Inkjet printing ink composition and recording method

Abstract

Provided are an inkjet printing ink composition and a recording method for an inkjet printing product having excellent light resistance. The inkjet printing ink composition comprises a sulfonic acid group-containing dye whose ligand is coordinated to a metal atom, wherein the ligand is represented by the following formula (1). [Chemical 1] #imgabs0# (wherein, at least one of R1 and R3 represents SO3 ‑ or SO3Y, R1 and R3 do not represent SO3 ‑ or SO3Y represents a halogen atom or a hydrogen atom, R2 and R4 independently represent a hydrogen atom, a halogen atom, a sulfo group, a nitro group, an aryl group, a sulfonamide group, a carboxyl group, an alkyl group having 1 to 4 carbon atoms, SO2NHR5 or COOR5, X represents a metal atom, Y represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom, and R5 represents a hydrogen atom or an alkyl group).

Description

Technical Field

[0001] The present invention relates to an inkjet printing ink composition and a recording method. Background Art

[0002] Inkjet recording methods can record high-definition images using relatively simple equipment and are rapidly developing in various fields. Among them, various studies have been conducted to obtain high-quality recorded materials more stably.

[0003] For example, Patent Document 1 discloses an inkjet ink for printing and dyeing polyamide fibers, aiming to provide an inkjet ink with excellent color reproduction, high fastness, and excellent storage stability. This inkjet ink is characterized by containing 6 to 12% by mass of CI No. Acid Red 447 as a dye, at least one of water and a glycol ether, and at least two of polyols as solvents.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2008-266537.

[0007] However, the inkjet ink disclosed in Patent Document 1 mainly contains a specified amount of CI No. Acid Red 447 as a dye, thereby achieving excellent color reproduction and high fastness when printing and dyeing polyamide fibers. However, the fastness, especially light fastness, of the printed products obtained by inkjet printing still has room for improvement. Summary of the Invention

[0008] To solve the above-mentioned problems, the present inventors conducted intensive research and found that the use of an inkjet printing ink composition containing a sulfonic acid group-containing dye in which a specific ligand is coordinated to a metal atom results in excellent light fastness of printed products obtained by inkjet printing, thereby completing the present invention.

[0009] That is, the present invention is an inkjet printing ink composition comprising a sulfonic acid group-containing dye in which a ligand is coordinated to a metal atom, wherein the ligand is represented by the following formula (1).

[0010] [Chemistry 1]

[0011]

[0012] (wherein, at least one of R1 and R3 represents SO3 - or SO3Y, R1 and R3 do not represent SO3 -or SO3Y represents a halogen atom or a hydrogen atom, R2 and R4 each independently represent a hydrogen atom, a halogen atom, a sulfo group, a nitro group, an aryl group, a sulfonamide group, a carboxyl group, an alkyl group having 1 to 4 carbon atoms, SO2NHR5 or COOR5, X represents a metal atom, Y represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom, and R5 represents a hydrogen atom or an alkyl group.)

[0013] In the inkjet printing ink composition according to the present invention, it is preferred that the metal atom is a chromium atom. Furthermore, it is preferred that one of R1 and R3 in the formula (1) represents SO3 - or SO3Y and the other represents a halogen atom or a hydrogen atom ligand coordinated to the metal atom of the first dye, and both R1 and R3 in the formula (1) represent SO3 - or SO3Y ligand coordinated to the metal atom. Furthermore, the content ratio of the second dye to the first dye is more preferably 1 / 100 or more and 1 / 1 or less by mass, and further preferably, the content of the second dye is 0.1% by mass or more and 50% by mass or less relative to the total amount of the inkjet printing ink composition.

[0014] Furthermore, the inkjet textile printing ink composition according to the present invention preferably contains a third dye in which a ligand represented by the following formula (2) is coordinated to a metal atom.

[0015] [Chemistry 2]

[0016]

[0017] (In the formula, R6 and R8 each independently represent a halogen atom or a hydrogen atom, R7 and R9 each independently represent a hydrogen atom, a halogen atom, a sulfo group, a nitro group, an aryl group, a sulfonamide group, a carboxyl group, an alkyl group having 1 to 4 carbon atoms, SO2NHR5 or COOR5, X represents a metal atom, Y represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom, and R5 represents a hydrogen atom or an alkyl group.)

[0018] Furthermore, the content ratio of the third dye to the sulfonic acid group-containing dye is more preferably 1 / 99 or more and 1 / 1 or less in terms of mass ratio, and the content of the third dye is even more preferably 0.1% by mass or more and 20% by mass or less relative to the total amount of the inkjet printing ink composition.

[0019] Furthermore, in the inkjet printing ink composition of the present invention, the content of the sulfonic acid group-containing dye is 0.01% to 50% by mass relative to the total amount of the inkjet printing ink composition, and the composition preferably contains a compound having a lactam structure. More preferably, the compound having a lactam structure is 2-pyrrolidone, 2-azetidinone, 2-piperidone, ε-caprolactam, 4-ethyl-2-azetidinone, N-methyl-2-pyrrolidone, or 3-amino-2-piperidone. Furthermore, it is further preferred that the content of the compound having a lactam structure is 1.0% to 20% by mass relative to the total amount of the inkjet printing ink composition.

