manufactured by BYK Japan KK).

[0055] The content of the surfactant is preferably 0.01 to 1.5 mass %, 0.05 to 1.0 mass %, or 0.10 to 0.75 mass %, relative to the total amount of the treatment liquid composition. By having the content of the surfactant within the above range, the effects of the present invention can be more effectively and reliably achieved.

[0056] 1.10.Water The treatment liquid composition contains water, which may be, for example, ion-exchanged water, ultrafiltered water, reverse osmosis water, pure water such as distilled water, or ultrapure water.

[0057] The content of water is preferably 60 to 98 mass % relative to the total amount of the treatment liquid composition, and may be adjusted appropriately depending on the application.

[0058] Specifically, the water content of the treatment liquid composition used together with the textile printing ink for the inkjet system is preferably 70 to 98 mass %, 80 to 96 mass %, or 85 to 94 mass %, relative to the total amount of the treatment liquid composition. When the water content is within the above range, the ejection stability of the treatment liquid composition in the inkjet system tends to be further improved.

[0059] The water content of the treatment liquid composition used together with the analog textile printing ink is preferably 60 to 95 mass %, 65 to 90 mass %, or 70 to 85 mass %, relative to the total amount of the treatment liquid composition. When the water content is within the above range, the coatability of the treatment liquid composition in analog textile printing tends to be further improved.

[0060] 1.11.Dye The treatment liquid composition may contain or not contain a dye. When the treatment liquid composition contains a dye, it is possible to color a fabric using the treatment liquid composition, depending on the analog textile printing method. In particular, when jet dyeing is performed as the analog textile printing method, it is preferable that the treatment liquid composition contains a coloring material.

[0061] On the other hand, in analog textile printing other than jet dyeing and digital textile printing such as inkjet printing, the treatment liquid composition is not intended to color the textile but is used to improve the fixation of the textile printing ink, and in this respect it is at least distinguished from the textile printing ink. That is, it is also preferable that the treatment liquid composition does not contain any dye. In this embodiment, "does not contain any dye" also means a state in which the dye is substantially not contained. More specifically, a state in which the dye is substantially not contained means that the content of the colorant is preferably 0.1% by mass or less, 0.05% by mass or less, or 0.01% by mass or less, relative to the total amount of the treatment liquid composition. The lower limit of the colorant content is not particularly limited, but is 0% by mass.

[0062] When the treatment liquid composition contains a colorant for applications such as jet dyeing, the dye preferably has a triazine skeleton, a phthalocyanine skeleton, or a vinyl sulfone skeleton. Specific examples of such dyes include Reactive Black 39, which has a triazine skeleton, and Reactive Cyan 15, which has a phthalocyanine skeleton, as well as reactive black, navy, cyan, blue, and brown dyes having these skeletons, which will be described later.

[0063] 1.12.Other Ingredients The treatment liquid composition may further contain components other than those described above, as necessary. Such components are not particularly limited, but examples thereof include solubilizing agents, viscosity modifiers, antioxidants, preservatives, antifungal agents, corrosion inhibitors, chelating agents for capturing metal ions that affect dispersion, other additives, and solvents other than those described above.

[0064] The treatment liquid composition of this embodiment can be prepared by a known method, for example, by mixing the components in any order and, if necessary, performing filtration or the like to remove impurities and foreign matter. The components can be mixed, for example, by sequentially adding the components to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer, and stirring and mixing the components. Filtration methods include, for example, centrifugal filtration and filter filtration.

[0065] 1.13. Recording Media The recording medium used in this embodiment is not particularly limited, but may be a fabric, and examples of fibers constituting the fabric include natural fibers such as cellulose, cotton, linen, silk, and wool, regenerated fibers such as viscose, rayon, and cupra, blends of these natural fibers with regenerated fibers, and blends of these natural fibers with artificial fibers such as polyester fibers, nylon fibers, triacetate fibers, diacetate fibers, and polyamide fibers.

[0066] Among these, the treatment liquid composition of the present embodiment is preferably used by adhering it to a fabric containing one or more fibers selected from the group consisting of cellulose, viscose, and linen. By using it on such a recording medium, fixability and color development tend to be further improved, and color unevenness tends to be further suppressed.

