Acid dye black ink composition for inkjet

Abstract

To provide an ink composition that has excellent recovery property from clogging, continuous discharge performance, storage stability, and hue of black.SOLUTION: According to the present invention, an acid dye black ink composition for inkjet comprises a water-soluble dye (A), another water-soluble dye (B) different from the dye (A), and a compound (C), wherein the dye (A) is one or more selected from the group consisting of a compound represented by formula (1) below and a compound represented by formula (2) below, the compound (C) is one or more selected from the group consisting of a compound represented by formula (3) below and a compound represented by formula (4) below, and the mass ratio of the compound (C) relative to the dye (A) (compound (C) / dye (A)) ranges from 1 / 20000 to 20 / 20000.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an acid dye black ink composition for inkjet printing. [Background technology]

[0002] As described in Patent Document 1, CI Acid Black 172 and other inks such as CI Acid Black 52:1 and CI Acid Black 194 are widely used as acid dye black inks for dyeing fabrics containing animal fibers such as wool and silk, and amide fibers such as nylon. Both of these inks contain chromium. Recently, the use of such dyes has been discouraged due to safety and environmental considerations, but there are no suitable acid dye black inks that can replace them. Furthermore, while it is possible to reproduce black by layering multiple inks such as yellow, magenta, and cyan, the brightness increases and a deep black cannot be achieved.

[0003] On the other hand, dark colors can be achieved by using navy blue ink. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2023-48107 Summary of the Invention [Problem to be solved by the invention]

[0005] However, to reproduce black using a dark blue ink, it is necessary to use multiple ink colors in addition to the dark blue ink. In this case, the dye solid content increases, making it very difficult to ensure ejection reliability, such as clogging recovery and continuous ejection, as well as storage stability at low temperatures. Another method is to use a reactive dye black ink instead, but this has the problem of uneven dyeing when printed on nylon, resulting in an insufficient black color. [Means for solving the problem]

[0006] The present invention provides an ink composition for inkjet black acid dyes, comprising a water-soluble dye (A), a water-soluble dye (B) different from the dye (A), and a compound (C), wherein the dye (A) is at least one selected from the group consisting of compounds represented by the following formula (1) and compounds represented by the following formula (2), the compound (C) is at least one selected from the group consisting of compounds represented by the following formula (3) and compounds represented by the following formula (4), and the mass ratio of the compound (C) to the dye (A) (the compound (C) / the dye (A)) is 1 / 20,000 or more and 20 / 20,000 or less.

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[0011] (In formula (4), R 1is a hydrogen atom, -NH2, or a phenylamino group, and R 2 is a hydrogen atom or -NH2, and R 3 is a hydrogen atom or a sulfo group. 1 , R 2 , and R 3 cannot simultaneously become a hydrogen atom. 1 When is a phenylamino group, R 2 and R 3 cannot simultaneously become a hydrogen atom. [Brief explanation of the drawings]

[0012] [Figure 1] 1 is a flowchart illustrating an example of an inkjet recording method. [Figure 2] Table 1 shows the composition of an inkjet acid dye black ink composition. [Figure 3] Table 2 shows the composition of an inkjet acid dye black ink composition. [Figure 4] Table 3 shows the evaluation results. [Figure 5] Table 4 shows the evaluation results. DETAILED DESCRIPTION OF THE INVENTION

[0013] Below, we will explain in detail the embodiment of the present invention (hereinafter referred to as the ``present embodiment''), but the present invention is not limited to this and various modifications are possible within the scope of the gist of the present invention.

[0014] 1. Acid dye black ink composition for inkjet printing The inkjet acid dye black ink composition (hereinafter also referred to as "ink composition") of this embodiment contains a water-soluble dye (A), a water-soluble dye (B) different from the dye (A), and a compound (C), wherein the dye (A) is one or more compounds selected from the group consisting of compounds represented by the following formula (1) and compounds represented by the following formula (2), the compound (C) is one or more compounds selected from the group consisting of compounds represented by the following formula (3) and compounds represented by the following formula (4), and the mass ratio of the compound (C) to the dye (A) (compound (C) / dye (A)) is 1 / 20,000 or more and 20 / 20,000 or less.

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[0019] In formula (4), R 1 is a hydrogen atom, -NH2, or a phenylamino group, and R 2 is a hydrogen atom or -NH2, and R 3 is a hydrogen atom or a sulfo group. 1 , R 2 , and R 3 cannot simultaneously become a hydrogen atom. 1 When is a phenylamino group, R 2 and R 3 cannot simultaneously become a hydrogen atom.

[0020] According to this embodiment, an ink composition having excellent clogging recovery properties, continuous ejection properties, storage stability, and black hue can be obtained.

[0021] Although the reason why such excellent effects are obtained by this embodiment is not clear, the inventors presume as follows.

[0022] Inkjet acid dye black ink compositions containing multiple dyes generally tend to contain a high dye content, which makes them prone to dye precipitation due to water evaporation or low-temperature storage. To prevent this, ink compositions typically contain a water-soluble organic solvent, such as glycerin. However, adding a large number of dyes and a water-soluble organic solvent can cause the ink's physical properties, particularly its viscosity, to deviate from inkjet suitability, resulting in poor jetting performance. The inventors discovered that an inkjet acid dye black ink composition that achieves high ink density while maintaining jetting characteristics can be achieved by incorporating a navy blue dye represented by formula (1) and / or formula (2). However, such dyes tend to have relatively high solubility in water but low solubility in organic solvents. Therefore, ink compositions containing such dyes tend to precipitate and crystallize relatively easily upon water evaporation or a decrease in temperature. Once the dye crystallizes, it becomes extremely difficult to redissolve the dye. For these reasons, conventional ink compositions containing such dyes have tended to have poor clogging recovery, continuous jetting, and storage stability. Furthermore, ink compositions containing conventional navy blue dyes have different dyeing performance depending on the type of fabric, making it difficult to consistently produce a good black color on a variety of fabrics.

