Ink set and inkjet printing method

Abstract

To provide an ink set in which a printed matter has excellent color development and light resistance.SOLUTION: There is provided an ink set which is used by adhering to a fabric to which a treatment liquid composition comprising an acid compound and a thickener is adhered, wherein the ink set comprises a first inkjet ink composition containing a first dye having a monochlorotriazine group or a vinylsulfonyl group, water and a water-soluble organic solvent and a second inkjet ink composition containing a second dye having a sulfonic acid group and a Cr element and having no monochlorotriazine group or vinyl sulfonyl group, water and a water-soluble organic solvent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an ink set and an inkjet recording method. [Background technology]

[0002] The inkjet recording method is capable of recording high-resolution images using a relatively simple device and has been rapidly developing in various fields. In the process, various studies have been conducted on ejection stability, storage stability, etc. For example, Patent Document 1 discloses an aqueous ink composition for dyeing polyamide-based inks, which contains at least one dye selected from acid dyes, direct dyes, and reactive dyes as a pigment and further contains a specific compound, ethylene glycol, with the aim of providing an ink composition with excellent ejection stability and storage stability. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2010 / 109867 Summary of the Invention [Problem to be solved by the invention]

[0004] The coloring material to be blended in the ink composition for textile printing must be selected depending on the type of fabric, the liquid properties of the ink composition, etc., so the range of choices for the materials used for recording is not substantially wide. Incidentally, even when the ink composition disclosed in Patent Document 1 is used, the color development of the obtained textile print can be said to be good, but there is still room for improvement in terms of lightfastness. [Means for solving the problem]

[0005] The ink set of the present invention is an ink set to be used by being applied to a fabric to which a treatment liquid composition containing an acid compound and a thickener has been applied, and comprises: a first inkjet ink composition containing a first dye having a monochlorotriazine group or a vinylsulfonyl group, water, and a water-soluble organic solvent; and a second inkjet ink composition containing a second dye that does not have a monochlorotriazine group or a vinylsulfonyl group but has a sulfonic acid group and a Cr element, water, and a water-soluble organic solvent.

[0006] The recording method of the present invention includes a discharge step of discharging the first inkjet ink composition or the second inkjet ink composition provided in the ink set described above from a recording head onto an area of ​​a fabric to which a treatment liquid composition containing an acid compound and a thickener has been applied. [Brief explanation of the drawings]

[0007] [Figure 1] Table 1 shows the composition of the ink set used in the examples and the evaluation results thereof. [Figure 2] Table 2 shows the composition of the ink set used in the examples and the evaluation results thereof. [Figure 3] FIG. 1 is a diagram illustrating an example of an inkjet recording apparatus used in an inkjet recording method. DETAILED DESCRIPTION OF THE INVENTION

[0008] 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.

[0009] 1. Ink set The ink set of this embodiment (hereinafter also referred to as "the present ink set") is an ink set to be used by being deposited on a fabric to which a treatment liquid composition containing an acid compound and a thickener has been deposited, and comprises a first inkjet ink composition containing a first dye having a monochlorotriazine group or a vinylsulfonyl group, water, and a water-soluble organic solvent, and a second inkjet ink composition containing a second dye that does not have a monochlorotriazine group or a vinylsulfonyl group but has a sulfonic acid group and a Cr element, water, and a water-soluble organic solvent.

[0010] Conventionally, colorants to be incorporated into ink compositions for textile printing have had to be selected depending on, for example, the type of fabric and the properties of the ink composition. For example, for fabrics such as cotton, a basic pretreatment solution is often used followed by an ink composition containing a reactive dye. On the other hand, for fibers having amide groups, such as silk or nylon, an acidic pretreatment solution is often used followed by an ink composition containing an acidic dye. However, when an acidic dye is used on fabrics that have been pretreated with acid, the dye molecules tend to adhere to the fabric surface, but lightfastness is poor. On the other hand, when fibers having amide groups are treated with a basic pretreatment solution, the dye molecules tend not to adhere to the fabric surface, resulting in poor color development. As such, poor color development or lightfastness can occur depending on the type of fiber, and there has been a demand for an ink set that can achieve both color development and lightfastness even when recording is performed using a variety of fibers.

[0011] In contrast to this, in the present embodiment, an ink set is provided that includes a first inkjet ink composition containing a first dye having a monochlorotriazine group or a vinylsulfonyl group, and a second inkjet ink composition containing a second dye that does not have a monochlorotriazine group or a vinylsulfonyl group, but has a sulfonic acid group and a Cr element, making it possible to obtain a printed item that has excellent color development and lightfastness.

