Inkjet recording method

Abstract

To provide an inkjet recording method which is excellent in strike through resistance of an obtained printed matter.SOLUTION: An inkjet recording method includes: a treatment liquid adhesion step of attaching a treatment liquid containing an organic acid and water to an arbitrary place on a fabric by an inkjet method; a color ink adhesion step of attaching droplets of a color ink composition containing a pigment, anionic first resin particles and water to an arbitrary place by an inkjet method; and a transparent ink adhesion step of attaching droplets of a transparent ink composition containing anionic second resin particles and water to an arbitrary place by an inkjet method, wherein in the treatment liquid adhesion step, an amount of an acidic group derived from an organic acid attached to an arbitrary place is 4.5 mmol / m2 or more, and a shortest time difference |α| until the other of the color ink composition and the treatment liquid composition is attached to an arbitrary place after the one thereof is attached to the arbitrary place is within 5 minutes.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Inkjet recording methods are capable of recording high-resolution images using relatively simple equipment and have been rapidly developing in various fields. Various studies have been conducted on color development, fastness, and the like. For example, Patent Document 1 discloses a method for producing a printed textile, with the aim of providing a printed textile that suppresses bleeding and has excellent friction properties, etc., by applying an ink containing a colorant and water to a recording medium using an inkjet system, applying a treatment liquid A to the recording medium to which the ink has been applied, and applying a treatment liquid B to the recording medium to which the treatment liquid A has been applied, wherein the treatment liquid B contains a water-dispersible resin, and the treatment liquid A contains a flocculant that aggregates the water-dispersible resin in the treatment liquid B. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2022-180836 Summary of the Invention [Problem to be solved by the invention]

[0004] However, in the recording method carried out by the conventional configuration as in Patent Document 1, there is room for improvement in the strike-through resistance and rub fastness of the resulting printed textile. [Means for solving the problem]

[0005] The inkjet recording method of the present invention comprises a treatment liquid application step of applying a treatment liquid composition containing an organic acid and water to a desired location on a fabric by an inkjet method; a colored ink application step of applying droplets of a colored ink composition containing a pigment, anionic first resin particles, and water to the desired location by an inkjet method; and a clear ink application step of applying droplets of a clear ink composition containing anionic second resin particles and water to the desired location by an inkjet method, wherein the amount of acidic groups derived from the organic acid applied to the desired location in the treatment liquid application step is 4.5 mmol / m 2 The shortest time difference |α| between when one of the colored ink composition and the treatment liquid composition is deposited on the given location and when the other is deposited on the given location is within 5 minutes. [Brief explanation of the drawings]

[0006] [Figure 1] Table 1 shows the formulations of the treatment liquid compositions used in the examples. [Figure 2] Table 2 shows the compositions of colored ink compositions used in the examples. [Figure 3] Table 3 shows the formulation of the clear ink composition used in the examples. [Figure 4] Table 4 shows the compositions and recording methods used in the examples, as well as the evaluation results. [Figure 5] Table 5 shows the compositions and recording methods used in the examples, as well as the evaluation results. [Figure 6] Table 6 shows the compositions and recording methods used in the examples, as well as the evaluation results. [Figure 7] Table 7 shows the compositions and recording methods used in the examples, as well as the evaluation results. [Figure 8] Table 8 shows the compositions and recording methods used in the examples, as well as the evaluation results. [Figure 9] FIG. 2 is a diagram illustrating an example of a recording apparatus used in the recording method of the present embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0007] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail with reference to the drawings as necessary, but the present invention is not limited to this, and various modifications are possible without departing from the spirit of the present invention. In the drawings, the same elements are given the same reference numerals, and redundant explanations will be omitted. Furthermore, positional relationships such as up, down, left, and right will be based on the positional relationships shown in the drawings unless otherwise specified. Furthermore, the dimensional ratios of the drawings are not limited to those shown in the drawings.

[0008] [Inkjet recording method] The inkjet recording method according to this embodiment (hereinafter also referred to as the present recording method) comprises a treatment liquid application step of applying a treatment liquid composition containing an organic acid and water to a desired location on a fabric by an inkjet method; a colored ink application step of applying droplets of a colored ink composition containing a pigment, anionic first resin particles, and water to the desired location by an inkjet method; and a clear ink application step of applying droplets of a clear ink composition containing anionic second resin particles and water to the desired location by an inkjet method, wherein the amount of acidic groups derived from the organic acid applied to the desired location in the treatment liquid application step is 4.5 mmol / m 2 As described above, the shortest time difference |α| between when one of the colored ink composition and the treatment liquid composition is deposited at an arbitrary location and when the other is deposited at an arbitrary location is within 5 minutes.

[0009] In recent years, in inkjet pigment printing, studies have been conducted on a printing method that combines the ink application process with the pretreatment liquid process, which is performed to reduce ink bleeding and improve color development, in a single printing device. This method simplifies the process and can eliminate the discharge of waste liquid. In particular, the wet-on-wet method, which omits the drying step between the treatment liquid application process and the ink application process, has the advantage of allowing for smaller and faster devices.

[0010] In the treatment liquid, organic acids and polyvalent metal salts are used as coagulants to aggregate the ink. Polyvalent metal salts have strong coagulation power and tend to produce printed matter with good color development and reduced strike-through, but the resulting printed matter tends to have poor wet rub fastness. On the other hand, organic acids undergo a neutralization reaction with the anionic components of the ink, thereby reducing the hydrophilicity of the anionic components, thereby producing printed matter with excellent wet rub fastness. Furthermore, the use of organic acids causes dispersion breakdown of the anionic components, resulting in aggregation near the surface of the fabric, which also improves color development to a certain extent. However, organic acids have a relatively weak coagulation power of the ink components due to dispersion breakdown, which can cause the colorant to penetrate into the fabric and reach the back surface of the ink (hereinafter also referred to as "strike-through").

[0011] The cause of strike-through is not particularly limited, but it is thought that the treatment liquid containing the organic acid dries out before the ink lands, reducing the effects of the acid neutralization reaction and dispersion destruction.

