Inkjet composition set

Abstract

We provide an inkjet composition set with excellent wet friction fastness. [Solution] An inkjet composition set comprising a colored ink composition and a processing liquid composition, wherein the colored ink composition contains a pigment, resin particles, a basic compound A, and water, and the processing liquid composition contains an acid compound and water, and may also contain a basic compound B, and the molar concentration of acidic groups from the acid compound Ca1 (mol / kg), the molar concentration of basic groups from the basic compound A Cb1 (mol / kg), and the molar concentration of basic groups from the basic compound B Cb2 (mol / kg) satisfy the relationship Ca1 - (Cb1 + 1.5Cb2) ≥ 0.10 (mol / kg).

Description

[Technical Field]

[0001] This invention relates to an inkjet composition set. [Background technology]

[0002] Inkjet recording methods are rapidly developing in various fields because they enable the recording of high-resolution images with relatively simple equipment. In this context, various studies have been conducted on color development and wash fastness. For example, Patent Document 1 discloses an inkjet processing solution containing a water-soluble cationic polymer and an organic acid salt, wherein the content of the water-soluble cationic polymer is 0.1% by weight or more and less than 10% by weight of the total processing solution. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] WO2023 / 042761 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, when using a processing liquid composition obtained by a conventional configuration such as that described in Patent Document 1, there was room for improvement in the wet friction fastness of the resulting printed material. [Means for solving the problem]

[0005] The present invention provides an inkjet composition set comprising a processing liquid composition and a colored ink composition, wherein the processing liquid composition contains an acid compound and water, the processing liquid composition may or may not contain a basic compound A, and the colored ink composition contains a pigment, resin particles, a basic compound B, and water, and the molar concentration Ca1 (mol / kg) of the acidic group due to the acid compound, the molar concentration Cb1 (mol / kg) of the basic group due to the basic compound A, and the molar concentration Cb2 (mol / kg) of the basic group due to the basic compound B satisfy the following formula (1). Ca1-(Cb1+1.5Cb2)≧0.10(mol / kg)...Formula (1) (In equation (1), Ca1 > 0, Cb1 ≥ 0, and Cb2 > 0.) [Brief explanation of the drawing]

[0006] [Figure 1] Table 1 shows the composition of the composition set used in the example and its evaluation results. [Figure 2] Table 2 shows the composition of the composition set used in the example and its evaluation results. [Figure 3] Table 3 shows the composition of the composition set used in the example and its evaluation results. [Figure 4] Table 4 shows the composition of the composition set used in the example and its evaluation results. [Figure 5] Table 5 shows the composition of the composition set used in the example and its evaluation results. [Figure 6] Table 6 shows the composition of the composition set used in the comparative example and its evaluation results. [Figure 7] Table 7 shows the composition of the colored ink composition. [Figure 8] Table 8 shows the composition of the clear ink composition. [Modes for carrying out the invention]

[0007] Hereinafter, embodiments of the present invention (hereinafter referred to as "the present embodiment") will be described in detail with reference to the drawings as necessary. However, the present invention is not limited thereto, and various modifications are possible without departing from the gist thereof.

[0008] Conventionally, organic acids and polyvalent metal salts have been used as flocculants for aggregating ink in a processing liquid. Although polyvalent metal salts have strong flocculation power and tend to provide a recording material with suppressed color development and bleeding, they tend to produce aggregates that are easily soluble in water near the surface of the recording material, so the wet rubbing fastness of the obtained recording material tends to decrease. On the other hand, it is known that an organic acid reacts with an anion component in the ink to neutralize it, thereby reducing the hydrophilicity of the anion component, and thus a recording material having good wet rubbing fastness can be obtained.

[0009] By the way, even when an organic acid is used, depending on the concentration relationship between the organic acid compound and the base compound that undergo a neutralization reaction in the mixed state of the processing liquid composition and the ink composition, sufficient wet rubbing fastness may not be obtained, and detailed studies have been required on the conditions for an optimal neutralization reaction.