[0012] The first inkjet ink composition uses a first dye having a monochlorotriazine group or a vinylsulfonyl group. The presence of such a functional group stabilizes the molecular structure of the first dye, further improving lightfastness. The first inkjet ink composition may also function as a reactive dye ink, which exhibits excellent color development properties by strongly bonding to functional groups, such as hydroxyl groups, on the fabric surface. The second inkjet ink composition uses a second dye having a sulfonic acid group and Cr element, instead of a monochlorotriazine group or a vinylsulfonyl group. This allows for improved lightfastness due to the chromium element, instead of the structural stabilization provided by the monochlorotriazine group or the vinylsulfonyl group. The second inkjet ink composition may also function as an acid dye ink, which exhibits excellent color development properties by strongly bonding to functional groups, such as amino groups or carboxyl groups, on the fabric surface. This allows the ink set to be widely used on a variety of fabrics with different fiber types. However, the reasons for this are not limited to those mentioned above.

[0013] Each of the compositions contained in this ink set will be described in detail below.

[0014] 1.1. Fabric with treatment liquid composition attached This ink set is used by applying it to a fabric to which a treatment liquid composition containing an acid compound and a thickener has been applied. The material of the fabric to be treated is not particularly limited, but examples include polyamide fibers, polyester fibers, nylon fibers, triacetate fibers, diacetate fibers, and blends thereof. To more effectively and reliably achieve the lightfastness effect of the present invention, it is preferable that the fabric contains an amide group, more preferably polyamide fibers, and even more preferably polyamide fibers. This further improves the binding ability of the second dye, which tends to further improve color development.

[0015] It is preferable that the present ink set further comprises a treatment liquid composition. By including the treatment liquid composition of this embodiment, the lightfastness effect of the present invention can be more effectively and reliably achieved. As such a treatment liquid composition, the following compounds can be used in combination.

[0016] 1.1.1. Acid compounds When the treatment liquid composition contains an acid compound, the color development of the resulting printed textile is improved. The acid compound may be used alone or in combination of two or more.

[0017] Examples of acid compounds include ammonium salts such as ammonium sulfate, ammonium acetate, and ammonium tartrate, and protonic acids such as formic acid, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, boric acid, acetic acid, carbonic acid, formic acid, benzoic acid, chlorous acid, hypochlorous acid, sulfurous acid, hyposulfite, nitrous acid, hyponitrous acid, phosphorous acid, and hypophosphorous acid. Among these, from the viewpoint of more effectively and reliably achieving the lightfastness effect of the present invention, it is preferable to include one or more selected from the group consisting of ammonium sulfate, ammonium acetate, formic acid, and boric acid, and it is more preferable to include ammonium sulfate.

[0018] In the treatment liquid composition, the content of the acid compound is preferably from 0.1 to 10 parts by mass, from 1 to 5 parts by mass, or from 2 to 4 parts by mass, relative to 100 parts by mass of the treatment liquid composition. By setting the content of the acid compound within the above range, the binding strength of the second dye is further improved, and therefore color development, light fastness, and water fastness tend to be further improved.

[0019] When the acid compound includes ammonium sulfate or ammonium acetate, the total content of ammonium sulfate and ammonium acetate is preferably from 0.1 to 10 parts by mass, from 1 to 5 parts by mass, or from 2 to 4 parts by mass, per 100 parts by mass of the treatment liquid composition. By keeping the total content of ammonium sulfate and ammonium acetate within the above ranges, the binding strength of the second dye is further improved, and therefore color development, light fastness, and water fastness tend to be further improved.

[0020] When the acid compound contains formic acid or boric acid, the total content of formic acid and boric acid is preferably 0.01 to 3 parts by mass, and 0.05 to 1 part by mass, per 100 parts by mass of the treatment liquid composition. By keeping the total content of formic acid and boric acid within the above range, the binding strength of the second dye is further improved, which tends to further improve color development, lightfastness, and waterfastness. It also has the effect of suppressing the growth of mold and fungi.

[0021] 1.1.2. Thickeners The thickener contained in the treatment liquid composition improves the fixation of the dye to the fabric, improves the color development and lightfastness of the printed textile, and also prevents bleeding. One type of thickener may be used alone, or two or more types may be used in combination.