[0020] The recording method of the present invention relates to a recording method in which an inkjet printing ink composition is ejected by an inkjet method and attached to a recording medium, wherein the recording medium is a cloth. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a flowchart showing an example of the recording method according to this embodiment. DETAILED DESCRIPTION

[0022] Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “this embodiment”) will be described in detail with reference to the drawings as needed. However, the present invention is not limited thereto and can be variously modified within the scope of the present invention.

[0023] In this specification, "printing" refers to recording ink onto a recording medium, such as fabric (hereinafter also referred to as "printing"). Furthermore, "inkjet printing" refers to recording ink onto a recording medium, such as fabric, using an inkjet method and is a type of inkjet printing. A "recorded article" refers to an image formed by recording ink onto a recording medium, such as fabric.

[0024] Ink composition

[0025] The inkjet printing ink composition of this embodiment (hereinafter referred to as "ink composition") contains a sulfonic acid group-containing dye (hereinafter also referred to as "dye of this embodiment") having a ligand coordinated to a metal atom, wherein the ligand is represented by the following formula (1).

[0026] [Chemistry 3]

[0027]

[0028] (wherein, at least one of R1 and R3 represents SO3 - or SO3Y, R1 and R3 do not represent SO3 -or SO3Y represents a halogen atom or a hydrogen atom, R2 and R4 each independently represent a hydrogen atom, a halogen atom, a sulfo group, a nitro group, an aryl group, a sulfonamide group, a carboxyl group, an alkyl group having 1 to 4 carbon atoms, SO2NHR5 or COOR5, X represents a metal atom, Y represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom, and R5 represents a hydrogen atom or an alkyl group.)

[0029] Here, the metal atom is not particularly limited as long as it is a metal atom capable of coordinating with the ligand represented by formula (1). Examples thereof include chromium (Cr) atoms, iron (Fe) atoms, cobalt (Co) atoms, and copper (Cu) atoms. From the perspective of improving light resistance, chromium (Cr) atoms are preferred. Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, and butyl groups.

[0030] The halogen atom is not particularly limited, and examples thereof include a chlorine (Cl) atom, a fluorine (F) atom, a bromine (Br) atom, and an iodine (I) atom. From the viewpoint of improving light resistance, a chlorine (Cl) atom is preferred.

[0031] The alkali metal atom and the alkaline earth metal atom are not particularly limited, and examples thereof include lithium (Li) atoms, sodium (Na) atoms, potassium (K) atoms, beryllium (Be) atoms, magnesium (Mg) atoms, calcium (Ca) atoms, and barium (Ba) atoms. From the perspective of improving light resistance, sodium (Na) atoms are preferred.

[0032] The ratio of the metal atom to the ligand represented by formula (1) coordinated to the metal atom is (metal atom): (ligand represented by formula (1) coordinated to the metal atom), and is preferably 1:2 to 2:3, more preferably 1:1, in terms of mass ratio, from the perspective of obtaining more excellent color development properties. Within this range, the ligand is more likely to coordinate to the metal atom to form a complex, thus tending to obtain more excellent color development properties.

[0033] The main reason for the excellent light fastness of the ink composition of the present embodiment is believed to be as follows. However, the main reason is not limited to this. That is, when the existing ink composition uses a dye containing a ligand containing a sulfonic acid group coordinated with respect to the metal atom, because the ink composition contains this polarized dye, it can obtain excellent blocking recovery and storage stability. However, if the content of the dye is increased to a degree that obtains excellent storage stability, the fastness, particularly light fastness and water resistance of the printed dye obtained by inkjet printing will deteriorate. On the other hand, since the ink composition of the present embodiment contains a sulfonic acid group-containing dye that is coordinated with respect to the metal atom by a specific ligand containing a sulfonic acid group, even if the content of the dye is increased to a degree that can obtain excellent blocking recovery and storage stability, the fastness, particularly light fastness and water resistance of the printed dye obtained by inkjet printing will also be excellent. That is, the ink composition of the present embodiment can obtain a printed dye obtained by inkjet printing that has excellent light fastness. Furthermore, in the printed product obtained by inkjet printing, it is possible to achieve both excellent blocking recovery and storage stability as well as excellent light resistance and water resistance.

[0034] dye

[0035] The ink composition of this embodiment includes the dye of this embodiment and has excellent light resistance.

[0036] The specific dye of this embodiment is not particularly limited. From the perspective of more reliably achieving the effect of the present invention, it is preferred that one of R1 and R3 in formula (1) represents SO3 - or SO3Y and the other represents a halogen atom or a hydrogen atom ligand coordinated to the metal atom of the first dye, and both R1 and R3 in formula (1) represent SO3 - Or a second dye in which the ligand of SO3Y is coordinated relative to the metal atom.

[0037] When a first dye and a second dye are included, the content ratio of the second dye to the first dye is preferably 1 / 100 or more and 1 / 1 or less, more preferably 1 / 75 or more and 1 / 1.5 or less, and even more preferably 1 / 50 or more and 1 / 2 or less, in terms of achieving both excellent blocking recovery and excellent storage stability and excellent light resistance and water resistance.

[0038] When a first dye is included, the content of the first dye relative to the total amount of the ink composition is preferably 0.01% to 50% by mass, more preferably 0.1% to 30% by mass, and even more preferably 1.0% to 15% by mass. Since the dye content in this embodiment is 1.0% or more by mass, light fastness and water resistance tend to be further improved. Furthermore, since the dye content in this embodiment is 50% or less by mass, blocking recovery and storage stability tend to be further improved. The total amount of the ink composition herein is 100% by mass, and the same applies hereinafter.