[0012] Therefore, in the present invention, by setting the timing for the deposition of the treatment liquid containing a predetermined amount of organic acid as an aggregating agent and the colored ink containing an anionic resin within 5 minutes, deposition by the wet-on-wet method is possible, and the neutralization reaction by the organic acid proceeds smoothly, promoting aggregation, suppressing strike-through and further improving color development.

[0013] The reason for this is that the treatment liquid and ink adhere to each other in a short time, making them more likely to mix. Furthermore, the amount of acidic groups in the treatment liquid is 4.5 mmol / m 2 It is believed that the inclusion of the organic acid containing the above-mentioned compounds and the anionic resin in the colored ink contributes to the rapid progress of the aggregation reaction near the fabric surface, although the factors are not limited to those mentioned above.

[0014] Furthermore, in the present invention, by further applying a transparent ink containing an anionic resin in addition to the colored ink composition, a film is formed by the transparent ink composition due to the effect of the organic acid in the reaction liquid, thereby further improving wet rub fastness.

[0015] In this specification, the term "any location" refers to an area of ​​the fabric to which the treatment liquid composition, the colored ink composition, and the clear ink composition are adhered, and at this any location, the layers formed by the above-mentioned compositions may be adhered in a state where they are partially or entirely overlapped.

[0016] This recording method is performed on fabrics, which may be made of 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, or may be blends of these fibers.

[0017] The fabric preferably has a hydroxyl group. Examples of such fabrics include fabrics containing cellulose such as cotton and hemp, and fabrics containing polyurethane. When the fabric has a hydroxyl group, a crosslinking reaction can occur between the hydroxyl groups of the fabric and an acidic component contained in the processing liquid composition described below, which tends to improve color development due to thickening and aggregation, and improve friction fastness due to improved adhesion between the fabric and the recording layer.

[0018] In the present recording method, the order in which the treatment liquid application step, colored ink application step, and clear ink application step are performed is not particularly limited. For example, as necessary, the treatment liquid application step and colored ink application step may be performed simultaneously, and then the clear ink application step may be performed, or the treatment liquid application step may be performed, and then the colored ink application step and the clear ink application step may be performed.

[0019] It should be noted that "simultaneously" here means, for example, that the shortest time difference between the deposition of each composition at any location is within 1 second. A specific device configuration uses an inkjet head having two or more nozzle rows, namely, a nozzle row for ejecting a treatment liquid, a nozzle row for ejecting a colored ink, and a nozzle row for ejecting a clear ink, and when two or more of the treatment liquid, colored ink, and clear ink are ejected from each nozzle row when the inkjet head and the fabric are scanned relative to each other, the order of landing is considered to be irrelevant and the inks are deemed to be deposited simultaneously.

[0020] In this recording method, the shortest time lag |α| between the deposition of one of the colored ink composition and the treatment liquid composition at a given location and the deposition of the other at a given location is 5 minutes or less. By setting the time lag |α| to 5 minutes (minutes) or less, the treatment liquid comes into contact with the colored ink composition in a wet state, and the neutralization reaction proceeds, thereby producing a printed product that exhibits excellent strike-through suppression, color development, and rub fastness. From the same perspective, the time lag |α| is preferably 1 minute or less, 1 second or less, 100 msec or less, or 10 msec or less. The lower limit of the time lag |α| is not particularly limited, as it also includes the case where the compositions are deposited substantially simultaneously as described above, but is, for example, 0 seconds or more, 1 msec or more.

[0021] In this recording method, the shortest time difference |β| between when one of the colored ink composition and the clear ink composition is applied to an arbitrary location on the fabric and when the other is applied to an arbitrary location is preferably 1.0 seconds or more and 5.0 seconds or less, 1.5 seconds or less and 4.5 seconds or less, or 2.0 seconds or more and 4.0 seconds or less. By keeping the time difference |β| within the above range, the abrasion fastness tends to be further improved.

[0022] Each step and each composition included in this recording method will be described in detail below.

[0023] 1. Treatment liquid application process The present recording method includes a treatment liquid application step of applying a treatment liquid composition containing an organic acid and water to a desired location on a fabric by an inkjet method, and the amount of acidic groups derived from the organic acid applied to the desired location is 4.5 mmol / m 2 Specifically, the treatment liquid composition may be deposited by ejecting droplets of the treatment liquid composition onto any desired location on the fabric using an inkjet head. The amount of acidic groups is 4.5 mmol / m in at least a portion of the area where the treatment liquid composition is deposited. 2 It is sufficient that the concentration is 4.5 mmol / m or more in all regions. 2 It is also preferable that it is more than this.

[0024] The amount of acidic groups derived from the organic acid is preferably 6.0 to 60 mmol / m 2 and 10 to 50 mmol / m 2 and 15 to 40 mmol / m 2 When the amount of acidic groups derived from an organic acid attached to a fabric is within the above range, the neutralization reaction with the ink composition easily proceeds, and the resulting printed product tends to be excellent in rub fastness, color development, and strike-through resistance. The method for measuring the amount of acidic groups derived from an organic acid is not particularly limited, but can be measured, for example, by acid-base titration. Examples of acidic groups derived from organic acids include acidic groups derived from organic acids described below. Examples of acidic groups include a carboxy group and a phosphate group.

[0025] The amount of treatment liquid applied, X, is preferably 5 to 90 g / m per unit area of ​​the recording region of the fabric. 2 and 10 to 80 g / m 2 and 15 to 60 g / m 2 and 17 to 30 g / m 2 When the amount of treatment liquid applied, X, is within the above range, the resulting printed product tends to be even more excellent in rub fastness and strike-through resistance. In this specification, the amount of application and the amount of coating have the same value.

[0026] 1.1. Treatment liquid composition The treatment liquid composition used in this recording method contains an organic acid and water. Note that the treatment liquid is different from the colored ink composition used for coloring fabrics and the transparent ink composition (overcoat liquid) described below used for protecting printed areas, and is an auxiliary liquid used together with these. The treatment liquid may be any liquid that can aggregate or thicken the components of the colored ink composition and the transparent ink composition.

[0027] 1.1.1.Organic acids The organic acid contained in the processing liquid of the present recording method preferably has a molecular weight of 5,000 or less, 4,000 or less, or 3,000 or less. By setting the molecular weight of the organic acid within the above range, the abrasion fastness, resistance to strike-through, and color development tend to be even better. The organic acid may be used alone or in combination of two or more.