[0022] Examples of thickeners include natural gums such as guar gum and locust bean gum, starches, seaweeds such as sodium alginate, plant skins such as pectic acid, cellulose derivatives such as methylcellulose, ethylcellulose, hydroxyethylcellulose, and carboxymethylcellulose, processed starches such as roasted starch, alpha starch, carboxymethyl starch, carboxyethyl starch, and hydroxyethyl starch, processed natural gums such as shirat gum and roasted bean gum, algin derivatives, and synthetic glues and emulsions such as polyvinyl alcohol and polyacrylic esters. Among these, hydroxyethylcellulose is preferred from the viewpoint of more effectively and reliably achieving the lightfastness effect of the present invention.

[0023] In the treatment liquid composition, the content of the thickener is preferably from 1 to 15 parts by mass, from 2 to 10 parts by mass, or from 3 to 7 parts by mass, relative to 100 parts by mass of the treatment liquid composition. By keeping the content of the thickener within the above range, the application properties of the treatment liquid composition and its retention in the fabric tend to be further improved.

[0024] 1.1.3.Ureas The processing liquid composition preferably contains a urea. The inclusion of a urea tends to improve dye fixation, lightfastness, and color development. Examples of ureas include urea, dimethylurea, ethyleneurea, tetramethylurea, thiourea, monomethylthiourea, dimethylthiourea, and 1,3-dimethyl-2-imidazolidinone. Among these, urea is preferably used from the same viewpoint as above.

[0025] In the treatment liquid composition, the content of the urea is preferably from 1 to 30 parts by mass, from 2 to 20 parts by mass, or from 3 to 10 parts by mass, relative to 100 parts by mass of the treatment liquid composition. By setting the content of the urea within the above range, the coatability and ejection stability of the treatment liquid composition tend to be further improved.

[0026] Preservatives The processing liquid composition preferably contains a preservative. Examples of preservatives include, but are not limited to, 1,2-benzothiazolin-3-one, 3,4-isothiazolin-3-one, 4,4-dimethyloxazolidine, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolon-3-one, benzotriazole, 2-bromo-2-nitro-1,3-propanediol-based preservatives, and hexahydro-1,3,5-tris-(2-hydroxyethyl)-S-triazine-based preservatives. To more effectively and reliably achieve the lightfastness effect of the present invention, 1,2-benzothiazolin-3-one is preferred.

[0027] In the treatment liquid composition, the content of the preservative is preferably from 0.001 to 1 part by mass, and from 0.005 to 0.5 parts by mass, per 100 parts by mass of the treatment liquid composition. By keeping the content of the preservative within the above range, the effect of improving lightfastness according to the present invention tends to be more effective and reliable.

[0028] 1.1.5.Water Examples of water used in the treatment liquid composition include pure water and ultrapure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water, with ion-exchanged water being preferred. From the viewpoint of more effectively and reliably achieving the effects of the present invention, the content of water is preferably 50 parts by mass or more and 95 parts by mass or less, or 70 parts by mass or more and 92 parts by mass or less, relative to the total amount of the treatment liquid composition.

[0029] The treatment liquid composition may contain components other than the above-mentioned compounds. The content of the other components is preferably 5 parts by mass or less, 3 parts by mass or less, or 1 part by mass or less, relative to the total mass of the treatment liquid composition.

[0030] 1.2. First Inkjet Ink Composition The first inkjet ink composition (hereinafter referred to as the first ink composition) provided in this ink set contains a first dye having a monochlorotriazine group or a vinylsulfonyl group, water, and a water-soluble organic solvent.

[0031] 1.2.1.First dye The first dye has a monochlorotriazine group or a vinylsulfonyl group. By having the first dye have a monochlorotriazine group or a vinylsulfonyl group, the obtained printed material has excellent lightfastness. As the first dye, one type may be used alone, or two or more types may be used in combination.

[0032] The first dye preferably has a sulfonic acid group. When the first dye further has a sulfonic acid group, compatibility with fabrics (dyeability) tends to be further improved in addition to color development and light fastness.

[0033] The first dye is not particularly limited as long as it has a monochlorotriazine group or a vinylsulfonyl group, and examples of the dye having a monochlorotriazine group include CI Reactive Yellow 95, CI Reactive Red 31, CI Reactive Blue 15:1, CI Reactive Orange 13, CI Reactive Blue 49, CI Reactive Red 24:1, and CI Reactive Black 39.