[0067] 2. Ink set The ink set of this embodiment includes the dye printing treatment liquid composition described above and a textile printing ink containing a reactive dye and water. In this manner, the treatment liquid composition of this embodiment is preferably used together with a textile printing ink containing a reactive dye. By using such an ink set, fixability and color development are further improved, and color unevenness is further suppressed. In this embodiment, a single recording apparatus may be equipped with both the treatment liquid composition and the reactive dye textile printing ink.

[0068] Examples of reactive dyes contained in the textile printing ink include CI Reactive Yellow 2, 3, 6, 12, 18, 86, and 95; CI Reactive Orange 2, 5, 12, 13, 20, 35, and 99; CI Reactive Red 3, 4, 7, 12, 13, 15, 16, 24, 29, 31, 32, 33, 43, 45, 46, 58, and 59; CI Reactive Violet 1, 2, and 33; CI Reactive Blue 2, 3, 5, 7, 13, 14, 15, 19, 25, 26, 39, 40, 41, 46, 49, 72, 176, and 198; CI Reactive Green 5 and 8; CI Reactive Brown 1, 2, 7, 8, 9, 11, and 14; and CI Reactive Black 1, 2, 3, 5, 8, 10, 12, 13, and 39. In this specification, reactive dyes refer to compounds classified as reactive dyes in the Color Index.

[0069] In this embodiment, the fabric to which the treatment liquid composition has been applied by the inkjet method may be dried, and then the printing ink may be applied by the inkjet method. Alternatively, the fabric to which the treatment liquid composition has been applied by analog textile printing such as the rotary screen method may be dried, and then the printing ink may be applied by the inkjet method. Alternatively, the fabric may be immersed in the treatment liquid composition, dried, and then the printing ink may be applied by the inkjet method. In this way, when drying is performed after the application of the treatment liquid composition, the viscosity of the treatment liquid composition and the viscosity of the printing ink do not need to be the same.

[0070] The inks used are not limited to inkjet printing inks, and inks for analog printing such as rotary screen printing may also be used in combination.

[0071] 3. Recording method The recording method of this embodiment includes a treatment liquid application step of applying the above-mentioned dye printing treatment liquid composition to a fabric, and an ink application step of applying a textile printing ink containing a reactive dye and water to the fabric. The inkjet recording method of this embodiment also preferably includes a treatment liquid application step of applying the above-mentioned dye printing treatment liquid composition to a fabric, and an ink application step of applying an inkjet textile printing ink containing a reactive dye and water to the fabric by an inkjet method.

[0072] 3.1. Treatment liquid application process The treatment liquid application step is a step of applying a treatment liquid composition to a recording medium. The method for applying the treatment liquid composition to a fabric is not particularly limited, and for example, the fabric may be immersed in or passed through the treatment liquid composition, or the composition may be applied by an inkjet method. It is also preferable to apply the treatment liquid composition to the fabric by any of a spray processing method, a padding processing method, a screen method, and a kiss roll method. After applying the treatment liquid composition, the fabric may be dried once before applying the printing ink.

[0073] In this embodiment, the term "inkjet method" refers to a method of ejecting ink or a treatment liquid from a nozzle in an inkjet head. Examples of such methods include a method of driving a pressure generating means to eject a composition filled in a pressure generating chamber of the inkjet head from the nozzle, and a method of ejecting the composition by applying thermal energy. The method of applying pressure to the ink in the nozzle is not particularly limited, but examples include a piezo method in which a piezoelectric element is used to eject ink droplets, and a thermal method in which heat is used to eject ink droplets.

[0074] 3.2.Ink application process The ink application step is a step of further applying a textile ink onto the portion to which the treatment liquid composition has been applied. In the ink application step, it is also preferable to apply the textile ink by an inkjet method. When the treatment liquid application step and the ink application step are performed by the inkjet method, the treatment liquid application step and the ink application step may be performed in the same pass or in different passes. By performing the treatment liquid application step and the ink application step in the same pass, the productivity of the printed textile tends to be further improved.