[0039] When a second dye is included, the content of the second dye relative to the total amount of the ink composition is preferably 0.1% to 50% by mass, more preferably 0.15% to 10% by mass, and even more preferably 0.2% to 5.0% by mass. Since the dye content in this embodiment is 0.1% or more by mass, blocking recovery and storage stability tend to be further improved. Furthermore, since the dye content in this embodiment is 15% or less by mass, light resistance and water resistance tend to be further improved.

[0040] The dye content of this embodiment is preferably 0.01% to 50% by mass, more preferably 0.1% to 30% by mass, and even more preferably 1.0% to 15% by mass, relative to the total amount of the ink composition. A dye content of 1.0% or more in this embodiment tends to further improve lightfastness and waterfastness. Furthermore, a dye content of 50% or less in this embodiment tends to further improve blocking recovery and storage stability.

[0041] The ink composition of this embodiment may also contain dyes other than the dye of this embodiment (hereinafter referred to as "other dyes"). In addition, the dyes may be used alone or in combination of two or more.

[0042] The ink composition of this embodiment preferably contains a third dye having no sulfonic acid group and a ligand represented by the following formula (2) coordinated to a metal atom as an additional dye. The inclusion of the third dye tends to improve light resistance and water resistance.

[0043] [Chemistry 4]

[0044]

[0045] (In the formula, R6 and R8 each independently represent a halogen atom or a hydrogen atom, R7 and R9 each independently represent a hydrogen atom, a halogen atom, a sulfo group, a nitro group, an aryl group, a sulfonamide group, a carboxyl group, an alkyl group having 1 to 4 carbon atoms, SO2NHR5 or COOR5, X represents a metal atom, Y represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom, and R5 represents a hydrogen atom or an alkyl group.)

[0046] When a third dye is included, from the perspective of achieving both excellent blocking recovery and storage stability as well as excellent light resistance and water resistance, the content ratio of the third dye relative to the dye of this embodiment is preferably 1 / 100 or more and 2 / 1 or less, more preferably 1 / 50 or more and 1 / 1 or less, and further preferably 1 / 25 or more and 1 / 2 or less, in terms of mass ratio.

[0047] When a third dye is included, the content of the third dye relative to the total amount of the ink composition is preferably 0.1% to 20% by mass, more preferably 0.15% to 10% by mass, and even more preferably 0.2% to 5.0% by mass. Since the dye content in this embodiment is 0.1% or more by mass, light fastness and water fastness tend to be further improved. Furthermore, since the dye content in this embodiment is 15% or less by mass, blocking recovery and storage stability tend to be further improved.

[0048] The ink composition of this embodiment can be used as a yellow ink, magenta ink, cyan ink, red ink, blue ink, black ink, or orange ink, preferably as a black ink, by starting with the dye of this embodiment and adjusting the types and contents of various dyes and other components.

[0049] water

[0050] The ink composition of this embodiment can contain water. Examples of water include pure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water, as well as water that has been extensively freed of ionic impurities, such as ultrapure water. Furthermore, the use of water sterilized by ultraviolet irradiation or the addition of hydrogen peroxide can prevent the growth of mold and bacteria during long-term storage of the coagulant. This tends to further improve storage stability.

[0051] The water content is preferably 40% by mass or more, more preferably 50% by mass or more, and particularly preferably 60% by mass or more, relative to the total amount of the ink composition.

[0052] Compounds with lactam structure

[0053] The ink composition of this embodiment preferably includes a compound having a lactam structure. The compound having a lactam structure is not particularly limited as long as it has a lactam structure. The inclusion of the compound having a lactam structure improves the solubility of the dye in the ink composition and enhances clogging recovery.

[0054] The compound having a lactam structure is not particularly limited, and examples thereof include 2-pyrrolidone, 2-azetidinone, 2-piperidone, ε-caprolactam, 4-ethyl-2-azetidinone, N-methyl-2-pyrrolidone, and 3-amino-2-piperidone. The compound having a lactam structure preferably comprises one or more selected from 2-pyrrolidone, 2-azetidinone, 2-piperidone, ε-caprolactam, 4-ethyl-2-azetidinone, N-methyl-2-pyrrolidone, and 3-amino-2-piperidone.

[0055] The compounds having a lactam structure may be used alone or in combination of two or more.

[0056] The content of the compound having a lactam structure is preferably 30% by mass or less, more preferably 22% by mass or less, and even more preferably 15% by mass or less, relative to the total amount of the ink composition. Furthermore, it is preferably 5.0% by mass or greater, and more preferably 7.0% by mass or greater. When the content of the compound having a lactam structure is 30% by mass or less, storage stability tends to be further improved. Furthermore, when the content of the compound having a lactam structure is 5.0% by mass or greater, blocking recovery tends to be further improved.

[0057] Polyol derivatives

[0058] The ink composition of this embodiment preferably contains polyol derivatives. Polyol derivatives are not particularly limited and may be compounds having multiple hydroxyl groups or compounds synthesized from such compounds. Examples of compounds having multiple hydroxyl groups include the alkyl polyols described below. Examples of compounds synthesized from compounds having multiple hydroxyl groups include condensates and / or etherifications of such compounds, more specifically, the glycol ethers described below. The inclusion of polyol derivatives provides excellent storage stability and clogging recovery.

[0059] There are no particular restrictions on the types of polyol derivatives, and examples thereof include alkyl polyols and glycol ethers.