[0028] Specific examples of suitable compounds include organic acids such as lactic acid, succinic acid, phosphoric acid, polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, glutaric acid, fumaric acid, citric acid, tartaric acid, sulfonic acid, orthophosphoric acid, pyrrolidonecarboxylic acid, pyrronecarboxylic acid, pyrrolecarboxylic acid, furancarboxylic acid, pyridinecarboxylic acid, coumaric acid, thiophenecarboxylic acid, nicotinic acid, derivatives of these compounds, and salts thereof. Among these, from the viewpoint of further improving the strike-through resistance, color development, and rub fastness of printed textiles, it is preferable to include one or more selected from the group consisting of lactic acid, succinic acid, phosphoric acid, and polyacrylic acid.

[0029] The content of the organic acid is preferably 1.0 to 30.0 mass %, 1.5 to 20.0 mass %, 3.0 to 15.0 mass %, or 7.0 to 15.0 mass %, relative to the total amount of the treatment liquid composition. By setting the content of the organic acid within the above range, there is a tendency for the abrasion fastness, resistance to strike-through, and color development to be even more excellent.

[0030] 1.1.2. Organic solvents The treatment liquid may contain an organic solvent. The organic solvent is not limited as long as it is water-soluble, and examples thereof include polyhydric alcohols, glycol ethers, nitrogen-containing solvents, esters, and cyclic esters. Among these, polyhydric alcohols are preferred from the viewpoint of further improving rub fastness, strike-through resistance, and color development. The organic solvent may be used alone or in combination of two or more.

[0031] Polyhydric alcohols can be classified into, for example, polyols and alkanediols. Specific examples of polyol compounds include glycerin, ethylene glycol, propylene glycol, 1,2-propanediol, 1,2-butanediol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, dipropylene glycol, and trimethylolpropane. Among these, it is preferable for the treatment liquid to contain at least one of glycerin and propylene glycol, from the viewpoint of more effectively and reliably achieving the effects of the present invention.

[0032] Specific examples of alkanediol compounds include 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2-ethyl-2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,3-butanediol, 2-ethyl-1,3-hexanediol, 3-methyl-1,5-pentanediol, and 2-methylpentane-2,4-diol.

[0033] Furthermore, specific examples of glycol ether compounds include triethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, 3-methoxy-3-methyl-1-butanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether.

[0034] The content of the organic solvent is preferably 10 to 50 mass %, 15 to 45 mass %, or 20 to 40 mass %, relative to the total amount of the treatment liquid composition. By keeping the content of the organic solvent within the above range, there is a tendency for the abrasion fastness, resistance to strike-through, and color development to be even more excellent. From the same viewpoint, the content of the polyhydric alcohols or polyols is preferably 10 to 50 mass %, 15 to 45 mass %, or 20 to 40 mass % relative to the total amount of the treatment liquid composition.

[0035] Surfactants The treatment liquid may contain a surfactant. Examples of surfactants include acetylene glycol surfactants, fluorine-based surfactants, and silicone-based surfactants, with acetylene glycol surfactants being preferred. By using an acetylene glycol surfactant, the effects of the present invention can be more effectively and reliably achieved. The surfactants may be used alone or in combination of two or more.

[0036] Examples of acetylene glycol surfactants include Surfynol 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 (all trade names, manufactured by Air Products Japan Co., Ltd.), and Olfine B. , Y, P, A, STG, SPC, E1004, E1010, PD-001, PD-002W, PD-003, PD-004, EXP.4001, EXP.4036, EXP.4051, AF-103, AF-104, AK-02, SK-14, AE-3 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), Acetylenol E00, E00P, E40, E100 (all trade names, manufactured by Kawaken Fine Chemicals Co., Ltd.). From the viewpoint of more effectively and reliably achieving the effects of the present invention, it is preferable to use Olfine E1010.

[0037] The content of the surfactant is preferably 0.1 to 5.0 mass %, 0.5 to 3.0 mass %, or 0.8 to 2.0 mass %, relative to the total amount of the treatment liquid composition. By keeping the content of the surfactant in the treatment liquid within the above range, the effects of the present invention can be more effectively and reliably achieved.

[0038] 1.1.4.Water The treatment liquid contains water. The water is preferably water from which ionic impurities have been removed as much as possible, and examples of such water include pure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water, as well as ultrapure water.

[0039] The water content is preferably 30 to 90 mass %, more preferably 40 to 80 mass %, and even more preferably 50 to 75 mass %, relative to the total amount of the treatment liquid composition. By keeping the water content in the treatment liquid within the above range, the effects of the present invention can be more effectively and reliably achieved.

[0040] Antibacterial agents The treatment solution may contain an antibacterial agent, such as sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, 1,2-dibenzisothiazolin-3-one (trade names: Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL2, Proxel TN, and Proxel LV, available from Lonza Japan), or 4-chloro-3-methylphenol (such as Preventol CMK, available from Bayer), with Proxel XL2 being preferred.

[0041] The content of the antibacterial agent in the treatment liquid is preferably 0.01 to 1.0 mass %, more preferably 0.1 to 0.5 mass %, and even more preferably 0.2 to 0.4 mass %, relative to the total amount of the treatment liquid composition. By keeping the content of the antibacterial agent within the above range, the effects of the present invention can be achieved more effectively and reliably.

[0042] 1.1.6.Other Ingredients The processing liquid used in the present recording method may contain, as necessary, various additives other than those described above, such as a pH adjuster, a metal sealant, a softener, a dissolution aid, a viscosity adjuster, an ultraviolet absorber, an antioxidant, and a corrosion inhibitor.

[0043] 2. Colored ink application process This recording method includes a colored ink deposition step of depositing droplets of a colored ink composition containing a pigment, anionic first resin particles, and water at a desired location on the fabric. Specifically, the droplets of the colored ink composition may be ejected from an inkjet head and deposited at the desired location on the fabric. At the desired location on the fabric, the colored ink may be reacted with a treatment liquid that has been previously deposited, or the colored ink may be deposited in advance and then reacted with the treatment liquid.