[0075] 3.3.Steam process In the steaming process, steam is applied to the fabric with the printing ink attached, using a normal pressure steaming method or a high pressure steaming method. This promotes the fixation of the dye to the fabric. The steaming conditions are not particularly limited, but examples include steaming for 5 to 20 minutes at 80 to 150°C. After that, a washing process may be performed in which the fabric is washed to remove excess components, such as components contained in the treatment liquid composition and the printing ink that are not attached to the fabric, and a drying process may be performed in which the washed printed fabric is dried.

[0076] 4. Inkjet recording device When the treatment liquid composition and the textile ink are applied to the recording medium by an inkjet recording apparatus, the inkjet recording apparatus used is not particularly limited, and either a serial type or a line type can be used.

[0077] As an example of an inkjet recording device, a perspective view of a serial recording device is shown in Fig. 1. As shown in Fig. 1, the serial recording device 10 includes a conveying unit 120 and a recording unit 130. The conveying unit 120 conveys the recording medium F fed to the serial recording device to the recording unit 130, and ejects the recording medium after recording outside the serial recording device. Specifically, the conveying unit 120 has feed rollers and conveys the fed recording medium F in the sub-scanning direction T1.

[0078] The recording unit 130 in the recording device also includes a carriage 134 carrying an inkjet head 131 having nozzles that eject the treatment liquid composition and the textile ink onto the recording medium F sent from the conveying unit 120, and a carriage movement mechanism 135 that moves the carriage 134 in the main scanning directions S1 and S2 of the recording medium F.

[0079] Furthermore, the recording unit 130 in the recording device has nozzles that eject the treatment liquid composition and the textile ink.

[0080] In the case of a serial type recording device, an inkjet head 131 having a length smaller than the width of the recording medium is provided, and the head moves to perform recording in multiple passes (multi-pass). Also, in a serial type recording device, the head 131 is mounted on a carriage 134 that moves in a predetermined direction, and ink is ejected onto the recording medium by moving the head in conjunction with the movement of the carriage. This allows deposition in two or more passes (multi-pass). Note that a pass is also called a main scan. A sub-scan is performed to transport the recording medium between passes. In other words, main scans and sub-scans are performed alternately. [Example]

[0081] The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited to the following examples.

[0082] 1. Preparation of textile printing treatment composition Each component was placed in a mixing tank, mixed and stirred, and filtered through a membrane filter to obtain the textile printing treatment liquid composition shown in Tables 1 and 2. The numerical values ​​for each component shown in each example in the tables represent mass % unless otherwise specified.

[0083] Details of the product ingredients used in Tables 1 and 2 are as follows: [Dyeing aid] Sodium m-nitrobenzenesulfonate Sodium bicarbonate (also functions as a pH adjuster) Sodium carbonate (also functions as a pH adjuster) [pH adjuster] Formic acid Sodium hydroxide [ε-Caprolactam] ε-caprolactam [Moisturizer] urea [Water-soluble organic solvent] 1,3-butylene glycol [High molecular compound] Hydroxyethyl cellulose Sodium Alginate [Surfactants] Olfine PD-002W (product name, acetylene glycol surfactant, manufactured by Nissin Chemical Industry Co., Ltd.)

[0084] 1.1. Viscosity measurement method The viscosity of the treatment liquid composition prepared as above was measured at 20° C. using a Brookfield viscometer at a rotation speed of 20 rpm for 60 seconds.

[0085] 1.2.Method of measuring pH The pH of the treatment liquid composition prepared as described above was measured using a tabletop pH meter (model number: F-72, manufacturer: HORIBA) at a temperature of 20°C.

[0086] 2. Recording method 2.1. Rotary screen recording method The treatment liquid composition was applied to a cotton fabric and dried. Then, a screen for each color was set on a printing machine, and printing was performed on the fabric to which the treatment liquid composition had been applied. Specifically, a textile printing ink was supplied into the screen, and the screen was rotated, causing the printing ink to pass through the openings in the screen and be transferred to the fabric. In this way, a solid pattern was printed.

[0087] The ink-adhered fabric was then treated at 102°C for 10 minutes using a high-temperature steamer (HT-3-550 model, manufactured by Tsujii Senki Kogyo Co., Ltd.), and then dried. Excess dye and other components on the fabric were then washed away, yielding a printed fabric.