[0060] The alkyl polyol is not particularly limited, and examples thereof include glycerol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol (1,2-propylene glycol), dipropylene glycol, 1,3-propylene glycol (1,3-propane diol), isobutylene glycol (2-methyl-1,2-propane diol), 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2-butene-1,4-diol, 1,2-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 1,7-heptanediol, and 1,8-octanediol.

[0061] The glycol ether is not particularly limited, and examples thereof include glycol diethers and glycol monoethers.

[0062] Specific examples of glycol diethers are not particularly limited, and include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol dimethyl ether, and dipropylene glycol diethyl ether.

[0063] Specific examples of glycol monoethers are not particularly limited, and include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether.

[0064] The polyol derivatives may be used alone or in combination of two or more.

[0065] The content of polyol derivatives relative to the total amount of the ink composition is preferably 0.1% to 50% by mass, more preferably 1.0% to 40% by mass, and even more preferably 10% to 25% by mass. A content of 25% or less of polyol derivatives tends to further improve storage stability. Furthermore, a content of 0.1% or more of polyol derivatives tends to further improve blocking recovery.

[0066] surfactants

[0067] From the perspective of wettability, the ink composition preferably contains a surfactant. The surfactant is not particularly limited, and examples thereof include acetylene glycol surfactants, fluorine-based surfactants, and silicone-based surfactants.

[0068] The acetylene glycol surfactant is not particularly limited, but is preferably selected from at least one of alkylene oxide adducts of 2,4,7,9-tetramethyl-5-decyn-4,7-diol and 2,4,7,9-tetramethyl-5-decyn-4,7-diol, and alkylene oxide adducts of 2,4-dimethyl-5-decyn-4-ol and 2,4-dimethyl-5-decyn-4-ol. Commercially available acetylene glycol surfactants are not particularly limited, and examples thereof include the E series such as Olfin PD002W, Olfin 104 series, and Olfin E1010 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), and Surfynol 104, 465, 61, and DF110D (all trade names, manufactured by Air Products Japan, Inc.). The acetylene glycol-based surfactant may be used alone or in combination of two or more.

[0069] There are no particular restrictions on fluorine-based surfactants, for example, perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines and perfluoroalkyl amine oxide compounds. There are no particular restrictions on commercially available fluorine-based surfactants, for example, S-144, S-145 (above are trade names, manufactured by Asahi Glass Co., Ltd.); FC-170C, FC-430, Fluorad-FC4430 (above are trade names, manufactured by Sumitomo 3M Co., Ltd.); FSO, FSO-100, FSN, FSN-100, FS-300 (above are trade names, manufactured by DuPont); FT-250, 251 (above are trade names, manufactured by Neos Co., Ltd.). Fluorine-based surfactants can be used alone or in combination of two or more.

[0070] The silicone-based surfactant is not particularly limited, and examples thereof include polysiloxane-based compounds and polyether-modified silicones. There are no particular restrictions on commercially available silicone surfactants. Specific examples include BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK-348, and BYK-349 (all trade names, manufactured by BYK Chemical 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 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). The silicone-based surfactant may be used alone or in combination of two or more.

[0071] The surfactant content is preferably from 0.05% to 2.5% by mass, and more preferably from 0.1% to 1.5% by mass, relative to the total amount of the ink composition. When the surfactant content is within this range, the wettability of the ink composition attached to the recording medium tends to be further improved.

[0072] The ink composition may suitably contain various additives as other ingredients, such as a pH adjuster (e.g., triethanolamine, tripropanolamine), wax, a solubility aid, a viscosity modifier, an antioxidant, an antifungal / antiseptic (e.g., proxel XL2, proxel GXL (these are trade names, manufactured by LONZA Japan Co., Ltd.)), an antifungal agent, an anticorrosive agent, a chelating agent for capturing metal ions that affect dispersion (e.g., sodium ethylenediaminetetraacetic acid), and the like.

[0073] The ink composition of this embodiment is preferably used in the textile printing method described below.

[0074] The recording method of this embodiment is a method of making the above-mentioned ink composition adhere to the cloth to perform recording. The recording method of this embodiment is described below for each step ( Figure 1 ).

[0075] Pre-treatment process (ST1)

[0076] The recording method of this embodiment may include a pre-treatment step of applying a pre-treatment liquid containing at least one of an alkaline agent and a hydrotrope to the fabric. This further improves the dyeing properties of the dye.

[0077] As a method of applying the pretreatment liquid to the fabric, for example, there can be cited a method of immersing the fabric in the pretreatment liquid, a method of applying the pretreatment liquid using a roller coater, a method of spraying the pretreatment liquid (for example, an inkjet method, a spray method), etc. Any method can be used.

[0078] The pretreatment liquid may contain at least one of an alkaline agent and a hydrotrope. The content of these components in the pretreatment liquid can be appropriately set according to the type of fabric, etc., and is not particularly limited.

[0079] When a dye is used, it is preferred to use an alkaline agent in order to further improve the dyeing properties of the dye. Specific examples of the alkaline agent include sodium carbonate, sodium bicarbonate, sodium hydroxide, trisodium phosphate, sodium acetate, and the like.

[0080] From the viewpoint of improving the color development of the recorded image, it is preferable to use a hydrotrope. Examples of the hydrotrope include ureas.