[0044] In this recording method, in the recording area where the color ink is adhered, the adhesion amount Y of the color ink composition per unit area is 10 g / m 2 It is preferable that the amount of adhesion Y is 10 to 45 g / m or more. By satisfying such a relationship, the obtained printed product tends to be more excellent in rub fastness. From the same viewpoint, the amount of adhesion Y is 10 to 45 g / m 2 and 20 to 40 g / m 2 and 17 to 80 g / m 2 It is more preferable that the amount of adhesion Y of the colored ink composition per unit area is 10 g / m 2 However, according to the present recording method, when the amount Y of the color ink composition applied per unit area is 10 g / m or more, the amount Y of the color ink composition applied per unit area is 10 g / m or more. 2 In the region where the amount of acidic groups derived from organic acids is 4.5 mmol / m or more, 2 By satisfying the above, it is possible to improve the resistance to strike-through and the durability to rubbing.

[0045] 2.1. Colored ink composition The colored ink composition contains a pigment, anionic first resin particles, and water. The anionic first resin particles contained in the colored ink composition react with the acidic component of the treatment liquid, reducing the affinity for water and promoting aggregation near the surface, resulting in improved abrasion resistance, color development, and strike-through resistance.

[0046] 2.1.1.Pigments Examples of pigments that can be used include organic pigments such as azo pigments (e.g., azo lakes, insoluble azo pigments, condensed azo pigments, and chelate azo pigments), polycyclic pigments (e.g., phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments), nitro pigments, nitroso pigments, and aniline black; inorganic pigments such as carbon black (e.g., furnace black, thermal lamp black, acetylene black, and channel black), metal oxides, metal sulfides, and metal chlorides; and extender pigments such as calcium carbonate and talc. Among these, inorganic pigments such as carbon blacks are preferred for achieving the effects of the present invention more effectively and reliably. One type of pigment may be used alone, or two or more types may be used in combination.

[0047] The pigment is preferably a self-dispersing pigment. By including a self-dispersing pigment, the neutralization reaction with the organic acid in the treatment liquid tends to proceed more easily, and the strike-through resistance, rub fastness, and color development tend to be improved.

[0048] Examples of carbon blacks include CI (Colour Index Generic Name) Pigment Black 1, 7, and 11. Commercially available carbon blacks may be used, such as Mitsubishi Chemical Corporation's No. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, and No. 2200B, Columbia Carbon's Raven (registered trademark) 5750, 5250, 5000, 3500, 1255, and 700, CABOT's Rega1 (registered trademark) 400R, 330R, and 660R, Mogul (registered trademark) L, and Monarch (registered trademark) 700, 800, 880, 900, 1000, 1100, 1300, and 1400, and Degussa's Color Black Examples include FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Printex (registered trademark) 35, U, V, 140U, and Special Black 6, 5, 4A, and 4. It is also preferable to use one prepared by the method described in the Examples below.

[0049] The pigment content in the colored ink is preferably 1 to 10 mass %, 2 to 8 mass %, or 3 to 7 mass % relative to the total amount of the colored ink composition. By keeping the pigment content within the above range, the effects of the present invention can be more effectively and reliably achieved. The pigment content in the colored ink is based on the mass % of the pigment solid content.

[0050] 2.1.2. Anionic first resin particles The anionic first resin particles may be, for example, particles in which the resin constituting the resin particles has an anionic group. Examples of the anionic group include a sulfonic acid group, a carboxyl group, a phosphate group, and a hydroxyl group. The resin particles are particles containing a resin, and may be in either an emulsion state or a solution state. However, from the viewpoint of suppressing an increase in the viscosity of the ink, it is preferable to use the resin particles in an emulsion state.

[0051] More specifically, examples of the anionic first resin particles include urethane resins, polycarbonate resins, (meth)acrylic resins, styrene resins, silicone resins, styrene-acrylic resins, fluorene resins, polyolefin resins, rosin-modified resins, terpene resins, polyester resins, polyamide resins, epoxy resins, vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, and ethylene-vinyl acetate resins. Among these, urethane resins are preferred from the viewpoint of more effectively and reliably achieving the effects of the present invention.

[0052] Urethane resins are resins that contain urethane bonds in their molecules. Examples of urethane resins include polyether-type urethane resins that contain ether bonds in their main chains in addition to urethane bonds, polyester-type urethane resins that contain ester bonds in their main chains, and polycarbonate-type urethane resins that contain carbonate bonds in their main chains. Specific commercially available products include ETERNACOLL UW-1501F, UW-1527F, and UW-5002 (all of which are product names manufactured by Ube Industries, Ltd.), Takelac WS-5000, W-6061, W-6110, WS-5984, and WS-5100 (all of which are product names manufactured by Mitsui Chemicals, Inc.), Permarin UA-150, UA-200, and U-coat UX-390 (all of which are product names manufactured by Sanyo Chemical Industries, Ltd.), and Hydran WLS-210 (product name manufactured by DIC Corporation). Among these, from the viewpoint of more effectively and reliably achieving the effects of the present invention, polycarbonate-type urethane resins are preferred, and UW-1527F is a preferred commercially available product thereof.

[0053] The content of the anionic first resin particles in the color ink is preferably 1 to 15 mass %, 3 to 10 mass %, or 5 to 7 mass % relative to the total amount of the color ink composition. By setting the content of the anionic first resin particles within the above range, the effects of the present invention can be more effectively and reliably achieved. The above content is based on the mass % of the solid content of the anionic first resin particles.

[0054] 2.1.3. Organic Solvents The colored ink may contain an organic solvent. The organic solvent is not particularly limited as long as it is water-soluble, and the same types as those used in the treatment liquid may be used. Preferred are polyhydric alcohols and glycol ethers.

[0055] The colored ink preferably contains glycerin as an organic solvent for polyhydric alcohols and triethylene glycol monobutyl ether as an organic solvent for glycol ethers. By containing these compounds, the effects of the present invention can be more effectively and reliably achieved.