[0023] The water-soluble dye (A) has a specific structure and produces a dark navy blue color. To address the above-mentioned problems, the present inventors discovered that adding a predetermined amount of a compound having a structure similar to the skeleton of the water-soluble dye (A) to an ink composition containing the water-soluble dye (A) reduces the likelihood of dye precipitation due to water evaporation or low-temperature storage. Furthermore, the ink composition tends to inhibit dye crystallization even if the dye solidifies due to water evaporation or a drop in temperature. This ensures dye resolubility and provides excellent clogging recovery and storage stability. It is believed that this effect is achieved because the compound's structure is similar to that of the water-soluble dye (A) and is relatively close to the molecular structure of the water-soluble dye (A), thereby inhibiting dye crystallization. It is believed that this also reduces dye and compound precipitation, i.e., the occurrence of continuous ejection problems due to the formation of foreign matter. Furthermore, since the crystallization and formation of foreign matter of the dye can be inhibited, the ink composition can stably produce an excellent black color on a variety of fabrics. From the above, it is presumed that the ink composition of this embodiment can provide an ink composition that has excellent clogging recovery properties, continuous ejection properties, storage stability, and a black hue, although the reasons are not limited to these.

[0024] Next, each component contained in the ink composition will be described.

[0025] 1.1.Water-soluble dye (A) The ink composition of this embodiment contains a water-soluble dye (A) (hereinafter also referred to as "dye (A)"). The dye (A) is one or more types selected from the group consisting of compounds represented by the above formula (1) and compounds represented by the above formula (2). The dye (A) may be used alone or in combination of two or more types.

[0026] The dye (A) is preferably at least one selected from the group consisting of compounds represented by the following formula (12) and compounds represented by the following formula (13): Use of such a water-soluble dye tends to make it possible to obtain an ink composition that has better clogging recovery properties, continuous ejection properties, storage stability, and a black hue.

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[0029] The dye (A) is more preferably a compound represented by the above formula (12). Use of such a water-soluble dye tends to result in an ink composition that has superior lightfastness, as well as superior clogging recovery properties, continuous ejection properties, storage stability, and black hue.

[0030] In this embodiment, the compound represented by formula (12) can be obtained by purifying commercially available CI Acid Blue 113 using a known method. The compound represented by formula (13) can be obtained by purifying commercially available CI Acid Blue 116 using a known method. Examples of such purification methods include activated carbon filtration, microfiltration, and ultrafiltration. To ensure more reliable purification, it is preferable to perform pretreatment, such as dissolving CI Acid Blue 113 or CI Acid Blue 116 in water and then adjusting the pH or exchanging heavy metals, prior to purification.

[0031] The mass ratio of the compound (C) described below to the dye (A) (compound (C) / dye (A)) is 1 / 20,000 or more and 20 / 20,000 or less. A mass ratio of 1 / 20,000 or more can favorably suppress dye crystallization and ensure the resolubility of the dye, thereby achieving excellent clogging recovery and storage stability. A mass ratio of 20 / 20,000 or less can favorably suppress the precipitation of the dye or compound, i.e., the occurrence of continuous ejection problems due to the formation of foreign matter.

[0032] The mass ratio of the water-soluble dye (B) described below (hereinafter also referred to as "dye (B)") to the dye (A) (dye (B) / dye (A)) is preferably 1: 2 or more and 2: 1 or less. When the mass ratio is within this range, an ink composition having excellent clogging recovery properties, continuous ejection properties, and storage stability, as well as an excellent black hue, tends to be obtained.

[0033] The content of dye (A) is preferably 0.5% by mass or more and 20.0% by mass or less, more preferably 1.0% by mass or more and 15.0% by mass or less, and even more preferably 2.0% by mass or more and 10.0% by mass or less, based on the total amount of the ink composition. When the content of dye (A) is within the above range, an ink composition having better clogging recovery properties, continuous ejection properties, storage stability, and black hue tends to be obtained.

[0034] 1.2.Water-soluble dye (B) The ink composition of this embodiment contains a water-soluble dye (B) different from the dye (A). Examples of the dye (B) include acid dyes, reactive dyes, and direct dyes. The dye (B) may be used alone or in combination of two or more.

[0035] The dye (B) preferably contains an azo-based water-soluble dye. When the dye (B) contains an azo-based water-soluble dye, an ink composition tends to be obtained that has better clogging recovery, continuous dischargeability, and storage stability, as well as better black hue and lightfastness. The reason for such excellent effects is unclear, but the inventors speculate as follows: That is, by using an azo-based water-soluble dye as the water-soluble dye, the difference in dyeing performance for fabrics can be reduced. Furthermore, compared to other dyes such as xanthene dyes, azo-based water-soluble dyes have better lightfastness and can reduce changes in hue over time. Therefore, it is speculated that the use of an azo-based water-soluble dye tends to result in an ink composition that has better clogging recovery, continuous dischargeability, and storage stability, as well as better black hue and lightfastness. However, the reason is not limited to this.

[0036] The dye (B) preferably contains a yellow dye and a magenta dye. When the dye (B) contains the above dyes, an ink composition having a better black hue tends to be obtained.

[0037] Examples of acid dyes include CI Acid Red 1, 6, 8, 9, 13, 14, 18, 19, 24, 26, 27, 32, 35, 37, 42, 51, 52, 57, 80, 82, 83, 85, 87, 88, 89, 92, 94, 95, 97, 106, 111, 114, 115, 118, 119, 127, 128, 131, 133, 134, 138, 143, 145, 151, 154, 155, 158, 249, 252, 257, 260, 265, 266, 274, 276, 289, 299, 301, 336, 337, and 361; and CI Acid Violet. 5, 7, 11, 15, 34, 41, 43, 48, 49, 51, 54, 66, 97, 126 etc; CIAcid Yellow CIAcid Blue 1, 7, 9, 22, 23, 25, 27, 29, 40, 41, 43, 45, 49, 59, 62, 74, 76, 78, 80, 83, 87, 90, 92, 93, 100, 102, 103, 104, 114, 117, 120, 127, 1 CIAcid Black 1, 2, 7, 24, 26, 29, 31, 48, 94, 234 etc; CIAcid Orange 1, 7, 8, 10, 19, 20, 24, 28, 33, 41, 45, 51, 56, 63, 67, 94, 95, etc.; CI Acid Green 3, 7, 9, 19, 20, 25, 27, 28, 36, 40, 41, 44, etc.; CI Acid Brown 2, 4, 13, 14, 20, 27, 48, 53, 100, 101, 103, 106, etc.