[0034] Specific examples of commercially available dyes having a vinylsulfonyl group include CI Reactive Yellow 15, CI Reactive Yellow 37, CI Reactive Yellow 42; CI Reactive Orange 16, CI Reactive Orange 74, CI Reactive Orange 107; CI Reactive Red 23, CI Reactive Red 35, CI Reactive Red 106, CI Reactive Red 180, CI Reactive Red 218; CI Reactive Violet 5, CI Reactive Blue 19, CI Reactive Blue 21, CI Reactive Blue 38, CI Reactive Blue 229; CI Reactive Brown 18; CI Reactive Black 5, CI Reactive Black 14, and CI Reactive Black 31.

[0035] The first dye preferably includes CI Reactive Yellow 95, CI Reactive Red 31, CI Reactive Blue 15:1, CI Reactive Orange 13, CI Reactive Blue 49, CI Reactive Red 24:1, or CI Reactive Black 39. By including these dyes, water resistance tends to be further improved in addition to color development and light fastness.

[0036] The content of the first dye is preferably 0.5 parts by mass to 25 parts by mass, 1 part by mass to 15 parts by mass, or 3 parts by mass to 10 parts by mass, relative to 100 parts by mass of the first ink composition. By keeping the content of the first dye within the above range, water resistance, in addition to color development and light resistance, tends to be further improved.

[0037] 1.2.2. Water-soluble organic solvents The first ink composition contains a water-soluble organic solvent. Examples of the water-soluble organic solvent include polyhydric alcohols, glycol ethers, and 2-pyrrolidones. The water-soluble organic solvent may be used alone or in combination of two or more.

[0038] Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,3-pentanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-2,4-pentanediol, trimethylolpropane, glycerin, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, and 1,2-octanediol. Among these, from the viewpoint of more effectively and reliably achieving the light resistance effect of the present invention, it is preferable to include one or more selected from triethylene glycol, 3-methyl-1,5-pentanediol, and glycerin.

[0039] Glycol ethers can be classified into, for example, alkylene glycol monoethers and alkylene glycol diethers, and more specifically, include triethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether. Among these, triethylene glycol monobutyl ether is preferred from the viewpoint of more effectively and reliably achieving the lightfastness effect of the present invention.

[0040] Examples of 2-pyrrolidones include unsubstituted 2-pyrrolidone, as well as substituted 2-pyrrolidones such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, and N-(2-hydroxyethyl)-2-pyrrolidone.

[0041] The content of the water-soluble organic solvent in the first ink composition is preferably 1 part by mass to 50 parts by mass, 5 parts by mass to 40 parts by mass, or 10 parts by mass to 30 parts by mass, relative to 100 parts by mass of the first ink composition. By keeping the content of the water-soluble organic solvent in the first ink composition within the above range, the effect of improving lightfastness according to the present invention tends to be more effectively and reliably achieved.

[0042] The content of the polyhydric alcohol is preferably 1 to 40 parts by mass, 2 to 30 parts by mass, or 5 to 25 parts by mass, relative to 100 parts by mass of the first ink composition. By keeping the content of the polyhydric alcohol within the above range, the effect of improving lightfastness according to the present invention tends to be more effective and reliable.

[0043] The content of the glycol ether is preferably 0.5 to 20 parts by mass, 1 to 10 parts by mass, or 2 to 8 parts by mass, relative to 100 parts by mass of the first ink composition. By keeping the content of the glycol ether within this range, the effect of improving lightfastness according to the present invention tends to be more effective and reliable.

[0044] Surfactants The first ink composition may contain a surfactant. Examples of surfactants include acetylene glycol surfactants, silicone surfactants, and fluorine surfactants. One type of surfactant may be used alone, or two or more types may be used in combination.

[0045] Examples of acetylene glycol surfactants include Surfynol (registered trademark) 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG50, 104S, 420, 440, 465, 485, SE, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, and DF110D (manufactured by Nissin Chemical Industry Co., Ltd.), and Olfine (registered trademark) B. , Y, P, A, STG, SPC, E1004, E1010, D-10PG, PD-001, PD-002W, PD-003, PD-004, EXP.4001, EXP.4036, EXP.4051, AF-103, AF-104, AK-02, SK-14, AE-3 (manufactured by Nissin Chemical Industry Co., Ltd.), and Acetylenol (registered trademark) E00, E00P, E40, E100 (manufactured by Kawaken Fine Chemicals Co., Ltd.). Among these, Surfynol 104PG50 is preferred from the viewpoint of more effectively and reliably achieving the lightfastness effect of the present invention.

[0046] 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.).

[0047] Examples of fluorine-based surfactants include fluorine-modified polymers, and examples of commercially available products include BYK-340 (manufactured by BYK Japan KK).