[0081] The pretreatment agent may contain a paste. Examples of the paste include starches such as corn and wheat; cellulosics such as carboxymethyl cellulose and hydroxymethyl cellulose; polysaccharides such as sodium alginate, gum arabic, locust bean gum, tragacanth gum, guar gum, and tamarind seeds; proteins such as gelatin and casein; natural water-soluble polymers such as tannin and lignin; and synthetic water-soluble polymers such as polyvinyl alcohol compounds, polyethylene oxide compounds, acrylic acid compounds, and maleic anhydride compounds.

[0082] The pretreatment agent may contain components commonly used in pretreatment liquids for dyeing and printing, such as water, a paste, an anti-reducing agent, a preservative, a mildew preventer, a chelating agent, a pH adjuster, and a surfactant.

[0083] The recording method of this embodiment may further include a pretreatment liquid drying step, after the pretreatment liquid step, to dry the pretreatment liquid applied to the fabric. The pretreatment liquid can be dried naturally, but from the perspective of increasing the drying speed, drying with heating is preferred. In the pretreatment liquid drying step, when heating is involved, the heating method is not particularly limited; examples include hot pressing, atmospheric steam, high-pressure steam, and thermosetting. Furthermore, the heat source for heating is not limited to the following; examples include infrared light (lamp).

[0084] In the recording method of this embodiment, the material of the fabric used is not particularly limited. Examples include natural fibers such as cotton, linen, wool, and silk; synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, and polyurethane; and biodegradable fibers such as polylactic acid. These fibers may also be blended. The fabric may be any form, such as a woven, knitted, or nonwoven fabric made from the fibers listed above. In particular, when a dye is used in the inkjet printing ink composition, fabrics composed of fibers primarily composed of cellulose (such as cotton, linen, and rayon) are preferred for dyeability.

[0085] The recording method of this embodiment may also use a fabric that has been pre-treated with at least one of the above-mentioned alkaline agent and hydrotrope. In this case, the pre-treatment step may not be performed.

[0086] Printing process (ST2)

[0087] The recording method of this embodiment includes a printing step of applying the ink composition for inkjet printing to a fabric. Specifically, ink droplets ejected by an inkjet recording method are caused to adhere to the fabric, thereby forming an image on the fabric. The inkjet recording method may be any method, including charge deflection, continuous, and on-demand methods (piezoelectric, bubble jet (registered trademark)). Among these inkjet recording methods, a method using a piezoelectric inkjet recording device is particularly preferred.

[0088] Heat treatment process (ST3)

[0089] The recording method of this embodiment may also include a heat treatment step for heat-treating the fabric printed with the ink composition. This heat treatment step allows the dye to be effectively applied to the fabric. Conventional methods can be used for the heat treatment step, including, for example, the HT method (high-temperature steam method), the HP method (high-pressure steam method), and the thermosol method.

[0090] The temperature in the heat treatment step is preferably within a range of 90° C. to 110° C. from the viewpoint of reducing damage to the fabric and improving the dyeability of the fabric with the colorant.

[0091] Cleaning process (ST4)

[0092] The recording method of this embodiment may also include a washing step for washing the printed material. The washing step is preferably performed after the heat treatment step to effectively remove the dye that has not been dyed on the fiber. The washing step can be performed using water, for example, or soaping can be performed as needed.

[0093] Example

[0094] The present invention will be described in detail below by way of examples. The present invention is not limited in any way by the following examples. Hereinafter, "parts" and "%" are by mass unless otherwise specified.

[0095] Preparation Example 1 (Dye used in Example 1)

[0096] Process 1

[0097] After adding 40 parts of 2-amino-6-nitrophenol to 400 parts of water, a 25% aqueous sodium hydroxide solution was added to obtain an aqueous solution with a pH of 7.5-8.0. To this aqueous solution, 30 parts of 35% hydrochloric acid was added, and the mixture was cooled to 5-10°C in an ice bath. Then, 50 parts of a 40% aqueous sodium nitrite solution was added and the mixture was reacted at the same temperature for approximately 30 minutes. Subsequently, 2 parts of aminosulfonic acid was added and stirred for 5 minutes to obtain a diazo reaction solution.

[0098] On the other hand, after adding 54 parts of 1-(4-chlorophenyl)-3-methyl-5-pyrazolone to 400 parts of water, a 25% aqueous sodium hydroxide solution was added to obtain an aqueous solution with a pH of 8.5 to 9.0. The solution was then cooled to 5 to 10°C in an ice bath. A 25% aqueous sodium hydroxide solution was added to the aqueous solution at intervals to maintain the pH at 8.5 to 9.0 and the temperature at 5 to 10°C. The diazo reaction solution obtained above was added dropwise over 15 minutes. The reaction was continued for a further 3 hours while maintaining the pH at 8.5 to 9.0 and the temperature at 5 to 10°C. The precipitated solid was separated by filtration to obtain 380 parts of an azo compound represented by the following formula (3) as a wet cake.

[0099] [Chemistry 5]

[0100]

[0101] Process 2

[0102] The entire amount of the wet cake obtained in step 1, 65 parts of potassium chromium sulfate 12hydrate, and 21 parts of sodium acetate were added to 700 parts of dimethylformamide, and the mixture was reacted at 110-120°C for about 4 hours. After cooling to 20-30°C, insoluble matter was removed by filtration to obtain a filtrate.

[0103] Separately, 112 parts of tetrabutylammonium bromide were added to 5000 parts of water to obtain an aqueous solution. The filtrate obtained above was added dropwise to the aqueous solution over approximately 30 minutes, and the precipitated solid was separated by filtration to obtain 230 parts of a wet cake. The entire amount of the obtained wet cake was resuspended in 1000 parts of water and stirred for 1 hour, followed by filtration and drying to obtain 70 parts of the azo compound represented by formula (3). The maximum absorption wavelength of this azo compound was 499 nm (ethanol).