[0038] The acid dye preferably includes a yellow acid dye and a magenta acid dye. The yellow acid dye preferably includes one or more selected from the group consisting of yellow acid dyes and orange acid dyes, more preferably one or more selected from the group consisting of CI Acid Yellow 3, CI Acid Yellow 79, and CI Acid Orange 94. The magenta acid dye preferably includes one or more selected from the group consisting of red acid dyes and purple acid dyes, more preferably one or more selected from the group consisting of CI Acid Red 52, CI Acid Red 249, CI Acid Violet 48, and CI Acid Violet 54. When the dye (B) contains the above-mentioned acid dye, it tends to be possible to obtain an ink composition having a better black hue.

[0039] Examples of direct dyes include CI Direct Red 2, 4, 9, 23, 26, 31, 39, 62, 63, 72, 75, 76, 79, 80, and 81; CI Direct Violet 7, 9, 47, 48, and 51; CI Direct Yellow 8, 9, 11, 12, 27, 28, 29, 33, 39, 41, 44, 50, 59, 86, 87, 96, 106, 130, and 142; CI Direct Blue 1, 10, 15, 55, 67, 71, 77, 78, 87, 106, 108, 109, 120, 151, 159, 163, and 168; and CI Direct Black. 9, 17, 19, 22, 32, 51, 56, 80, 91, 154, 166, 168, 199, etc.

[0040] Examples of reactive dyes include CI Reactive Yellow 1, 2, 3, 5, 13, 14, 15, 17, 18, 20, 21, 23, 25, 26, 27, 35, 37, 81, 95, 161, etc.; CI Reactive Red 1, 3, 3:1, 4, 13, 17, 21, 22, 23, 24, 24:1, 29, 35, 40, 41, 43, 45, 49, 66, 79, 96, 108, 141, 180, 218, 226, 245, etc.; CI Reactive Violet 8, 16, 34, etc.; CI Reactive Blue 1, 2, 5, 13, 19, 28, 29, 49, etc.; and CI Reactive Orange. 1, 2, 4, 5, 7, 12, 13, 14, 16, 20, 29, 33, 35, 38, 64, 67, 72, 72:1, 78, 82, 84, 86, 87, 91, 99, 99:1, 107, 113, 122, 124, 125, etc.; CI Reactive Black 5, 31, 39, etc.

[0041] The content of dye (B) is preferably 0.5% by mass or more and 20.0% by mass or less, more preferably 1.0% by mass or more and 15.0% by mass or less, and even more preferably 2.0% by mass or more and 10.0% by mass or less, based on the total amount of the ink composition. When the content of dye (B) is within the above range, an ink composition having better clogging recovery properties, continuous ejection properties, storage stability, and black hue tends to be obtained.

[0042] 1.3. Compound (C) The ink composition of this embodiment contains a compound (C). The compound (C) is one or more compounds selected from the group consisting of compounds represented by the above formula (3) and compounds represented by the above formula (4). The compound (C) may be used alone or in combination of two or more types.

[0043] The compound represented by formula (4) above is preferably one or more compounds selected from the group consisting of compounds represented by formula (5), compounds represented by formula (6), and compounds represented by formula (7): Use of such a compound (C) tends to make it possible to obtain an ink composition that has an excellent black hue, as well as better clogging recovery properties, continuous ejection properties, and storage stability.

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[0047] The compound represented by formula (3) above is preferably a compound represented by formula (8) below. The compound represented by formula (4) above is preferably one or more selected from the group consisting of compounds represented by formula (9) below, compounds represented by formula (10) below, and compounds represented by formula (11) below, and is more preferably a compound represented by formula (9) below. Use of such compound (C) tends to make it possible to obtain an ink composition that has an excellent black hue, as well as even better clogging recovery properties, continuous ejection properties, and storage stability.

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[0052] The content of compound (C) is preferably 0.0001% by mass or more and 0.0100% by mass or less, and more preferably 0.0002% by mass or more and 0.0070% by mass or less, based on the total amount of the ink composition. When the content of compound (C) is within the above range, it tends to be possible to obtain an ink composition that has an excellent black hue, as well as better clogging recovery properties, continuous ejection properties, and storage stability.

[0053] 1.4. Diol-based water-soluble organic solvent (D) The ink composition of this embodiment preferably further contains a diol-based water-soluble organic solvent (D) (hereinafter also referred to as "diol-based organic solvent"). The content of the diol-based organic solvent (D) is preferably 50% by mass or more relative to 100% by mass of the dye solid content. The diol-based organic solvent (D) may be used alone or in combination of two or more.

[0054] When an ink composition contains a predetermined amount of diol-based organic solvent (D), it tends to be possible to obtain an ink composition with better clogging recovery, continuous dischargeability, and storage stability. While the reason for such excellent effects is unclear, the inventors speculate as follows: The dye (A), which is the dark blue ink, has a relatively high solubility in water. Furthermore, the diol-based organic solvent (D) has a lower viscosity than triol-based water-soluble organic solvents such as glycerin and monool-based water-soluble organic solvents such as methanol, and is less likely to thicken the ink composition. Therefore, the diol-based organic solvent (D) can suitably dissolve the dye (A) in the ink composition, suppress dye crystallization, and ensure the resolubility of the dye. Therefore, it is speculated that when an ink composition contains a predetermined amount of diol-based organic solvent (D), it is possible to obtain an ink composition with better clogging recovery, continuous dischargeability, and storage stability. However, the reason is not limited to this.