[0048] The content of the surfactant in the first ink composition is preferably 0.01 to 3 parts by mass, and 0.05 to 1 part by mass, relative to 100 parts by mass of the first ink composition. By keeping the content of the surfactant in the first ink composition within this range, the effect of improving lightfastness according to the present invention tends to be more effective and reliable.

[0049] 1.2.4. pH adjusters The first ink composition may contain a pH adjuster. Examples of pH adjusters include inorganic acids (e.g., sulfuric acid, hydrochloric acid, nitric acid, etc.), inorganic bases (e.g., lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonia, etc.), organic bases (e.g., triethanolamine, diethanolamine, monoethanolamine, triisopropanolamine), and organic acids (e.g., adipic acid, citric acid, succinic acid, etc.). Among these, from the viewpoint of more effectively and reliably achieving the effects of the present invention, organic bases are preferred, and triisopropanolamine is more preferred. One pH adjuster may be used alone, or two or more pH adjusters may be used in combination.

[0050] The content of the pH adjuster in the first ink composition is preferably 0.1 to 3 parts by mass, and 0.3 to 1 part by mass, per 100 parts by mass of the first ink composition. By keeping the content of the pH adjuster in the first ink composition within this range, the effect of improving lightfastness according to the present invention tends to be more effective and reliable.

[0051] 1.2.5. Chelating Agents The first ink composition may contain a chelating agent. Examples of chelating agents include ethylenediaminetetraacetic acid or salts thereof (e.g., disodium dihydrogen ethylenediaminetetraacetate), 3-hydroxy-2,2'-iminodisuccinic acid or salts thereof (e.g., tetrasodium 3-hydroxy-2,2'-iminodisuccinate), and iminodisuccinic acid or salts thereof (e.g., tetrasodium iminodisuccinate). Among these, tetrasodium iminodisuccinate is preferred from the viewpoint of more effectively and reliably achieving the effects of the present invention. One type of chelating agent may be used alone, or two or more types may be used in combination.

[0052] The content of the chelating agent in the first ink composition is preferably 0.005 parts by mass to 1 part by mass, or 0.01 parts by mass to 0.1 parts by mass, per 100 parts by mass of the first ink composition. By keeping the content of the chelating agent in the first ink composition within this range, the effect of improving lightfastness according to the present invention tends to be more effective and reliable.

[0053] Preservatives The first ink composition may contain a preservative. Examples of trade names for preservatives include Proxel XL2, Proxel CRL, Proxel BDN, Proxel GXL, Proxel IB, and Proxel TN. Among these, Proxel XL2, Proxel GXL, and the like are preferred from the viewpoint of more effectively and reliably achieving the effects of the present invention. One type of preservative may be used alone, or two or more types may be used in combination.

[0054] The content of the preservative in the first ink composition is preferably 0.01 parts by mass to 1 part by mass, and 0.05 parts by mass to 0.5 parts by mass, relative to 100 parts by mass of the first ink composition. By keeping the content of the preservative in the first ink composition within this range, the effect of improving lightfastness according to the present invention tends to be more effective and reliable.

[0055] 1.2.7.Water Examples of water include pure water and ultrapure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water, with ion-exchanged water being preferred. From the viewpoint of more effectively and reliably achieving the effects of the present invention, the content of water is preferably 50 parts by mass or more and 90 parts by mass or less, or 60 parts by mass or more and 80 parts by mass or less, relative to the total amount of the first ink composition.

[0056] The first ink composition may contain components other than the above-mentioned compounds. The content of the other components is preferably 5 parts by mass or less, 3 parts by mass or less, or 1 part by mass or less, relative to the total mass of the first ink composition.

[0057] 1.3. Second Inkjet Ink Composition The second inkjet ink composition (hereinafter also referred to as the second ink composition) of this ink set contains a second dye that does not have a monochlorotriazine group or a vinylsulfonyl group, but has a sulfonic acid group and a Cr element, water, and a water-soluble organic solvent.

[0058] Preferably, the first ink composition in the ink set is a chromatic ink, and the second ink composition is an achromatic ink. By configuring the ink set in this manner, it is possible to record images on a variety of fabrics, and lightfastness also tends to be excellent.

[0059] 1.3.1.Second dye The second dye does not have a monochlorotriazine group or a vinylsulfonyl group, but has a sulfonic acid group and a Cr element. By having the dye does not have a monochlorotriazine group or a vinylsulfonyl group, but has a sulfonic acid group and a Cr element, the resulting printed material has excellent color development and lightfastness. As the second dye, one type may be used alone, or two or more types may be used in combination.