[0088] As the rotary screen type textile printing ink, in Examples 1 to 5 and Comparative Examples 1 to 3, Kayacelon Black C-HK (manufactured by Nippon Kayaku Co., Ltd.), which contains a reactive dye, was used to produce printed textiles.

[0089] 2.2. Inkjet printing method Each treatment liquid composition was applied to a cotton fabric and dried. Each printing ink (GENESTA RE) was set in a Monna Lisa inkjet printing machine (Monna Lisa Evo Tre 16-180, manufactured by Seiko Epson Corporation), and a solid pattern was printed at 900 × 600 dpi on the fabric to which the treatment liquid composition had been applied.

[0090] The ink-adhered fabric was then treated at 102°C for 10 minutes using a high-temperature steamer (HT-3-550 model, manufactured by Tsujii Senki Kogyo Co., Ltd.), and then dried. Excess dye and other components on the fabric were then washed away, yielding a printed fabric.

[0091] In Examples 6 and 7 and Comparative Examples 4 and 5, the inkjet printing ink used to create the printed textiles was CYAN GENESTA RE 10L (manufactured by Seiko Epson Corporation), which contains an acid dye.

[0092] 3. Evaluation Method 3.1.Color development The color difference between the color sample of each ink used to form the solid pattern and the solid pattern of the printed material obtained by each of the above methods was measured using a colorimeter i1Pro (manufactured by X-Rite). (Evaluation criteria) AA: Color difference (ΔE) less than 0.4 A: Color difference (ΔE) is 0.4 or more and less than 0.8 B: Color difference (ΔE) is 0.8 or more and less than 1.2 C: Color difference (ΔE) is 1.2 or more and less than 2.0 D: Color difference (ΔE) is 2.0 or more

[0093] 3.2. Fixability The optical density of the solid patterns on the printed textiles obtained by each of the above methods was measured using a colorimeter i1Pro (manufactured by X-Rite). For Examples 1 to 5 and Comparative Examples 1 to 3, which were performed using the rotary screen method, fixability was evaluated based on the relative optical density values ​​of Examples 1 to 5 and Comparative Examples 1 to 3, when the optical density of Comparative Example 1 was set to 100. For Examples 6 to 7 and Comparative Examples 4 to 5, which were performed using the inkjet method, fixability was evaluated based on the relative optical density values ​​of Examples 6 to 7 and Comparative Examples 4 to 5, when the optical density of Comparative Example 4 was set to 100. (Evaluation criteria) AA: Relative optical density value is 97 to 100 A: Relative optical density is 95 or more and less than 97 B: Relative optical density value is 90 or more and less than 95 C: Relative optical density value is 85 or more and less than 90 D: Relative optical density value is less than 85

[0094] 3.3. Suppression of color unevenness For the solid patterns of the printed textiles obtained by each of the above methods, the optical density at the four vertices of a 10 cm square was measured using a colorimeter i1Pro (manufactured by X-Rite), and color unevenness was evaluated based on the difference in optical density at the four points. (Evaluation criteria) A: Optical density difference is less than 0.8 B: Optical density difference is 0.8 or more and less than 1.2 C: Optical density difference is 1.2 or more and less than 2.0 D: Optical density difference is 2.0 or more

[0095] 3.4. Nitride content of wastewater The printed fabric obtained as described above before the washing process was washed with water, and the amounts of ammonium salts, nitrates, and other nitrides, including urea, contained in the washed water were quantified. The amount of ammonium salts was quantified by the indophenol method, which utilizes the color development that occurs when nitrates react with phenol in the presence of hypochlorite, in accordance with JIS K0102. The amount of nitrates was quantified by a colorimetric method, in accordance with JIS K0400, utilizing the color development that occurs when nitrates react with sulfosalicylic acid, which is obtained by adding sodium salicylate and sulfuric acid, followed by alkaline treatment. The amount of other nitrides, including urea, was quantified by decomposing the sample with persulfate and sulfuric acid, followed by colorimetric measurement of nitrates, in accordance with the above-mentioned JIS K0400. (Evaluation criteria) A: Total nitride content is 250 ppm or less D: Total nitride content exceeds 250 ppm

[0096] 4. Evaluation Results The compositions of the treatment liquids used in each example and the evaluation results are shown in Tables 1 and 2. Tables 1 and 2 show that by performing printing using a treatment liquid composition for dye printing containing ε-caprolactam and a dyeing auxiliary and having a pH of 4.0 to 12, the resulting printed textiles have excellent fixability and color development, color unevenness is suppressed, and the nitride content of wastewater can be reduced, thereby reducing the amount of water used for drainage.