[0055] The diol-based organic solvent (D) is not particularly limited as long as it has two hydroxyl groups in its structure and is a water-soluble organic solvent. Examples of such diol-based organic solvents (D) include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 3-methyl-1,5-pentanediol.

[0056] The diol organic solvent (D) is preferably an alkyl diol having from 2 to 10 carbon atoms and having hydroxyl groups at both ends, and more preferably contains one or more selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,2-hexanediol, and 3-methyl-1,5-pentanediol. When the ink composition contains such a diol organic solvent (D) in a predetermined amount, it tends to be possible to obtain an ink composition that has even better clogging recovery properties, continuous ejection properties, and storage stability.

[0057] The content of the diol organic solvent (D) is preferably 75% by mass or more, more preferably 100% by mass or more, and even more preferably 120% by mass or more, based on 100% by mass of the dye solid content. The upper limit of the content is, for example, 200% by mass or less. When the content of the diol organic solvent (D) is within the above range, it tends to be possible to obtain an ink composition having even better clogging recovery properties, continuous ejection properties, and storage stability.

[0058] The content of the diol organic solvent (D) is preferably 5.0% by mass or more and 25.0% by mass or less, and more preferably 10.0% by mass or more and 20.0% by mass or less, based on the total amount of the ink composition. When the content of the diol organic solvent (D) is within the above range, an ink composition having even better clogging recovery properties, continuous ejection properties, and storage stability can be obtained.

[0059] 1.5.Surfactants The ink composition may contain a surfactant. The surfactant has the function of reducing the surface tension of the ink composition and adjusting the wettability with a recording medium. The surfactant may be used alone or in combination of two or more types.

[0060] Examples of surfactants include acetylene glycol surfactants, silicone surfactants, and fluorine surfactants.

[0061] Examples of acetylene glycol surfactants include Surfynol (registered trademark) 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, and DF110D (manufactured by Nissin Chemical Industry Co., Ltd.); Olfine (registered trademark) Examples of the acetylene compounds include (trademarks) 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, and SK-14; AE-3 (manufactured by Nissin Chemical Industry Co., Ltd.); and Acetylenol (registered trademark) E00, E00P, E40, and E100 (manufactured by Kawaken Fine Chemicals Co., Ltd.).

[0062] Examples of silicone surfactants include polysiloxane compounds such as polyether-modified organosiloxanes. Commercially available polyether-modified organosiloxanes include, for example, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, and BYK-348 (manufactured by BYK Japan K.K.), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6004, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, and KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0063] Examples of fluorine-based surfactants include fluorine-modified polymers, such as BYK-340 (manufactured by BYK Japan KK).

[0064] The content of the surfactant is preferably from 0.01% to 10% by mass, and more preferably from 0.05% to 5.0% by mass, relative to the total amount of the ink composition. When the content of the surfactant is within the above range, an ink composition having better clogging recovery properties, continuous ejection properties, storage stability, and black hue tends to be obtained.

[0065] 1.6. Amines The ink composition may contain amines. The amines may function as pH adjusters. The amines may be used alone or in combination of two or more.

[0066] Examples of amines include diethanolamine, triethanolamine, and triisopropanolamine.

[0067] The content of the amines is preferably from 0.01% to 10% by mass, and more preferably from 0.05% to 5.0% by mass, relative to the total amount of the ink composition. When the content of the amines is within the above range, it tends to be possible to obtain an ink composition that has better clogging recovery properties, continuous ejection properties, storage stability, and a black hue.

[0068] 1.7.Ureas The ink composition may contain ureas. Ureas tend to function as a moisturizing agent for the ink composition and as a dyeing aid that improves the dyeing ability of the dye. The ureas may be used alone or in combination of two or more.

[0069] Examples of ureas include urea, ethylene urea, tetramethyl urea, thiourea, and 1,3-dimethyl-2-imidazolidinone.

[0070] The content of the urea compound is preferably 0.1% by mass or more and 10% by mass or less, based on the total amount of the ink composition. When the content of the urea compound is within this range, an ink composition having better clogging recovery properties, continuous ejection properties, storage stability, and black hue tends to be obtained.

[0071] 1.8.Water The ink composition may contain water. Examples of water include pure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water, as well as ultrapure water from which ionic impurities have been removed as much as possible. Water sterilized by ultraviolet irradiation or the addition of hydrogen peroxide is preferred because it can suppress the growth of mold and bacteria when the ink composition is stored for a long period of time.

[0072] The water content is preferably 30.0% by mass or more and 80.0% by mass or less relative to the total amount of the ink composition. By keeping the water content within this range, an increase in the viscosity of the ink composition can be suppressed.

[0073] 1.9. Other water-soluble organic solvents The ink composition may contain other water-soluble organic solvents different from the diol organic solvent (D), as long as the effects of the present invention are achieved. The other water-soluble organic solvents may be used alone or in combination of two or more.

[0074] Examples of such other water-soluble organic solvents include glycerin; glycol monoethers such as diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, diethylene glycol monobutyl ether, dipropylene glycol monopropyl ether, ethylene glycol phenyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether; and alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, 2-butanol, tert-butanol, iso-butanol, n-pentanol, 2-pentanol, 3-pentanol, and tert-pentanol.

[0075] The content of the other water-soluble organic solvent is preferably 0.1% by mass or more and 10% by mass or less, based on the total amount of the ink composition. When the content of the other water-soluble organic solvent is within the above range, an ink composition having better clogging recovery properties, continuous ejection properties, storage stability, and black hue tends to be obtained.

[0076] 1.10.Other Ingredients The ink composition may contain various additives that can be typically used in ink compositions, other than the above components, such as sugars, preservatives, antifungal agents, solubilizing agents, viscosity adjusters, pH adjusters, antioxidants, ultraviolet absorbers, oxygen absorbers, rust inhibitors, corrosion inhibitors, and chelating agents. The additives may be used alone or in combination of two or more.

[0077] The total content of the additives is preferably 0.01% by mass or more and 10.0% by mass or less relative to the total amount of the ink composition.