[0010] In the present invention, in an inkjet composition set including a colored ink composition and a processing liquid composition, when the molar concentration Ca1 of acidic groups by an acid compound contained in the processing liquid composition, the molar concentration Cb2 of a base compound B contained in the colored ink composition, and the molar concentration Cb1 of basic groups by a base compound A contained in the processing liquid composition satisfy the conditions of the following formula (1), it has been found that a recording material excellent in wet rubbing fastness can be obtained. Ca1 - (Cb1 + 1.5Cb2) ≥ 0.10 (mol / kg) ··· Formula (1)

[0011] This is because the acid compound in the processing liquid composition causes dispersion breakdown of the resin particles in the colored ink composition and tends to form aggregates with low solubility in water. By increasing the amount of acidic groups more than a predetermined amount, it is presumed that the dispersion breakdown is promoted and the ink components eluted from the printed matter during wet rubbing are reduced, resulting in good wet rubbing fastness.

[0012] However, on the other hand, the coloring ink composition may contain a basic compound for the purpose of reducing skin irritation and improving storage stability. Also, from the same perspective, the treatment liquid composition may contain a basic compound as needed. Since such a basic compound reacts with an acid compound, it is likely to compete with the reaction between the acid compound and the resin particles. Among basic compounds, particularly the basic compound contained in the ink composition tends to have a large effect of inhibiting the role of the acid compound.

[0013] Therefore, in the present embodiment, as shown in the above formula (1), it is defined that the acidic group is more than a predetermined amount. Thereby, the amount of the acid compound is defined such that the dispersion destruction effect is not inhibited by the basic compound contained in the treatment liquid composition and the ink composition. Also, as described above, since the basic compound contained in the ink composition has a large effect of inhibiting the role of the acid compound, this point is corrected by a coefficient with respect to the molar concentration Cb2. Thereby, it is considered that when the above formula (1) is satisfied, the recording material is particularly excellent in wet rubbing fastness.

[0014] In this specification, "acid" and "acid compound" refer to those having a pH of less than 7 when made into a 0.1 mass% aqueous solution at 25°C. Also, "base" and "base compound" refer to those having a pH of more than 7 when made into a 0.1 mass% aqueous solution at 25°C. Further, in the ink composition, a compound contained as a "chelating agent" shall not be treated as an acid compound in the present embodiment.

[0015] Hereinafter, each component contained in the inkjet composition set will be described in detail.

[0016] <Inkjet Composition Set> The inkjet composition set according to this embodiment (hereinafter also simply referred to as the "composition set") comprises a processing liquid composition and a colored ink composition, wherein the processing liquid composition contains an acid compound and water, and the processing liquid composition may or may not contain a basic compound A, and the colored ink composition contains a pigment, resin particles, a basic compound B, and water, and the molar concentration Ca1 (mol / kg) of the acidic group due to the acid compound, the molar concentration Cb1 (mol / kg) of the basic group due to the basic compound A, and the molar concentration Cb2 (mol / kg) of the basic group due to the basic compound B satisfy the following formula (1). Ca1-(Cb1+1.5Cb2)≧0.10(mol / kg)...Formula (1) (In equation (1), Ca1 > 0, Cb1 ≥ 0, and Cb2 > 0.)

[0017] In formula (1), the value of Ca1-(Cb1+1.5Cb2) is preferably between 0.10 and 8.0. By keeping the value of Ca1-(Cb1+1.5Cb2) within the above range, the number of basic groups is not excessively reduced, and the effect of wet friction fastness according to the present invention tends to be more effective and reliable. From a similar viewpoint, the value of Ca1-(Cb1+1.5Cb2) is more preferably between 0.15 and 7.0, even more preferably between 0.15 and 6.0, even more preferably between 0.15 and 5.0, and even more preferably between 0.40 and 3.0.

[0018] 1. Processing liquid composition The processing liquid composition included in the composition set is used by adhering it to a recording medium, and contains an acid compound and water, and may optionally contain a base compound A. The composition set may contain one processing liquid composition or two or more. In addition, the acid compound and base compound A may partially form a neutralized salt in the processing liquid composition.

[0019] The pH of the treatment solution composition is preferably between 1.5 and 7.0. By setting the pH of the treatment solution composition within the above range, the wet friction fastness effect according to the present invention tends to be more effective and reliable. From a similar viewpoint, the pH of the treatment solution composition is more preferably between 2.0 and 6.5, even more preferably between 2.5 and 6.5, and still more preferably between 2.5 and 5.5.