[0056] The content of the organic solvent in the color ink is preferably 5 to 30 mass %, 10 to 25 mass %, or 15 to 20 mass %, relative to the total amount of the color ink composition. By keeping the content of the organic solvent within the above range, the abrasion fastness, resistance to strike-through, and color development tend to be even better. From the same viewpoint, the content of polyhydric alcohols is 5 to 30% by mass, and preferably 10 to 25% by mass, relative to the total amount of the color ink composition, and the content of glycol ethers is 0.5 to 5% by mass, and preferably 1 to 3% by mass, relative to the total amount of the color ink composition.

[0057] 2.1.4. pH adjusters The colored ink composition may contain a pH adjuster. Examples of pH adjusters include, but are not limited to, suitable combinations of acids, bases, weak acids, and weak bases. Examples of such acids and bases include inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, and inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium dihydrogen phosphate, disodium hydrogen phosphate, potassium carbonate, sodium carbonate, sodium bicarbonate, and ammonia. Examples of organic bases include triethanolamine (TEA), diethanolamine, monoethanolamine, tripropanolamine, triisopropanolamine, diisopropanolamine, and trishydroxymethylaminomethane (THAM). Examples of organic acids include adipic acid, citric acid, succinic acid, lactic acid, N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES), and 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPE). Other examples of suitable buffers include Good's buffers such as acetamidoglycine, tricine, glycineamide, bicine, phosphate buffer, citrate buffer, and Tris buffer. Among these, triethanolamine is preferred from the viewpoint of achieving the effects of the present invention more effectively and reliably.

[0058] The content of the pH adjuster in the color ink is preferably 0.1 to 5 mass %, 0.3 to 3 mass %, or 0.5 to 1.5 mass %, relative to the total amount of the color ink composition. By setting the content of the pH adjuster within the above range, the effects of the present invention can be more effectively and reliably achieved.

[0059] Regarding the surfactant, antibacterial agent, water, and other components that may be contained in the colored ink, the types used in the treatment liquid composition described above can be used within the same content range.

[0060] 3. Transparent ink application process This recording method includes a transparent ink application step in which droplets of a transparent ink composition containing anionic second resin particles and water are applied to a desired location by an inkjet method. Specifically, droplets of the transparent ink composition may be ejected from an inkjet head and applied to a desired location on the fabric. The transparent ink composition may be applied to the desired location on the fabric simultaneously with a treatment liquid or colored ink, or may be applied to a previously applied treatment liquid or colored ink in a form where the transparent ink composition is further mixed with the treatment liquid or colored ink. Applying the transparent ink composition provides excellent abrasion resistance.

[0061] The amount of transparent ink applied Z is preferably 5 to 50 g / m per unit area of ​​the recording region of the fabric. 2 and 10 to 45 g / m 2 and 20 to 40 g / m 2 and 17 to 80 g / m 2 When the amount Z of deposited transparent ink is within the above range, the resulting printed item tends to be even more excellent in rub fastness and strike-through resistance.

[0062] In this recording method, it is preferable that the deposition amount per unit area of ​​the treatment liquid X, the deposition amount per unit area of ​​the colored ink composition Y, and the deposition amount per unit area of ​​the transparent ink composition Z satisfy the relationship of the following formula (1). By satisfying this relationship, the obtained printed material tends to have even better color development. From the same viewpoint, the value of (Y+Z) / X below is preferably 1.2 or more, and more preferably 1.4 or more. (Y+Z) / X ≧ 1.1 …(1)

[0063] In the present recording method, it is preferable that the area A of the first region to which the treatment liquid is adhered, the area B of the second region to which the colored ink composition is adhered, and the area C of the third region to which the clear ink composition is adhered satisfy the relationship of the following formula (2). By satisfying this relationship, the obtained printed textile tends to be even more excellent in abrasion fastness, color development, and strike-through resistance. C ≥ A ≥ B … (2)

[0064] 3.1. Transparent ink composition The clear ink composition contains anionic second resin particles and water.

[0065] 3.1.1. Anionic second resin particles The second anionic resin particles contained in the clear ink composition are not particularly limited, but may be the same as the first anionic resin particles used in the colored ink composition described above.

[0066] The content of the anionic second resin particles in the clear ink composition is preferably 3 to 30 mass %, 5 to 20 mass %, or 7 to 15 mass %, relative to the total amount of the clear ink composition. By keeping the content of the anionic second resin particles within the above range, the effects of the present invention can be more effectively and reliably achieved.

[0067] 3.1.2. Organic Solvents The transparent ink may contain an organic solvent. The organic solvent is not particularly limited as long as it is water-soluble, and the same types as those used in the treatment liquid may be used. Preferred are polyhydric alcohols and glycol ethers.

[0068] The transparent ink preferably contains glycerin as an organic solvent for polyhydric alcohols and triethylene glycol monobutyl ether as an organic solvent for glycol ethers. By containing these compounds, the effects of the present invention can be more effectively and reliably achieved.

[0069] The content of the organic solvent in the clear ink is preferably 5 to 40 mass %, 10 to 30 mass %, or 15 to 25 mass %, relative to the total amount of the clear ink composition. By keeping the content of the organic solvent within the above range, the abrasion fastness, resistance to strike-through, and color development tend to be even better. From the same viewpoint, the content of polyhydric alcohols is 5 to 40% by mass, and preferably 10 to 30% by mass, relative to the total amount of the transparent ink composition, and the content of glycol ethers is 0.5 to 5% by mass, and preferably 1 to 3% by mass, relative to the total amount of the transparent ink composition.

[0070] The surfactants, organic solvents, antibacterial agents, water, and other components that may be contained in the clear ink can be the same as those used in the treatment liquid composition described above, within the same content ranges.Furthermore, the pH adjusters can be the same as those used in the colored ink compositions described above, within the same content ranges.

[0071] 4. Other processes The present recording method may include a step other than the above-mentioned treatment liquid application step, colored ink application step, and clear ink application step. For example, the method may further include a step of heating the fabric after the above steps. The heating method is not particularly limited, but examples thereof include a heat press method, a normal pressure steam method, a high pressure steam method, and a Thermofix method.

[0072] 5. Inkjet recording device An example of an inkjet printing apparatus equipped with an inkjet head that can be used in the recording method according to this embodiment will be described with reference to FIG.