[0078] 1.11. Physical properties of ink composition The viscosity of the ink composition at 20°C is preferably 1.5 mPa·s or more and 15 mPa·s or less, more preferably 1.5 mPa·s or more and 7 mPa·s or less, and even more preferably 1.5 mPa·s or more and 5.5 mPa·s or less.

[0079] From the viewpoint of ensuring appropriate wetting and spreading properties on a recording medium, the upper limit of the surface tension of the ink composition at 25°C is preferably 40 mN / m or less, more preferably 38 mN / m or less, even more preferably 35 mN / m or less, even more preferably 32 mN / m or less, and even more preferably 30 mN / m or less. From the same viewpoint, the lower limit of the surface tension is preferably 15 mN / m or more, more preferably 20 mN / m or more, even more preferably 25 mN / m or more, and even more preferably 27 mN / m or more. In this specification, the surface tension can be measured using a surface tensiometer CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.) as the surface tension when a platinum plate is wetted with the ink composition at room temperature and normal pressure. If the surface tension of the ink composition is within the above range, continuous ejection properties and initial filling properties in ink jet recording can be improved.

[0080] 1.9. Method for producing ink composition The ink composition can be prepared by mixing dye (A), dye (B), compound (C), and optionally diol-based organic solvent (D), surfactant, amines, ureas, water, and other components in any order, and then removing impurities and foreign matter by filtration or other means as necessary. The components can be mixed by sequentially adding the components to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer, stirring, and mixing them. Filtration methods include centrifugal filtration and filter filtration.

[0081] 2. Inkjet recording method The inkjet recording method of this embodiment is carried out using the inkjet acid dye black ink composition of this embodiment. Specifically, the inkjet recording method includes a step of ejecting the ink composition from an inkjet head and depositing it on a recording medium. FIG. 1 shows an example of the inkjet recording method of this embodiment. This inkjet recording method includes an ink depositing step and a heating step, in this order. Next, the recording medium, the inkjet recording apparatus that can be used in the recording method, and the steps will be described.

[0082] 2.1. Recording Media Examples of the recording medium include absorbent recording media and fabrics, with fabrics being preferred.

[0083] Examples of absorbent recording media include those containing fabrics, plain paper such as electrophotographic paper, and inkjet paper, which have high ink composition permeability, as well as art paper, coated paper, and cast paper used in general offset printing, which have relatively low ink composition permeability.

[0084] Examples of raw yarns for fabrics include blends of silk, cotton, wool, nylon, polyester, polyamide, and polyurethane; biodegradable fibers such as polylactic acid; and natural and synthetic fibers such as rayon. Fabrics may be made from one type of fiber or a blend of two or more types of fibers. Fabrics may be made from the above-listed fibers in any form, such as woven fabric, knitted fabric, or nonwoven fabric.

[0085] The raw yarn of the fabric is preferably nylon, wool, or silk, and more preferably nylon or silk. The ink composition can stably produce an excellent black color even on fabrics other than nylon and silk.

[0086] When the recording medium is a fabric, the inkjet recording method includes a transporting step of transporting the recording medium containing the fabric, and a recording step of recording an ink composition on the recording medium. The recording method of this embodiment may also be a textile printing method in which the recording medium contains a fabric. The textile printing method may further include a heating step and a washing step in addition to the recording step.

[0087] 2.2. Inkjet recording device The inkjet recording apparatus can be either a serial type or a line type. These types of inkjet recording apparatuses are equipped with an inkjet head, and while changing the relative positional relationship between the recording medium and the inkjet head, droplets of an ink composition are ejected from the nozzle holes of the inkjet head at a predetermined timing and in a predetermined volume (mass), thereby depositing the ink composition on the recording medium to form a predetermined image.

[0088] The inkjet recording apparatus can employ any known configuration, such as a drying unit, a roll unit, a winding unit, etc. The inkjet recording apparatus may have, for example, a transport unit for transporting the recording medium, an image layer forming unit for recording an image using an ink composition, a drying unit, and an overall drying unit for heating and blowing air onto the recording surface.

[0089] The conveying means is, for example, composed of a roller. In this case, it may have multiple rollers. Another method is to convey the recording medium by adhering it to or absorbing it on a rubber belt or the like. The position and number of conveying means can be arbitrarily selected as long as the recording medium can be conveyed. The conveying means may include a roll mechanism, a tray, various platens, and the like.

[0090] The image layer forming unit records an image layer by ejecting an ink composition onto the recording surface of the recording medium. The image layer forming unit is equipped with an inkjet head equipped with nozzles, and a nozzle row is assigned to each predetermined ink composition.

[0091] The drying means can be used to heat and dry the image layer formed on the recording surface and / or remove volatile components from the recording medium. The drying means may be located anywhere, taking into consideration the timing of the deposition process, the transport path of the recording medium, and other factors. Examples of image layer drying means include a method of applying heat to the recording medium by platen heating or the like, a method of blowing air onto the image on the recording medium, and a combination of these methods. Specific examples of means used in these methods include forced air heating, radiant heating, conductive heating, high-frequency drying, and microwave drying.

[0092] 2.3. Each step of the recording method The step of depositing the ink composition on a recording medium can be carried out using an inkjet recording apparatus. That is, the ink composition is filled into an inkjet head so that it can be ejected from a predetermined nozzle, and then ejected onto a recording medium at a predetermined timing in this state, thereby depositing the ink composition on the recording medium.

[0093] The recording method may include a step of heating the recording medium as appropriate. For example, when an inkjet recording apparatus is used, the heating step may use the drying means described above. The drying means is not limited to an inkjet recording apparatus, and other drying means may be used as appropriate. By including a heating step in the recording method, bleeding of the image is suppressed, and the image can be fixed more efficiently.

[0094] The recording method may include other steps, such as a step of applying another ink composition and a washing step.

[0095] In the recording method, the ink composition according to this embodiment is used, and therefore it is possible to record an image that has excellent clogging recovery properties, continuous ejection properties, and storage stability, as well as excellent black hue and lightfastness.