[0104] Process 3

[0105] While cooling the liquid of 20% fuming sulfuric acid by ice water and keeping its temperature below 10 ℃, 20 parts of the azo compound obtained by process 2 was slowly added thereto, and the reaction was carried out at a temperature of 15 ℃ for 8 hours. The reaction solution was injected into 400 parts of ice water, 30 parts of sodium chloride was added and stirred for 1 hour, and then the solid separated by filtration was washed with 25 parts of 10% sodium chloride aqueous solution to obtain a wet cake. The obtained wet cake was added to 400 parts of water and stirred for 30 minutes, and then the insoluble matter was filtered out. 40 parts of sodium chloride was added to the obtained mother liquor and stirred for 1 hour, and then the solid separated by filtration was dried to obtain a red wet cake as a dye. The obtained dye was analyzed by high performance liquid chromatography (HPLC).

[0106] The components in the dye were separated using HPLC under the following conditions.

[0107] HPLC conditions were as follows: ODS column: BEH-C18, 1.7 μm, 100 mm (manufactured by Waters), eluent: gradient fluid from 1% acetonitrile aqueous solution to 95% acetonitrile aqueous solution, flow rate: 0.5 ml / min, column temperature: 25° C., PDA detection: 254 nm.

[0108] As a result, it was confirmed that the area ratio of the compounds represented by formula (1-1), formula (1-2), and formula (2-1) was 95%:2.5%:2.5% based on HPLC.

[0109] In addition, the obtained compounds were subjected to mass analysis and determination 1 H-and 13 C-NMR confirmed that it had the following structure.

[0110] [Chemistry 6]

[0111]

[0112] [Chemistry 7]

[0113]

[0114] [Chemistry 8]

[0115]

[0116] Preparation Example 2 (Dye used in Example 2)

[0117] While cooling the liquid of 10% fuming sulfuric acid with ice water and keeping its temperature below 10°C, 20 parts of the azo compound obtained by process 2 of Example 1 were slowly added thereto, and the mixture was reacted at a temperature of 10°C for 4 hours. The reaction solution was injected into 400 parts of ice water, 30 parts of sodium chloride were added and stirred for 1 hour, and then the solids separated by filtration were washed with 25 parts of 10% sodium chloride aqueous solution to obtain a wet cake. The obtained wet cake was added to 400 parts of water and stirred for 30 minutes, and then the insoluble matter was filtered out. 40 parts of sodium chloride were added to the obtained mother liquor and stirred for 1 hour, and then the solids separated by filtration were dried to obtain a red wet cake as a dye. The obtained dye was analyzed by high performance liquid chromatography (HPLC).

[0118] The components in the dye were separated using HPLC under the following conditions.

[0119] HPLC conditions were as follows: ODS column: BEH-C18, 1.7 μm, 100 mm (manufactured by Waters), eluent: gradient fluid from 1% acetonitrile aqueous solution to 95% acetonitrile aqueous solution, flow rate: 0.5 ml / min, column temperature: 25° C., PDA detection: 254 nm.

[0120] As a result, it was confirmed that the area ratio of the compounds represented by formula (1-1), formula (1-2), and formula (2-1) was 45%:0%:55% by HPLC.

[0121] Preparation Example 3 (Dye used in Example 3)

[0122] While cooling the liquid of 30% fuming sulfuric acid with ice water and keeping its temperature below 10°C, 20 parts of the azo compound obtained in step 2 of Example 1 were slowly added thereto, and the mixture was reacted at a temperature of 25°C for 2 hours. The reaction solution was injected into 400 parts of ice water, 30 parts of sodium chloride were added and stirred for 1 hour, and then the precipitated solid was separated by filtration and washed with 25 parts of 10% sodium chloride aqueous solution to obtain a wet cake. The obtained wet cake was added to 400 parts of water and stirred for 30 minutes, and the insoluble matter was filtered out. After adding 40 parts of sodium chloride to the obtained mother liquor and stirring for 1 hour, the precipitated solid was separated by filtration and dried to obtain a red wet cake as a dye. The obtained dye was analyzed by high performance liquid chromatography (HPLC).

[0123] The components in the dye were separated using HPLC under the following conditions.

[0124] HPLC conditions were as follows: ODS column: BEH-C18, 1.7 μm, 100 mm (manufactured by Waters), eluent: gradient fluid from 1% acetonitrile aqueous solution to 95% acetonitrile aqueous solution, flow rate: 0.5 ml / min, column temperature: 25° C., PDA detection: 254 nm.

[0125] As a result, it was confirmed that the area ratio of the compounds represented by formula (1-1), formula (1-2), and formula (2-1) was 60%:37.5%:2.5% by HPLC.

[0126] Preparation Example 4 (Dye used in Example 4)

[0127] The dye obtained in step (3) of Example 1 and the dye obtained in Example 2 were mixed in half to prepare the dye used in Example 4.

[0128] Preparation Example 5 (Dyes used in Examples 5 and 6)

[0129] The dye obtained in Example 2 and the dye obtained in Example 3 were mixed in half to prepare the dyes used in Examples 5 and 6.