[0073] The inkjet printing device used in the following description is a serial printer in which a recording inkjet head is mounted on a carriage that moves in a predetermined direction, and the inkjet head moves along with the movement of the carriage, thereby ejecting droplets onto the fabric. The inkjet printing device applicable to the recording method according to this embodiment is not limited to a serial printer, but may also be a line printer. A line printer is a printer in which the inkjet head is formed wider than the width of the fabric, and ejects droplets onto the fabric without moving the inkjet head.

[0074] An inkjet textile printing apparatus is an apparatus that performs textile printing by causing droplets of an ink composition or a treatment liquid to land on a fabric using an inkjet head as a liquid ejection unit. Fig. 9 is a schematic perspective view showing an inkjet textile printing apparatus used in an embodiment.

[0075] 9, the printer 1 in this embodiment has an inkjet head 3, a carriage 4, a main scanning mechanism 5, a platen roller 6, and a control unit (not shown) that controls the overall operation of the printer 1. The carriage 4 mounts the inkjet head 3, and is detachable to accommodate liquid cartridges 7a, 7b, 7c, 7d, 7e, and 7f that contain the ink composition and treatment liquid to be supplied to the inkjet head 3.

[0076] The main scanning mechanism 5 has a timing belt 8 connected to the carriage 4, a motor 9 that drives the timing belt 8, and a guide shaft 10. The guide shaft 10 serves as a support member for the carriage 4 and is installed in the scanning direction of the carriage 4, i.e., the main scanning direction MS. The carriage 4 is driven by the motor 9 via the timing belt 8 and is capable of reciprocating along the guide shaft 10. This allows the main scanning mechanism 5 to function as a reciprocating mechanism for the carriage 4 in the main scanning direction MS.

[0077] The platen roller 6 has the function of transporting the fabric 2 to be printed in a sub-scanning direction SS perpendicular to the main scanning direction MS, i.e., in the length direction of the fabric 2. This transports the fabric 2 in the sub-scanning direction SS. A carriage 4 on which the inkjet head 3 is mounted can move back and forth in the main scanning direction MS, which roughly coincides with the width direction of the fabric 2, and the inkjet head 3 is configured to be able to scan relatively to the fabric 2 in the main scanning direction MS and the sub-scanning direction SS.

[0078] Liquid cartridges 7a, 7b, 7c, 7d, 7e, and 7f are six independent liquid cartridges. Liquid cartridges 7a, 7b, 7c, 7d, 7e, and 7f can contain ink compositions and treatment liquids used in the recording method of this embodiment. These liquid cartridges contain ink compositions and treatment liquids of colors such as black, cyan, magenta, yellow, white, and orange, which can be used in any combination. While FIG. 9 shows six liquid cartridges, this is not a limitation. A supply port (not shown) is provided at the bottom of each liquid cartridge 7a, 7b, 7c, 7d, 7e, and 7f for supplying the ink composition or treatment liquid contained in each liquid cartridge to the inkjet head 3.

[0079] The inkjet head 3 is a device for spraying and depositing ink compositions and treatment liquids supplied from liquid cartridges 7a, 7b, 7c, 7d, 7e, and 7f from multiple nozzles onto the fabric 2 under the control of a control unit (not shown). The inkjet head 3 has multiple nozzles that eject the ink compositions and treatment liquids onto the surface facing the fabric 2 to which the ink compositions and treatment liquids are to be deposited, thereby depositing them onto the fabric 2. These multiple nozzles are arranged in a row to form a nozzle row, and each nozzle row is individually positioned corresponding to each color ink composition and treatment liquid. Each color ink composition and treatment liquid is supplied to the inkjet head 3 from each liquid cartridge and ejected as droplets from the nozzles by an actuator (not shown) within the inkjet head 3. The ejected droplets of the ink composition and treatment liquid land on the fabric 2, depositing them on the fabric 2 and forming ink images, text, patterns, colors, etc. in the printing area of ​​the fabric 2. Note that a plurality of inkjet heads 3 may be provided on the carriage 4.

[0080] Here, the inkjet head 3 uses a piezoelectric element as an actuator, which is a driving means, but is not limited to this type. For example, an electromechanical transducer element that displaces a vibration plate as an actuator by electrostatic adsorption, or an electrothermal transducer element that ejects the ink composition as droplets by bubbles generated by heating may also be used.

[0081] The inkjet head 3 has a treatment liquid nozzle group that ejects a treatment liquid, and an ink composition nozzle group that ejects an ink composition. The ejecting nozzle group refers to a nozzle group used for recording in the recording method. When a main scan is performed, if there is an image to be recorded in the area of ​​the fabric facing the nozzle group, this is a group of nozzles that can eject ink or the like from the nozzles, and is a nozzle group that is continuous in the sub-scanning direction SS. Therefore, nozzle groups that exist but are not used for recording in the recording method are not included in the ejecting nozzle group.

[0082] The printer 1 may also be provided with a drying means and a heating means (neither of which are shown). The drying means and heating means are means for efficiently drying the treatment liquid and ink adhering to the fabric 2. There are no particular limitations on the installation positions of the drying means and heating means, as long as they are located in a position where they can dry and heat the fabric 2. For example, in the case of FIG. 9, the drying means and heating means can be installed in a position opposite the inkjet head 3 in order to efficiently dry the ink and treatment liquid adhering to the fabric 2.

[0083] Examples of drying means and heating means include a print heater mechanism that heats the fabric 2 by contacting it with a heat source, a mechanism that irradiates infrared rays or microwaves, which are electromagnetic waves with a maximum wavelength of about 2,450 MHz, and a dryer mechanism that blows hot air. The fabric 2 is heated before or when droplets ejected from the nozzles of the inkjet head 3 adhere to the fabric 2. The heating conditions, such as the timing of heating, heating temperature, heating time, etc., are controlled by a control unit.

[0084] The drying means and heating means may also be installed downstream in the transport direction of the fabric 2. In this case, the fabric 2 is heated after the ink and treatment liquid ejected from the nozzles are attached to the fabric 2 to form an image. This improves the drying properties of the ink and treatment liquid attached to the fabric 2. [Example]

[0085] The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited to the following examples.