[0096] 2.4.Printing method The textile printing method may be an inkjet textile printing method in which an ink composition is filled into an inkjet device and used. Examples of the inkjet device include a drop-on-demand type inkjet device. Drop-on-demand type inkjet devices include devices that employ an inkjet textile printing method using a piezoelectric element disposed in a head, and devices that employ an inkjet textile printing method using thermal energy from a heater or the like of a heat-generating resistor element disposed in a head.

[0097] 2.4.1.Transportation process The conveying step is a step of conveying a recording medium including a fabric. Examples of the means for conveying the recording medium include conveying means known in the inkjet system.

[0098] 2.4.2. Recording process The recording process is a process of recording an ink composition onto a recording medium. When an inkjet method is used, the ink composition is ejected by the inkjet method toward the surface (image forming area) of a fabric, which is at least a part of the recording medium, and adhered to the recording medium to form an image. The ejection conditions may be appropriately determined depending on the physical properties of the ink composition to be ejected.

[0099] 2.4.3.Heating process The textile printing method may further include a heating step of heating the recording medium to which the ink composition has been attached after the recording step. By including the heating step, the colorant can be more effectively dyed into the fibers that make up the fabric. Examples of heating methods include high-temperature steaming, high-pressure steaming, and thermosol methods.

[0100] In the heating step, the ink composition-adhering surface of the recording medium may or may not be pressurized. Examples of heating methods that do not pressurize the ink composition-adhering surface of the recording medium include oven drying, i.e., methods that do not involve pressing, such as conveyor ovens and batch ovens. By including such a heating step, the productivity of recorded materials is further improved. Examples of heating methods that pressurize the ink composition-adhering surface of the recording medium include heat pressing and wet-on-drying. In this embodiment, pressurization refers to applying pressure to the recording medium by contacting a solid.

[0101] The temperature during the heat treatment is preferably 80° C. or higher and 150° C. or lower, more preferably 90° C. or higher and 110° C. or lower. When the temperature during the heat treatment is within the above range, the colorant tends to be more effectively dyed onto the fibers constituting the fabric.

[0102] 2.4.4. Cleaning process The textile printing method may further include a washing step of washing the recording medium to which the ink composition has adhered after the heating step. The washing step can effectively remove the acid dye that has not adhered to the fiber. The washing step can be carried out using, for example, water.

[0103] In this way, a recorded matter such as a printed matter can be obtained in which an image derived from the ink composition is formed on a recording medium including a fabric.

[0104] 2.4.5. Treatment composition application step The fabric used for textile printing may be the fabric itself, or may be fabric that has been pretreated with a treatment liquid composition. That is, the textile printing method may include a step of applying the treatment liquid composition to the fabric, which is the recording medium. By pretreating the fabric, bleeding of the image can be reduced and the image can be dyed clearly and efficiently. The pretreatment of the fabric with the treatment liquid composition may be performed by any conventionally known method.

[0105] The treatment liquid composition typically contains a paste, a surfactant, a pH adjuster, a hydrotropic agent, and water, and may also contain silica depending on the application.

[0106] Examples of adhesives include natural gums such as guar gum and locust bean gum; starches; seaweeds such as sodium alginate and funori; plant skins such as pectic acid; cellulose derivatives such as methylcellulose, ethylcellulose, hydroxyethylcellulose, and etherified 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; synthetic glues such as polyvinyl alcohol and polyacrylic esters; and emulsions.

[0107] As the surfactant, reference may be made to the surfactants contained in the ink composition described above. Alternatively, a nonionic surfactant such as polyoxyethylene diisopropyl ether may be used.

[0108] Examples of pH adjusters include sodium m-benzenesulfonate, ammonium salts of acid, ammonium sulfate, sodium carbonate, and ammonium tartrate.

[0109] Hydrotropic agents include, for example, alkyl ureas such as urea, dimethyl urea, thiourea, monomethyl thiourea, and dimethyl thiourea.

[0110] The water contained in the ink composition may be referred to as the water.

[0111] The treatment liquid composition can be prepared by mixing the components in any order and, if necessary, removing impurities and foreign matter by filtration or the like. The components can be mixed by sequentially adding the components to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer, followed by stirring and mixing. Examples of filtration methods include centrifugal filtration and filter filtration.

[0112] Examples of methods for applying the treatment liquid composition to a fabric include a dip coating method in which the fabric is immersed in the treatment liquid composition, a roller coating method in which the treatment liquid composition is applied using a mangle roller, a roll coater, or the like, a spray coating method in which the treatment liquid composition is sprayed using a spray device, or an inkjet coating method in which the treatment liquid composition is sprayed by an inkjet method. Of these coating methods, the treatment liquid composition may be applied to the fabric using one method alone, or two or more methods may be combined to apply the treatment liquid composition to the fabric.

[0113] After the treatment liquid composition is applied to the fabric, it is preferable to heat and dry the fabric to which the treatment liquid composition is applied, as necessary. As the drying method, the above-mentioned heating step may be referred to. [Example]

[0114] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these. Unless otherwise specified, "parts" below refer to parts by mass.

[0115] 1. Preparation of the compound represented by formula (12) and the compound represented by formula (13) [Preparation of the compound represented by formula (12)] The compound represented by formula (12) can be a commercially available dye compound known as Acid Blue 113. 200 g of the commercially available compound was added to 1,800 g of water, and then a 15% aqueous solution of sodium hydroxide was added to adjust the pH to about 9.5, followed by stirring at 60°C for about 2 hours. After microfiltration and ultrafiltration using a 5 μm membrane filter, the filtrate was spray-dried to obtain a powder of the compound represented by formula (12).

[0116] [Preparation of compound represented by formula (13)] The compound represented by formula (13) can be a commercially available dye compound known as Acid Blue 116. The commercially available compound was dissolved in water in the same manner as above, filtered, and dried to obtain a powder of the compound represented by formula (13).