[0060] The second dye is not particularly limited as long as it does not have a monochlorotriazine group or a vinylsulfonyl group, but has a sulfonic acid group and a Cr element. Examples of trade names for such dyes include CI Acid Black 52:1, CI Acid Black 172, CI Acid Black 207, CI Acid Blue 161, CI Acid Blue 193, and CI Acid Brown 298. From the viewpoint of more effectively and reliably achieving the effects of the present invention, CI Acid Black 172 is preferred.

[0061] The content of the second dye is preferably from 0.1 to 20 parts by mass, from 0.5 to 15 parts by mass, or from 1 to 10 parts by mass, relative to 100 parts by mass of the second ink composition. By keeping the content of the second dye within the above ranges, water resistance, in addition to color development and light resistance, tends to be further improved.

[0062] In the second ink composition, the types and contents of compounds other than the second dye that can be contained can be the same as those in the first ink composition.

[0063] 2. Inkjet recording method The inkjet recording method of this embodiment (hereinafter also referred to as "the present recording method") includes a discharge step of discharge- ing from a recording head the first inkjet ink composition or the second inkjet ink composition provided in the ink set described above onto an area of ​​fabric to which a treatment liquid composition containing an acid compound and a thickener has been applied, and preferably further includes a treatment liquid composition application step of applying the treatment liquid composition to the fabric. The printed textile obtained by this inkjet recording method has excellent lightfastness.

[0064] As an example of an inkjet device that can be used for this recording method, a perspective view of a serial printer is shown in Figure 3. As shown in Figure 3, the serial printer 20 includes a conveying unit 220 and a recording unit 230. The conveying unit 220 conveys the fabric F fed to the serial printer to the recording unit 230 and discharges the fabric after recording outside the serial printer. Specifically, the conveying unit 220 has feed rollers and conveys the fed fabric F in the sub-scanning direction T1.

[0065] The recording unit 230 also includes a carriage 234 that mounts an inkjet head 231 having nozzles that eject an ink composition onto the fabric F sent from the transport unit 220, and a carriage movement mechanism 235 that moves the carriage 234 in the main scanning directions S1 and S2 of the fabric F. The inkjet head 231 may also have nozzles that eject the treatment liquid composition.

[0066] In the case of a serial printer, an inkjet head 231 having a length smaller than the width of the fabric is provided, and the head moves to perform recording in multiple passes (multi-pass). In a serial printer, the head 231 is mounted on a carriage 234 that moves in a predetermined direction, and the head moves in conjunction with the movement of the carriage to eject an ink composition onto the fabric F. A treatment liquid composition may also be ejected as necessary. In this way, recording is performed in two or more passes (multi-pass). 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.

[0067] The inkjet device of this embodiment is not limited to the serial printer, but may be a line printer, which uses a line head, an inkjet head having a length equal to or greater than the recording width of the fabric, to perform recording on the fabric in a single scan. [Example]

[0068] 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.

[0069] 1 and 2, Tables 1 and 2 are provided showing the compositions of the ink sets of the examples and comparative examples.

[0070] 1. Preparation of each composition of the ink set 1.1. Pretreatment solution A 50 parts by mass of hydroxyethyl cellulose, 50 parts by mass of urea, and 30 parts by mass of ammonium sulfate were thoroughly mixed, and then 1,000 parts by mass of ion-exchanged water was added in small amounts while stirring for 30 minutes at 60° C. Thereafter, 1 part by mass of formic acid, 1 part by mass of boric acid, and 0.1 part by mass of 1,2-benzothiazolin-3-one were further added to the stirred solution, and the mixture was stirred for 10 minutes. This solution was then filtered through a membrane filter with a pore size of 10 μm to obtain pretreatment solution A.

[0071] 1.2.Pretreatment solution B Pretreatment solution B was obtained in the same manner as pretreatment solution A, except that 30 parts by mass of ammonium acetate was used instead of 30 parts by mass of ammonium sulfate.

[0072] 1.3. Ink composition Each dye composition was obtained by placing each material in a mixing tank, mixing and stirring for 1 hour, and filtering through a 1 μm membrane filter (cellulose acetate filter paper, manufactured by Advantec Toyo Co., Ltd.). Tables 1 and 2 also indicate the presence or absence of a monochlorotriazine group, a sulfonic acid group, and Cr metal in each dye. The content of each component described below is based on 100 parts by mass of the ink composition.