[0130] Preparation Examples 6 to 8 (dyes used in Examples 7 to 9)

[0131] The dye obtained in step (3) of Example 1 was separated and purified using the separation function of HPLC to obtain only the compound of formula (1-1), thereby preparing the dyes used in Examples 7 to 9.

[0132] Preparation Example 9 (Dye used in Reference Example 1)

[0133] As the dye used in Reference Example 1, the azo compound obtained in Step 2 of Production Example 1 was used.

[0134] Materials for ink compositions

[0135] The main materials of the ink composition used in the production of the following recorded matter are as follows.

[0136] dye

[0137] Dyes of Preparation Examples 1 to 9

[0138] CI Acid Red 447 (trade name of DURA COLOR UK LTD.) [Lactam structure compound]

[0139] 2-Pyrrolidone

[0140] Polyol derivatives

[0141] glycerin

[0142] Triethylene glycol

[0143] Triethylene glycol monobutyl ether

[0144] surfactants

[0145] Olfine PD002W (trade name manufactured by Nissin Chemical Industry Co., Ltd.)

[0146] Other additives

[0147] Tripropanolamine

[0148] Proxel XL2 (trade name Proxel XL2 manufactured by Arch Chemicals)

[0149] Disodium EDTA

[0150] water

[0151] Ion exchange water

[0152] Preparation of ink composition

[0153] The materials were mixed and stirred thoroughly to obtain an ink composition according to the composition shown in Table 1. In Table 1, the numerical values ​​except for the content ratio are expressed in mass %, and the numerical values ​​represent the solid content concentration, and the total is 100.0 mass %.

[0154] Table 1

[0155]

[0156] Preparation of pretreatment solution

[0157] After thoroughly mixing 5 parts by mass of polyoxyethylene diisopropyl ether (ethylene oxide = 30 mol), 5 parts by mass of etherified carboxymethyl cellulose, 100 parts by mass of urea, and 10 parts by mass of sodium m-benzenesulfonate, 1000 parts by mass of ion-exchanged water were gradually added with stirring at 60°C for 30 minutes. Subsequently, 30 parts by mass of sodium carbonate was further added to the stirring solution, and the mixture was stirred for 10 minutes. The solution was then filtered through a membrane filter with a pore size of 10 μm to obtain a pretreatment solution.

[0158] The pretreatment liquid obtained as described above was applied to the fabric, and the fabric was squeezed with a mangle at a mangle rate of 20% and dried.

[0159] Production of printed and dyed fabrics

[0160] Each of the prepared ink compositions was filled into an ink cartridge of an inkjet printer (Seiko Epson, product name: PX-G930). Using this printer, each ink composition was applied to a fabric (100% silk; weight 90 g / m2) pretreated with the prepared pretreatment solution. 2 ) to record the image. The printing resolution is 1440×720dpi. By punching a full-page pattern with an occupancy rate of 100%, an image is formed on the recording medium, i.e., a cloth, and a printed product printed with ink is produced. The cloth printed with the image is boiled at 100°C for 20 minutes, and then washed at 55°C for 10 minutes with an aqueous solution containing 0.2 parts by mass of LaccolSTA (a product name of a surfactant manufactured by Meisei Chemical Co., Ltd.), and dried to obtain a printed product. Here, the "full-page pattern" refers to a pattern in which dots are recorded for all pixels in the smallest recording unit area specified by the recording resolution, i.e., the pixel.

[0161] Lightfastness

[0162] The printed fabrics of each example were exposed to light for 10 days at 23°C, 50% relative humidity, and 75,000 lux using a Xenon light fastness tester (SUGA Co., Ltd., product name: XL-75s). The hue of the samples before and after exposure was measured using a spectrophotometer (trade name "Spectrolino", manufactured by X-RITE) under the conditions of a D65 light source, a DIN_NB state, a 2-degree viewing angle, and a UV filter. The L*, a*, and b* values ​​of each printed fabric were measured, and the hue difference (ΔE) between the printed fabric before and after printing (initial and 10 days) was calculated based on the following formula: * ), and the light resistance was evaluated according to the following evaluation criteria.

[0163] ΔE * ={(ΔL * ) 2 +(Δa * ) 2 +(Δb * ) 2} 1 / 2 ...(Formula 2)

[0164] ΔL * =L * 1-L * 2......(Formula 3)

[0165] Δa * =a * 1-a * 2......(Formula 4)

[0166] Δb * =b * 1-b* 2......(Formula 5)

[0167] Among them, L * 1.a * 1.b * 1 represents the initial measured value of the printed material, L * 2.a * 2. b * 2 indicates the measured value after 10 days of exposure.

[0168] Evaluation Benchmarks

[0169] A: ΔE * Less than 10

[0170] B: ΔE * 10 or more and less than 12.5

[0171] C:ΔE * 12.5 or more and less than 15

[0172] D: ΔE * 15 or more

[0173] Water resistance

[0174] Each of the resulting printed textiles was subjected to a water resistance test according to the method described in JIS L0846:2004. The additional white cloth used in the test was the same as the first and second additional white cloths, using cotton (No. 3-3) as described in JIS L0803. These additional white cloths were purchased from the Japan Standards Association. The water resistance grade was evaluated using the following evaluation criteria based on the visual method (Article 10 a) of JIS L0801.