[0020] 1.1. Acid compounds Examples of acid compounds include organic acids and inorganic acids. From the viewpoint of further improving the wet friction fastness of the printed material and enhancing its irritation-reducing properties, the use of organic acids is preferable. One acid compound may be used alone, or two or more may be used in combination.

[0021] The acid compound preferably has a pKa in water at 25°C between 2.0 and 7.0. Having the pKa of the acid compound in water at 25°C within this range allows it to exhibit buffering capacity in the pH range of 2.5 to 6.5, and also allows for a lower neutralization rate with base compound A. As a result, it tends to exhibit excellent wet friction fastness and improved irritation mitigation. From a similar viewpoint, the pKa of the acid compound at 25°C is more preferably between 2.2 and 6.5, even more preferably between 2.5 and 6.0, and even more preferably between 2.8 and 5.8.

[0022] In this specification, if a compound has a pKa within a certain range, it means that if it has a single pKa, that pKa is within a predetermined range, and if it has multiple pKas, it means that one or more of the pKas are within the relevant range.

[0023] Suitable acid compounds include, for example, lactic acid, malonic acid, citric acid, adipic acid, succinic acid, malic acid, levulinic acid, phosphoric acid, glutaric acid, polyacrylic acid, acetic acid, glycolic acid, maleic acid, ascorbic acid, fumaric acid, tartaric acid, sulfonic acid, orthophosphoric acid, pyrrolidone carboxylic acid, pyrrone carboxylic acid, pyrrole carboxylic acid, furanic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, or derivatives of these compounds, or salts thereof. Among these, it is preferable that one or more are selected from the group consisting of lactic acid, acetic acid, malonic acid, citric acid, adipic acid, succinic acid, malic acid, levulinic acid, glutaric acid, dimethylolpropionic acid, propionic acid, and phosphoric acid; more preferably one or more are selected from the group consisting of lactic acid, acetic acid, levulinic acid, malic acid, malonic acid, citric acid, glutaric acid, phosphoric acid, and dimethylolpropionic acid; and even more preferably one or more are selected from the group consisting of lactic acid, levulinic acid, malic acid, malonic acid, citric acid, glutaric acid, phosphoric acid, and dimethylolpropionic acid. Including such an acid compound tends to make the effect of improving wet friction fastness according to the present invention even more effective and reliable.

[0024] In the treatment solution composition, the molal concentration Ca1 (mol / kg) of acidic groups derived from the acid compound is preferably 0.20 or more and 5.00 or less. By keeping Ca1 within the above range, the effect of improving wet frictional durability according to the present invention tends to be more effective and reliable. From a similar viewpoint, Ca1 (mol / kg) is more preferably 0.30 or more and 4.75 or less, more preferably 0.35 or more and 4.75 or less, even more preferably 0.40 or more and 3.50 or less, and even more preferably 0.50 or more and 3.50 or less.

[0025] The mass-based content of the acid compound is preferably 1.0 to 50% by mass, 2.0 to 40% by mass, 3.5 to 30% by mass, or 4.0 to 15% by mass, relative to the total amount of the treatment solution composition. By keeping the mass-based content of the acid compound within the above range, the effect of improving wet friction fastness according to the present invention tends to be more effective and reliable.

[0026] 1.2. Basic Compound A The treatment solution composition may or may not contain base compound A. Examples of base compound A include organic bases and inorganic bases. Among organic and inorganic bases, metal hydroxides or amine compounds are preferred. Using such a base compound A tends to make the effect of improving wet friction fastness according to the present invention more effective and reliable. Furthermore, using such a base compound A tends to improve the solubility of base compound A in water. From a similar viewpoint, alkali metal hydroxides, alkaline earth metal hydroxides, or amine compounds are more preferred, and alkaline earth metal hydroxides or amine compounds are even more preferred. Note that one type of base compound A may be used alone, or two or more types may be used in combination.