[0097] In the above examples, cotton was used as the cellulose-containing fabric, but similar evaluations were also carried out on linen or viscose fabrics, and the same effects as those of the above examples and comparative examples were obtained. [Explanation of symbols]

[0098] 10...serial type recording device, 120...conveying section, 130...recording section, 131...inkjet head, 134...carriage, 135...carriage moving mechanism, F...recording medium, S1, S2...main scanning direction, T1...sub-scanning direction.

Claims

1. ε-caprolactam, a dyeing assistant containing one or more selected from benzenesulfonate, sodium sulfate, sodium carbonate, and sodium hydrogencarbonate; pH is 4.0 to 12; A processing liquid composition for dye textile printing.

2. Contains no dyes, The dye textile printing treatment liquid composition according to claim 1.

3. Contains dyes, The dye has a triazine skeleton, a phthalocyanine skeleton, or a vinyl sulfone skeleton. The dye textile printing treatment liquid composition according to claim 1.

4. the ratio of the content of the ε-caprolactam to the content of the dyeing auxiliary is 2.5 to 50; The dye textile printing treatment liquid composition according to claim 1.

5. including polymeric compounds, The dye textile printing treatment liquid composition according to claim 1.

6. the polymer compound is one or more selected from the group consisting of guar gum, ethoxyguar gum, propoxyguar gum, ethoxypropoxyguar gum, tamarind gum, xanthan gum, carboxyethyl cellulose, carboxymethyl cellulose, ammonium cellulose, hydroxyethyl cellulose, sodium alginate, acrylic polymers, polyethylene glycol, polyacrylamide, acrylamide copolymers, AMPS polymers and copolymers, dextrin, carboxymethyl starch, and carbomer; The dye textile printing treatment liquid composition according to claim 5.

7. Contains a pH adjuster, The dye textile printing treatment liquid composition according to claim 1.

8. The pH adjuster may be triethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, isopropanolamine, sodium citrate, disodium citrate, trisodium citrate, monosodium succinate, disodium succinate, sodium acetate, sodium lactate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, trisodium phosphate, tripotassium phosphate, sodium gluconate , potassium gluconate, sodium tartrate, sodium hydrogen tartrate, potassium hydrogen tartrate, sodium fumarate, sodium malate, dipotassium hydrogen malate, disodium hydrogen malate, sodium dihydrogen pyrophosphate, citric acid, ammonium phosphate, ammonium sulfate, boric acid, lactic acid, boronic acid, maleic acid, malic acid, polyacrylic acid, tartaric acid, ammonium tartrate, ammonium lactate, acetic acid, ammonium acetate, ammonium nitrate, oxalic acid, ammonium oxalate, thiosulfate, ammonium thiosulfate, and formic acid. The dye textile printing treatment liquid composition according to claim 7.

9. The viscosity at 20°C is 2.0 mPa·s or more and 20,000 mPa·s or less. The dye textile printing treatment liquid composition according to claim 1.

10. The dyeing assistant contains a benzenesulfonate. The dye textile printing treatment liquid composition according to claim 1.

11. It is used by adhering it to a fabric containing one or more fibers selected from the group consisting of cellulose, viscose, and linen. The dye textile printing treatment liquid composition according to claim 1.

12. Used with textile printing inks containing reactive dyes, The dye textile printing treatment liquid composition according to claim 1.

13. a textile printing ink containing a reactive dye and water; and the dye printing treatment liquid composition according to any one of claims 1 to 12. Ink set.

14. a treatment liquid application step of applying the treatment liquid composition for dye textile printing according to any one of claims 1 to 12 to a fabric; and an ink applying step of applying a textile printing ink containing a reactive dye and water to the fabric.

15. The recording method according to claim 14, wherein in the treatment liquid application step, the dye textile printing treatment liquid composition is applied to the fabric by any one of a spraying method, a padding method, a screen method, and a kiss roll method.

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