[0117] 2. Preparation of Inkjet Acid Dye Black Ink Composition (Examples 1 to 20 and Comparative Examples 1 to 4) The components were placed in a mixing tank so as to obtain the composition shown in Table 1 or 2, and the mixture was mixed and stirred for 2 hours using a magnetic stirrer. The mixture was then filtered through a membrane filter with a pore size of 5 μm, thereby obtaining inkjet acid dye black ink compositions according to the examples and comparative examples. In Tables 1 and 2, the mass ratio (compound (C) / dye (A)) indicates the mass ratio of compound (C) to water-soluble dye (A), and the mass ratio (dye (B) / dye (A)) indicates the mass ratio of water-soluble dye (B) to water-soluble dye (A). The numerical values in Tables 1 and 2 indicate mass %. The mass % of the water-soluble dye (A) and the water-soluble dye (B) is shown as the solid content. Ion-exchanged water was used as water, and was added so that the mass of each ink composition became 100 mass %.

[0118] The components shown in Tables 1 and 2 are as follows: [Water-soluble dye (A)] Compound represented by formula (12): Compound represented by formula (12) obtained by the above preparation Compound represented by formula (13): Compound represented by formula (13) obtained by the above preparation

[0119] [Azo water-soluble dye (B)] Orange 94: CI Acid Orange 94 (commercially available) Red 249: CI Acid Red 249 (commercially available) Yellow 79: CI Acid Yellow 79 (commercially available) Violet 54: CI Acid Violet 54 (commercially available)

[0120] [Non-azo water-soluble dye (B)] Red 52: CI Acid Red 52 (commercially available) Yellow 3: CI Acid Yellow 3 (commercially available) Violet 48: CI Acid Violet 48 (commercially available) Blue87: CIDirect Blue 87 (commercially available)

[0121] [Compound (C)] 1-Naphthylamine: a compound represented by formula (9) 8-anilino-1-naphthalenesulfonic acid...compound represented by formula (11) 8-Amino-1-naphthalenesulfonic acid...Compound represented by formula (10) 3-aminobenzenesulfonic acid: a compound represented by formula (8) 6-anilino-2-naphthalenesulfonic acid: a compound represented by formula (7) 4-amino-1-naphthalenesulfonic acid: a compound represented by formula (6) 2-Amino-1-naphthalenesulfonic acid: a compound represented by formula (6) 1,8-Naphthalenediamine: a compound represented by formula (3) 2-Aminobenzenesulfonic acid: a compound represented by formula (3)

[0122] [Compound] 1-(N-phenylamino)-naphthalene 8-Aminonaphthalene-1,3,5-trisulfonic acid

[0123] [Diol-based water-soluble organic solvent (D)] Triethylene glycol Propylene glycol 1,2-Hexanediol

[0124] [Surfactant] E1010: Olfine (registered trademark) E1010 (product name, Nissin Chemical Industry Co., Ltd.)

[0125] [pH adjuster] Triethanolamine

[0126] [Other ingredients] ·urea

[0127] 3. Evaluation Method 3.1.Clogging recovery Each of the inkjet acid dye black ink compositions of Examples 1 to 10 and Comparative Examples 1 to 3 was filled into the cartridge of an inkjet printer EW-873T (product name, Seiko Epson Corporation), and it was confirmed that the ink composition was ejected from all inkjet heads. Thereafter, the inkjet printer was left in a state where it was not in the home position, i.e., the inkjet heads were displaced from the cap positions provided on the inkjet printer and were not capped, and the printer filled with the ink composition was left in an environment of 40°C for 3 days. After leaving it, ejection of the ink composition from all inkjet heads was confirmed, and clogging was evaluated according to the following criteria. The results are shown in Table 3. (standard) A: By performing cleaning 1 to 3 times, you can check that all inkjet heads are ejecting ink and that no clogging occurs. B: By performing cleaning four or five times, ejection from all inkjet heads can be confirmed and no clogging occurs. C: By performing cleaning six or seven times, ejection from all inkjet heads can be confirmed and no clogging occurs. D: There is an inkjet head that does not eject ink even after cleaning seven times, and clogging occurs.

[0128] 3.2.Intermittent Discharge Characteristics Each of the inkjet acid dye black ink compositions of Examples 1 to 10 and Comparative Examples 1 to 3 was filled into the cartridge of an inkjet digital textile printing machine ML-32000 (product name, Seiko Epson Corporation). Then, a one-minute idle run, which is a scan that does not eject ink, was performed. During this time, no flushing was performed, and during the idle run, a slight vibration was performed that does not eject ink. Then, the ink composition was ejected from all nozzles onto the printing medium, and the intermittent ejection characteristics were evaluated according to the following criteria. The results are shown in Table 3. (standard) A: Discharged normally within 3000 times. B: The number of discharges was normal when it exceeded 3,000 and was less than 5,000. C: Normal ejection occurred between 5,000 and 10,000 times. D: The discharge was not normal even after 10,000 discharges.

[0129] 3.3.Storage stability Approximately 50 mL of each of the inkjet acid dye black ink compositions of Examples 1 to 10 and Comparative Examples 1 to 3 was filled into a 100 mL glass storage bottle capable of sealing the ink. The storage bottle was then left at -15°C for 6 days. After leaving the storage bottle upside down, the bottom and glass wall of the storage bottle were visually inspected, and the storage stability was evaluated according to the following evaluation criteria. The results are shown in Table 3. (standard) A: No sediment or precipitate was observed on the bottom or glass wall of the storage bottle. B: A small amount of granular precipitate was observed on the bottom and glass wall of the storage bottle, but the precipitate dissolved when the storage bottle was left at room temperature. C: Precipitates were observed on the bottom and glass wall of the storage bottle, but the precipitates dissolved when the storage bottle was left at room temperature. D: Precipitates were observed on the bottom and glass wall of the storage bottle, and the precipitates did not dissolve even when the storage bottle was left at room temperature.