[0073] <Yellow ink: Y1> ·Dye: CIReactive Yellow95 6 parts by mass Water-soluble organic solvent: Triethylene glycol monobutyl ether 5 parts by mass 3-methyl-1,5-pentanediol 5 parts by mass Triethylene glycol 6 parts by mass Glycerin 10 parts by mass Surfactant: Surfynol 104PG50 0.1 parts by mass pH adjuster: Triisopropanolamine 0.5 parts by mass Chelating agent: 0.03 parts by mass of tetrasodium iminodisuccinate Preservative: Proxel XL2 0.1 parts by weight Water: Ion-exchanged water Remainder

[0074] The same water-soluble organic solvent, surfactant, pH adjuster, chelating agent, and preservative were used in the same amounts as in the yellow ink described above, except that the dye was replaced with the following. The amount of water was also adjusted according to the amount of dye used. <Yellow ink: Y2> ·Dye: CIAcid Yellow110 6 parts by mass <Magenta ink: M1> ·Dye: CIReactive Red31 6 parts by mass <Magenta ink: M2> ·Dye: CIAcid Red289 6 parts by mass <Cyan ink: C1> ·Dye: CIReactive Blue15:1 6 parts by mass <Cyan ink: C2> ·Dye: CIAcid Blue90 6 parts by mass <Orange Ink: Or1> ·Dye: CIReactive Orange13 6 parts by mass <Orange Ink: Or2> ·Dye: CIAcid Orange56 6 parts by mass <Blue Ink: Bl1> ·Dye: CIReactive Blue49 6 parts by mass <Blue Ink: Bl2> ·Dye: CIAcid Blue 120 6 parts by mass <Red Ink: R1> ·Dye: CIReactive Red24:1 6 parts by mass <Red Ink: R2> ·Dye: CIAcid Red447 6 parts by mass <Gray ink: Gr1> ·Dye: CIReactive Black39 1 part by mass <Gray ink: Gr2> ·Dye: CIAcid Black172 1 part by mass <Black ink: Bk1> ·Dye: CIReactive Black39 10 parts by mass <Black ink: Bk2> ·Dye: CIAcid Black172 10 parts by mass

[0075] 2. Recording method: Preparation of printed material Each pretreatment liquid obtained above was applied to the fabrics listed in Tables 1 and 2, and the fabrics were squeezed with a mangle at a pickup rate of 20% and dried. Each ink composition prepared above was filled into the cartridge of an inkjet printer (product name "PX-G930", manufactured by Seiko Epson Corporation). Using the printer, each ink composition was applied to the fabric that had been subjected to the above pretreatment, and an image was recorded.

[0076] Specifically, a solid pattern of each color was formed on a fabric at a printing resolution of 720 × 720 dpi and a print duty of 100%, after which the fabric was steamed at 100°C for 20 minutes, washed with an aqueous solution containing 0.2 parts by mass of LACCOL STA (product name, surfactant, manufactured by Meisei Chemical Industry Co., Ltd.) at 55°C for 10 minutes, and dried to obtain a printed fabric.

[0077] Here, the term "solid pattern" refers to a pattern in which dots are recorded for all pixels, which are the minimum recording unit area defined by the recording resolution.

[0078] 3. Evaluation Method 3.1.Color development For each of the printed products obtained above, the volume of the color reproduction range (Gamut) was measured, and the color development was evaluated according to the following evaluation criteria. (Evaluation criteria) A: The color gamut volume is 4,000 or more. B: The color gamut volume is between 35,000 and 40,000. C: The color gamut volume is between 25,000 and 35,000. D: The color gamut volume is greater than or equal to 1,5000 and less than 2,5000

[0079] 3.2.Lightfastness Using a Xenon lightfastness tester (Suga Testing Instruments Co., Ltd., product name "XL-75s"), the printed fabrics of each example were exposed for 10 days under conditions of 23°C, relative humidity 50% RH, and illuminance of 70,000 lux. The hue of the samples before and after exposure was measured using a spectrodensitometer (product name "Spectrolino", manufactured by X-RITE) under conditions of light source: D65, status: DIN_NB, viewing angle: 10 degrees, and filter: UV, and the hue difference (ΔE * ) was calculated and the lightfastness was evaluated according to the following evaluation criteria. In each ink set, the result of the ink with the lowest lightfastness was taken as the lightfastness of that ink set. ΔE * ={(ΔL * )2 +(Δa * ) 2 +(Δb * ) 2} 1 / 2 (Equation 1) ΔL * =L * 1-L * 2 (Equation 2) Δa * =a * 1-a * 2 (Equation 3) Δb * =b * 1-b * 2 (Equation 4) However, L * 1, a * 1, b * 1 indicates the measurement value of the initial printed item, and L * 2, a * 2, b * 2 indicates the measurement value after 10 days of exposure. (Evaluation criteria) A:ΔE * is less than 10 B:ΔE * is greater than or equal to 10 and less than 12.5 C:ΔE * is greater than or equal to 12.5 and less than 15 D:ΔE * is greater than or equal to 15 and less than 17.5 E:ΔE * is 17.5 or more