[0175] Evaluation Benchmarks

[0176] A: Level 5

[0177] B: Level 4 and between Level 4 and Level 5

[0178] C: Between Level 3 and Level 4

[0179] D: Level 3

[0180] Blockage recovery

[0181] An inkjet printer (Seiko Epson, product name: PX-G930) was filled with each of the prepared ink compositions and ejected from all nozzles. With the print head removed from its cap, the printer was left in an environment of 40°C, 20% RH for 7 days. Cleaning and printing for nozzle inspection were then repeated alternately. The number of cleanings required until normal ejection with no missing dots or bowing was measured. Blockage recovery was evaluated based on the number of cleanings according to the following evaluation criteria. Table 1 shows the results.

[0182] Evaluation Benchmarks

[0183] A: Less than 1 time

[0184] B: 2-3 times

[0185] C: 4-5 times

[0186] D: 6 or more times

[0187] Storage stability

[0188] Each ink composition obtained as described above was filled in a sample bottle and left at 60° C. for 7 days. The pH before (immediately after preparation) and after the leaving were measured, and the storage stability was evaluated according to the following evaluation criteria. Table 1 shows the obtained results.

[0189] Evaluation Benchmarks

[0190] A: The pH change is less than 1, and the pH value after standing is 6 or above.

[0191] B: The pH change is 1 or more and less than 2, and the pH value after standing is 6 or more

[0192] C: The pH change is 2 or more, and the pH value after standing is 6 or more

[0193] D: The pH value after standing is less than 6

[0194] Evaluation results

[0195] The ink compositions of each example prepared by including the dye of this embodiment all achieved a C rating or higher in terms of light resistance, water resistance, blocking recovery, and storage stability, indicating that they were excellent ink compositions. Furthermore, a comparison between Example 1 and Example 2 shows that the inclusion of the first and second dyes resulted in improved blocking recovery. A comparison between Example 1 and Example 3, and between Example 1 and Example 5, shows that the water resistance was improved by having the second dye content ratio relative to the first dye below a specified value. A comparison between Example 1 and Example 4, and between Example 1 and Example 5, shows that the blocking recovery was improved by having the third dye content ratio relative to the sulfonic acid group-containing dye below a specified value. A comparison between Example 5 and Example 6 shows that the inclusion of a compound having a lactam structure resulted in improved blocking recovery. A comparison between Example 7 and Reference Example 1 shows that the inclusion of the first dye resulted in improved blocking recovery and storage stability. A comparison between Example 7 and Examples 8 and 9 shows that the light resistance and blocking recovery were improved by having the dye content of this embodiment within the specified range.

Claims

1. An inkjet printing ink composition, characterized in that Include: A sulfonic acid group-containing dye in which a ligand is coordinated to a metal atom, wherein the ligand is represented by the following formula (1): The content of the sulfonic acid group-containing dye is 8% by mass or more and less than 15% by mass relative to the total amount of the inkjet printing ink composition. The inkjet printing ink composition comprises the formula (1) wherein one of R1 and R3 represents SO3 - or SO3Y and the other represents a first dye in which a ligand of a halogen atom or a hydrogen atom is coordinated with respect to a metal atom, The inkjet printing ink composition further comprises a compound having a lactam structure, wherein the content of the compound having a lactam structure is 1.0% by mass or more and 20% by mass or less relative to the total amount of the inkjet printing ink composition. The inkjet printing ink composition is an inkjet recording ink composition, [Chemistry 1] In the formula, R2 and R4 each represent a chlorine (Cl) atom, X represents a metal atom, and Y represents a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom.

2. The inkjet printing ink composition according to claim 1, wherein The metal atom is a chromium atom.

3. The inkjet printing ink composition according to claim 1 or 2, further comprising: In the formula (1), both R1 and R3 represent SO3 - Or a second dye in which the ligand of SO3Y is coordinated relative to the metal atom.

4. The inkjet printing ink composition according to claim 3, wherein The content ratio of the second dye to the first dye is 1 / 100 or more and 1 / 1 or less in terms of mass ratio.

5. The inkjet printing ink composition according to claim 3, wherein The content of the second dye is 0.1% by mass or more and 50% by mass or less relative to the total amount of the inkjet textile printing ink composition.

6. The inkjet printing ink composition according to claim 1, comprising: A third dye in which a ligand represented by the following formula (2) is coordinated to a metal atom, [Chemical 2] In the formula, R6 and R8 each independently represent a halogen atom or a hydrogen atom, R7 and R9 each independently represent a hydrogen atom, a halogen atom, a nitro group, an aryl group, an alkyl group having 1 to 4 carbon atoms, SO2NHR5 or COOR5, X represents a metal atom, Y represents a hydrogen atom, an alkali metal atom or an alkaline earth metal atom, and R5 represents a hydrogen atom or an alkyl group.

7. The inkjet printing ink composition according to claim 6, wherein The content ratio of the third dye to the sulfonic acid group-containing dye is 1 / 99 or more and 1 / 1 or less in terms of mass ratio.

8. The inkjet printing ink composition according to claim 6 or 7, wherein The content of the third dye is 0.1% by mass or more and 20% by mass or less relative to the total amount of the inkjet printing ink composition.

9. The inkjet printing ink composition according to claim 1, wherein The compound having a lactam structure is 2-pyrrolidone, 2-azetidinone, 2-piperidone, ε-caprolactam, 4-ethyl-2-azetidinone, N-methyl-2-pyrrolidone or 3-amino-2-piperidone.

10. A recording method, characterized in that: The invention relates to a recording method comprising ejecting the inkjet printing ink composition according to any one of claims 1 to 9 by an inkjet method and causing the ink to adhere to a recording medium, wherein the recording medium is a cloth.

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