[0086] 1 to 3, Tables 1 to 3 are provided showing the constitution of each composition of the examples and comparative examples.

[0087] 1. Preparation of each composition Each component was placed in a mixing tank, mixed and stirred, and then filtered through a membrane filter to obtain the treatment liquid composition, colored ink composition, and clear ink composition of each example, so as to obtain the composition shown in Tables 1 to 3. Note that the numerical value of each component shown in each example in the tables represents the ratio in mass % based on the total mass of the corresponding composition, unless otherwise specified.

[0088] Details of the abbreviations and product ingredients used are as follows:

[0089] 1.1. Treatment liquid composition [Organic acid] DL-lactic acid Succinic acid Citric acid Polyacrylic acid [Organic acid salt] Calcium lactate [Polyvalent metal salts] Magnesium sulfate [Organic solvents] Glycerin Propylene glycol [Surfactants] Olfine E1010 (trade name, acetylene glycol surfactant, manufactured by Nissin Chemical Industry Co., Ltd.) [Antibacterial agent] Proxel XL2 (brand name, manufactured by Lonza Japan) [water] Ion-exchanged water

[0090] 1.2.Colored ink [Anionic self-dispersing resin emulsion] Polycarbonate polyurethane (product name "UW1527F", manufactured by UBE) [Nonionic self-dispersing resin emulsion] Non-reactive urethane resin (product name "Superflex 500M", Daiichi Kogyo Seiyaku) [Anionic self-dispersing pigment] 500 g of carbon black powder (primary particle diameter = 18 nm, BET specific surface area = 180 m) prepared by the furnace method 2 / g, DBP absorption = 186 mL / 100 g) was added to 3750 g of ion-exchanged water and heated to 45 °C while stirring with a dissolver. Subsequently, while grinding using a sand mill with 0.8 mm diameter zirconia beads, 30,000 g of an aqueous solution of sodium hypochlorite (available chlorine concentration = 12%) was added dropwise at 45 °C over 3.5 hours. Grinding was continued for 30 minutes using the sand mill to obtain a reaction solution containing self-dispersible carbon black. This reaction solution was filtered through a 400-mesh wire screen to separate the zirconia beads, unreacted carbon black, and the reaction solution. A 5% aqueous solution of potassium hydroxide was added to the separated reaction solution to adjust the pH to 7.5. Desalting and purification were performed using an ultrafiltration membrane until the liquid conductivity reached 1.5 mS / cm. Further desalting and purification were performed using an electrodialysis device until the liquid conductivity reached 1.0 mS / cm. The liquid was concentrated until the concentration of self-dispersible carbon black reached 17% by mass. The concentrated liquid was centrifuged to remove coarse particles and then filtered through a 0.6 μm filter. Ion-exchanged water was added to the resulting filtrate, and the self-dispersible carbon black was diluted to a concentration of 15% by mass. The resulting mixture was dispersed to obtain a self-dispersible pigment dispersion.

[0091] [Anionic resin-dispersed pigment] To 15 parts by mass of carbon black, 10 parts by mass of ammonium salt of styrene-acrylic acid copolymer (weight average molecular weight 10,000) as a dispersant polymer component and 55 parts by mass of ion-exchanged water were added and mixed thoroughly, and then this mixture was dispersed in a sand mill (manufactured by Yaskawa Corporation) together with glass beads (diameter 1.7 mm, 1.5 times the amount of the mixture) for 2 hours. After dispersion, the glass beads were removed to obtain a resin-dispersed pigment dispersion. [Organic solvents] Glycerin Triethylene glycol monobutyl ether [Surfactants] Olfine E1010 (trade name, acetylene glycol surfactant, manufactured by Nissin Chemical Industry Co., Ltd.) [pH adjuster] Triethanolamine [Antibacterial agent] Proxel XL2 (brand name, manufactured by Lonza Japan) [water] Ion-exchanged water

[0092] 1.3.Transparent ink [Anionic self-dispersing resin emulsion] Polycarbonate polyurethane (product name "UW1527F", manufactured by UBE) [Nonionic self-dispersing resin emulsion] Non-reactive urethane resin (product name "Superflex 500M", Daiichi Kogyo Seiyaku) [Organic solvents] Glycerin Triethylene glycol monobutyl ether [Surfactants] Olfine E1010 (trade name, acetylene glycol surfactant, manufactured by Nissin Chemical Industry Co., Ltd.) [pH adjuster] Triethanolamine [Antibacterial agent] Proxel XL2 (brand name, manufactured by Lonza Japan) [water] Ion-exchanged water

[0093] 2. Printing recording method Using a modified PX-H8000 (Seiko Epson Corporation) printer, printing was performed on a 100% cotton white broadcloth recording medium under the conditions shown in Tables 4 to 8 below. Main scanning was performed multiple times (2, 4, 8, 12, or 16 times) over the same scanning area to form a solid pattern image on the A4-sized fabric recording medium. The resulting image was then heated and dried in an oven at 160°C for 3 minutes to produce printed textiles according to each example and comparative example. Note that a "solid pattern image" refers to an image in which dots are recorded in all pixels, which are the minimum recording unit area defined by the recording resolution (100% duty).

[0094] The inkjet head used was a head unit with a nozzle-to-nozzle distance of 600 dpi in the width direction of the recording medium and 600 nozzles. In each example, the head nozzle group ejecting the treatment liquid and the head nozzle group ejecting the colored ink composition had portions that were at the same position in the sub-scanning direction, and the head nozzle group ejecting the non-colored ink composition was located downstream in the sub-scanning direction from the head nozzle group ejecting the colored ink composition. This allowed the treatment liquid and the colored ink composition to be deposited on the same scanned area of ​​the fabric by the same main scan, and the non-colored ink composition to be deposited on the same scanned area of ​​the fabric by a main scan different from the same main scan.

[0095] 4 to 8 show the compositions and recording methods of the examples, and Tables 4 to 8 show the evaluation results. In Tables 4 to 8, the "simultaneous" deposition method indicates a simultaneous deposition process in which the treatment liquid composition and the colored ink composition are deposited on the same operation area of ​​the fabric by the same main scanning motion. Also, "post-deposition" indicates that a clear ink deposition process was carried out after the simultaneous deposition process, in which the clear ink composition was deposited on the fabric by a main scanning motion different from that of the simultaneous deposition process.