[0130] 3.4.Hue As fabrics for evaluation, silk fabric (silk habutae 14 momme, manufactured by Shikizome Co., Ltd.) and nylon fabric (nylon 6 taffeta, manufactured by Shikizome Co., Ltd.) were prepared, and the following pretreatment liquid was applied to these fabrics, which were then squeezed with a mangle at a pickup rate of 20% and dried to obtain Fabric 1 (silk) and Fabric 2 (nylon) for use in producing printed materials. Sodium alginate: 1.0% by mass Guar gum: 1.0% by mass Ammonium sulfate: 4.0% by mass Urea: 10.0% by mass Water: 84.0% by mass

[0131] Each of the inkjet acid dye black ink compositions of Examples 11 to 20 and Comparative Example 4 was filled into the cartridge of an inkjet printer EW-873T (product name, Seiko Epson Corporation). Then, the ink was applied to each of Fabrics 1 and 2 at a resolution of 720 dpi x 720 dpi with an ink dose of 23 mg / inch. 2 An inkjet acid dye black ink composition was applied under the conditions of (a) to (c) to form an image. Each of the fabrics 1 and 2 on which the images were formed was steamed at 102°C for 30 minutes, then washed at 55°C for 10 minutes using an aqueous solution containing 0.2% by mass of LACCOL STA (surfactant, manufactured by Meisei Chemical Industry Co., Ltd.), and dried to obtain each printed item.

[0132] The hue of each of the obtained recorded materials was evaluated. Specifically, the C* value, which is the saturation, of each of the obtained recorded materials was measured using a colorimeter (spectrodensitometer FD-7, manufactured by Konica Minolta) under measurement conditions [light source: D65, viewing angle 10 degrees, Status T]. Based on the obtained C* value, the hue was evaluated according to the following evaluation criteria. The results are shown in Table 4. (standard) A: The C* value is 5 or less. B: The C* value is greater than 5 and less than 10. C: The C* value is greater than 10 and less than or equal to 15. D:C* value is greater than 15.

[0133] 3.5.Lightfastness Using each of the recorded materials obtained in the above section 3.4. Hue, a lightfastness test was conducted using a xenon weather meter (X75L, manufactured by Suga Test Instruments Co., Ltd.) in accordance with Method A-2 of JIS L 0843:2006, and the lightfastness was evaluated according to the following evaluation criteria. The results are shown in Table 4. (standard) A: The test result is level 4 or above. B: The test result is between grade 3 and grade 4. C: The test result is between grade 2 and grade 3. D: The test result is below grade 2.

[0134] As shown in Tables 3 and 4, it was found that the ink composition of this embodiment can provide an ink composition having excellent clogging recovery properties, continuous ejection properties, storage stability, and black hue.

[0135] Furthermore, by comparing Examples 1 to 4 and 10 with Examples 5 to 9, it was found that by using one or more compounds selected from the group consisting of compounds represented by formula (8) and compounds represented by formula (11) as compound (C), an ink composition having better clogging recovery properties, continuous ejection properties, and storage stability can be obtained.

[0136] A comparison of Examples 1 and 11 with Examples 10 and 20 revealed that when the compound represented by formula (12) was used as the water-soluble dye (A), an ink composition having excellent lightfastness, as well as excellent clogging recovery properties, continuous ejection properties, storage stability, and black hue, could be obtained.

[0137] Comparing Examples 11 to 14 with Examples 15 and 16, it was found that when the mass ratio of the water-soluble dye (B) to the water-soluble dye (A) is 1 / 2 or more and 2 / 1 or less, an ink composition having excellent clogging recovery properties, continuous ejection properties, and storage stability, as well as an even better black hue, can be obtained.

[0138] A comparison of Examples 11 to 14 with Examples 17 to 19 revealed that when an azo-based water-soluble dye is used as the water-soluble dye (B), an ink composition having excellent clogging recovery properties, continuous ejection properties, and storage stability, as well as better black hue and lightfastness, can be obtained.

Claims

1. An ink composition comprising a water-soluble dye (A), a water-soluble dye (B) different from the dye (A), and a compound (C), The dye (A) is at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2), The compound (C) is at least one selected from the group consisting of a compound represented by the following formula (3) and a compound represented by the following formula (4), a mass ratio of the compound (C) to the dye (A) (the compound (C) / the dye (A)) is 1 / 20,000 or more and 20 / 20,000 or less; An acid dye black ink composition for inkjet printing. 【Chemical 1】 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 (In formula (4), R 1 is a hydrogen atom, -NH 2 or a phenylamino group, R 2 is a hydrogen atom or -NH 2 and R 3 is a hydrogen atom or a sulfo group. 1 , R 2 , and R 3 cannot be a hydrogen atom at the same time. 1 is a phenylamino group, R 2 and R 3 cannot simultaneously become a hydrogen atom.

2. 2. The ink composition according to claim 1, wherein the compound represented by formula (4) is at least one selected from the group consisting of a compound represented by formula (5), a compound represented by formula (6), and a compound represented by formula (7): 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】

3. The compound represented by formula (3) is a compound represented by formula (8) below:

2. The ink composition according to claim 1, wherein the compound represented by formula (4) is at least one selected from the group consisting of a compound represented by formula (9), a compound represented by formula (10), and a compound represented by formula (11): 【Chemistry 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】

4. The ink composition according to claim 3 , wherein the compound represented by formula (4) is a compound represented by formula (9).

5. The ink composition according to claim 1, wherein the dye (A) is at least one selected from the group consisting of compounds represented by the following formula (12) and compounds represented by the following formula (13): 【Chemistry 12】 【Chemistry 13】

6. The ink composition according to claim 1 , wherein the mass ratio of the dye (B) to the dye (A) (the dye (B) / the dye (A)) is 1 / 2 or more and 2 / 1 or less.

7. The ink composition according to claim 1 , wherein the dye (B) comprises an azo-based water-soluble dye.

8. Further containing a diol-based water-soluble organic solvent (D), The ink composition according to claim 1 , wherein the content of the organic solvent (D) is 50% by mass or more relative to 100% by mass of the dye solid content.

9. 2. The ink composition according to claim 1, wherein the organic solvent (D) comprises one or more solvents selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,2-hexanediol, and 3-methyl-1,5-pentanediol.

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