[0080] 3.3.Water resistance (durability) A water resistance test was carried out on each of the obtained printed textiles according to the method described in JIS L 0846:2004. The attached white cloth used in the test was the same for both the first attached white cloth and the second attached white cloth, and was cotton (No. 3-3) as described in JIS L 0803. Based on the visual method in clause 10 a) of JIS L 0801, water resistance was evaluated according to the following evaluation criteria. In each ink set, the result of the ink with the lowest water resistance is considered to be the water resistance of that ink set. (Evaluation criteria) A: Level 4 or above B: Grade 3 or above but less than grade 4 C: Grade 2 or above but less than grade 3 D: Less than grade 2

[0081] 3.4.Clogging recovery An inkjet printer (Seiko Epson Corporation, product name "PX-G930") was filled with each of the ink compositions prepared above, and ejection was performed from all nozzles. The printer was then turned off and left to stand for 14 days in an environment of 40°C and 20% RH. Cleaning and nozzle check printing were then alternately repeated, and the number of cleanings required to restore normal ejection without missing dots or deflection was counted. Clogging recovery was evaluated based on the number of cleanings using the following evaluation criteria. The results are shown in Tables 1 and 2. The results for the ink with the lowest clogging recovery in each ink set were used to determine the clogging recovery performance of that ink set. (Evaluation criteria) A: Cleaning was performed once or less and normal ejection was restored. B: Cleaning was performed 2-3 times and normal ejection was restored. C: Cleaning was performed 4 to 5 times and normal ejection was restored. D: Normal ejection did not recover even after cleaning five times.

[0082] 4. Evaluation Results The composition of the ink set used in each example and the evaluation results are shown in Tables 1 and 2. Tables 1 and 2 show that the ink set is used by being deposited on a fabric to which a treatment liquid composition containing an acid compound and a thickener has been deposited, and the ink set includes a first inkjet ink composition containing a dye having a monochlorotriazine group or a vinylsulfonyl group, water, and a water-soluble organic solvent, and a second inkjet ink composition containing a dye that does not have a monochlorotriazine group or a vinylsulfonyl group but has a sulfonic acid group and a Cr element, water, and a water-soluble organic solvent, and the printed material obtained using the ink set is excellent in lightfastness, etc. [Explanation of symbols]

[0083] 20...serial printer, 220...transport unit, 230...recording unit, 231...inkjet head, 234...carriage, 235...carriage moving mechanism, F...fabric, S1, S2...main scanning direction, T1...sub-scanning direction.

Claims

1. An ink set to be applied to a fabric to which a treatment liquid composition containing an acid compound and a thickener has been applied, a first ink-jet ink composition containing a first dye having a monochlorotriazine group or a vinylsulfonyl group, water, and a water-soluble organic solvent; a second ink-jet ink composition containing a second dye that does not have a monochlorotriazine group or a vinylsulfonyl group but has a sulfonic acid group and a Cr element, water, and a water-soluble organic solvent; Ink set.

2. the first ink-jet ink composition is a chromatic color ink, the second inkjet ink composition is an achromatic ink; The ink set according to claim 1 .

3. The fabric contains amide groups. The ink set according to claim 1 .

4. The fabric is a polyamide fiber. The ink set according to claim 1 .

5. The treatment liquid composition is further provided. The ink set according to claim 1 .

6. the first dye having a monochlorotriazine group or a vinylsulfonyl group has a sulfonic acid group; The ink set according to claim 1 .

7. The acid compound includes ammonium sulfate. The ink set according to claim 1 .

8. a discharge step of discharging the first inkjet ink composition or the second inkjet ink composition provided in the ink set according to any one of claims 1 to 7 from a recording head onto a region of the fabric to which a treatment liquid composition containing an acid compound and a thickener has been applied, Inkjet recording method.

9. The method further includes a treatment liquid composition applying step of applying the treatment liquid composition to a fabric. The inkjet recording method according to claim 8.

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