[0096] In Tables 4 to 8, the recording areas indicate the following relationship between the recording areas. Note that unless otherwise specified in the tables, it is Type 1. <Recording area> Type 1: The treatment liquid application process and the clear ink application process are carried out on an equal area, and the colored ink application process is carried out on a smaller area (the area that falls within the treatment liquid and clear ink areas). Type 2: The treatment liquid application process, colored ink application process, and transparent ink application process are performed on the same area. Type 3: The colored ink application step is performed on an area narrower than the area where the treatment liquid application step is performed, and the clear ink application step is performed on an area narrower than the area where the colored ink application step is performed.

[0097] Although not shown in the table, if the relationship of the recording area in Example 20 is changed to Type 3, the abrasion resistance will be inferior to that of Example 20, but an effect equivalent to the abrasion resistance evaluation B described below can be obtained.

[0098] In Comparative Example 8 in Table 8, the amount of treatment liquid 3 applied to a 100% cotton white broadcloth was 27.6 g / m 2 The fabric was uniformly coated using a roller so that the ink composition was uniformly applied. After coating, the fabric was heated in an oven at 160°C for 2 minutes. The fabric was then transferred to the device described above, and the colored ink composition application step and the clear ink composition application step were carried out in this order.

[0099] 3. Evaluation Method 3.1. Strike-through resistance The OD value of the black on the backside of the print was measured using a fluorescence spectrodensitometer (FD-7, manufactured by Konica Minolta) for the printed fabric obtained above, and the degree of strike-through was evaluated according to the following criteria: When the evaluation result is B or higher, it can be said that strike-through has been suppressed and contamination of the transport system has been prevented. (Evaluation criteria) A: The maximum OD value is less than 0.46 B: The maximum OD value is 0.46 or more and less than 0.6. C: The maximum OD value is 0.6 or more.

[0100] 3.2.Color development The black OD value of the printed surface of the printed textile obtained above was measured using a fluorescence spectrodensitometer (FD-7, manufactured by Konica Minolta), and the color development was evaluated according to the following criteria. If the evaluation result was B or higher, it can be said that good color development was obtained. (Evaluation criteria) AAA: Maximum OD value is 1.50 or more AA: The maximum OD value is 1.47 or more and less than 1.50. A: The maximum OD value is 1.44 or more and less than 1.46. B: The maximum OD value is 1.40 or more and less than 1.44. C: The maximum OD value is less than 1.40.

[0101] 3.3.Abrasion resistance The prints obtained above were tested for rub fastness using a test method in accordance with ISO105-X12. The wet rub fastness was tested and evaluated according to the following criteria. It can be said that good wet rub fastness is obtained. (Evaluation criteria) A: Rub fastness is grade 3 or higher B: Rub fastness is 2-3 or more and less than 3 C: Rub fastness is grade 2 or more but less than grade 2-3 D: Rub fastness is less than grade 2

[0102] 4. Evaluation Results From Tables 4 to 8, it can be seen that the method for producing a fabric having a treatment liquid composition containing an organic acid and water applied to a given location on the fabric by an inkjet method, a colored ink application step of applying droplets of a colored ink composition containing a pigment, anionic first resin particles, and water to the given location by an inkjet method, and a clear ink application step of applying droplets of a clear ink composition containing anionic second resin particles and water to the given location by an inkjet method, wherein the amount of acidic groups derived from the organic acid applied to the given location in the treatment liquid application step is 4.5 mmol / m 2 As described above, it can be seen that when recording is performed by an inkjet recording method in which the shortest time lag |α| between when one of the colored ink composition and the treatment liquid composition is adhered to the arbitrary location and when the other is adhered to the arbitrary location is 5 minutes or less, excellent resistance to strike-through and abrasion resistance are achieved. [Explanation of symbols]

[0103] 1...printer, 2...fabric, 3...inkjet head, 4...carriage, 5...main scanning mechanism, 6...platen roller, 7a, 7b, 7c, 7d, 7e, 7f...liquid cartridge, 8...timing belt, 9...motor, 10...guide shaft

Claims

1. a treatment liquid application step of applying a treatment liquid composition containing an organic acid and water to a desired location on a fabric by an inkjet method; a color ink applying step of applying droplets of a color ink composition containing a pigment, anionic first resin particles, and water to the arbitrary location by an ink jet method; a clear ink applying step of applying droplets of a clear ink composition containing anionic second resin particles and water to the given location by an ink jet method, In the treatment liquid application step, the amount of acidic groups derived from the organic acid attached to the arbitrary location is 4.5 mmol / m 2 That's all, the shortest time difference |α| between when one of the colored ink composition and the treatment liquid composition is deposited on the given location and when the other is deposited on the given location is within 5 minutes; Inkjet recording method.

2. The time difference |α| is within 10 msec. The inkjet recording method according to claim 1 .

3. the shortest time difference |β| between when one of the colored ink composition and the clear ink composition is applied to the given location and when the other is applied to the given location is 1.0 sec or more and 5.0 sec or less; The inkjet recording method according to claim 1 .

4. The molecular weight of the organic acid is 5000 or less. The inkjet recording method according to claim 1 .

5. The pigment is a self-dispersing pigment. The inkjet recording method according to claim 1 .

6. an adhesion amount X of the treatment liquid per unit area, an adhesion amount Y of the colored ink composition per unit area, and an adhesion amount Z of the transparent ink composition per unit area satisfy the relationship of the following formula (1), (Y+Z) / X ≧ 1.1…(1) The inkjet recording method according to claim 1 .

7. In the recording area where the colored ink is applied, the amount of the colored ink composition applied per unit area Y is 10 g / m 2 That's all. The inkjet recording method according to claim 1 .

8. an area A of the first region to which the treatment liquid is adhered, an area B of the second region to which the colored ink composition is adhered, and an area C of the third region to which the clear ink composition is adhered satisfy the relationship of the following formula (2): C ≧ A ≧ B ... (2) The inkjet recording method according to claim 1 .

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