[0027] The base compound A preferably contains one or more metal hydroxides selected from the group consisting of Li, Na, and K, or an amine compound containing 1 to 10 nitrogen atoms in its molecule, or one or more metal hydroxides selected from the group consisting of Li, Na, and K, or an amine compound containing 1 to 6 nitrogen atoms in its molecule. In particular, using such a base compound tends to further improve wet friction fastness, especially in cotton fabrics.

[0028] The metals constituting the metal hydroxide are preferably one or more selected from the group consisting of Li, Na, K, Ca, Mg, and Al, and more preferably at least one of Na and K. Using such metal hydroxides tends to make the recording material even more resistant to wet friction. From a similar viewpoint, the metal hydroxide is one or more selected from the group consisting of LiOH, NaOH, KOH, Ca(OH)2, Mg(OH)2, and Al(OH)3, and one or more selected from the group consisting of NaOH, KOH, Ca(OH)2, Mg(OH)2, and Al(OH)3. Using such metal hydroxides tends to make the recording material even more resistant to wet friction.

[0029] Preferably, the amine compound is one or more selected from the group consisting of alkanolamine compounds, polyhydric amine compounds, and polyamine compounds. Using such an amine compound tends to further improve the wet friction fastness of the recorded material.

[0030] Examples of alkanolamine compounds include triethanolamine, trippropanolamine, triisopropanolamine, and tripbutanolamine. Among these, triisopropanolamine is preferred from the viewpoint of more effectively and reliably improving the wet friction fastness of the recording material. Examples of polyvalent amine compounds include diethylenetriamine, dipropylenetriamine, dihexylentriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and hexaethyleneheptamine. Among these, dipropylenetriamine is preferred from the same viewpoint as described above.

[0031] Any polyamine compound that has an amino group in its structure will suffice, for example, Examples include polyamine resins, polyamide resins, and polyallylamine resins. As the polyamine compound, any commercially available product corresponding to the basic compound in this specification may be used. Examples of commercially available polyamine compounds include PAA-SA, PAA-01, 03, 05, 08, 15, 15C, 25, PAA-H-10C, PAA-D11-HCl, PAA-D41-HCl, PAA-D19-HCl, PAS-21CL, 22SA, 92, 92A, PAS-M-1, 1L, 1A, PAS-H-1L, 5L, 10L, PAS-J-81, 81L (all trade names, manufactured by Nitto Boseki Medical Co., Ltd.), FL-14 (manufactured by SNF Co., Ltd.), Arafix 100, 251S, 255, 255LOX (manufactured by Arakawa Chemical Co., Ltd.), and DK-6. Examples include 810, 6853, 6885; WS-4010, 4011, 4020, 4024, 4027, 4030 (manufactured by Seikoh PMC), Papiogen P-105 (manufactured by Senka), Sumirez Resin 650(30), 675A, 6615, SLX-1 (manufactured by Taoka Chemical Industry Co., Ltd.), Kachiomaster (registered trademark) PD-1, 7, 30, A, PDT-2, PE-10, PE-30, DT-EH, EPA-SK01, TMHMDA-E (manufactured by Yokkaichi Gosei Co., Ltd.), and Jetfix 36N, 38A, N700, 5052 (manufactured by Satoda Chemical Co., Ltd.). Among these, PAA-03 is preferred from the viewpoint of further effectively and reliably improving the wet friction fastness of the recording material.

[0032] Examples of polyallylamine resins include polyallylamine hydrochloride, polyallylamineamide sulfate, allylamine hydrochloride / diallylamine hydrochloride copolymer, allylamine acetate / diallylamine acetate copolymer, allylamine acetate / diallylamine acetate copolymer, allylamine hydrochloride / dimethylallylamine hydrochloride copolymer, allylamine / dimethylallylamine copolymer, polydiallylamine hydrochloride, polymethyldiallylamine hydrochloride, polymethyldiallylamineamide sulfate, polymethyldiallylamine acetate, polydiallyldimethylammonium chloride, diallylamine acetate / sulfur dioxide copolymer, diallylmethylethylammonium ethyl sulfate / sulfur dioxide copolymer, methyldiallylamine hydrochloride / sulfur dioxide copolymer, diallyldimethylammonium chloride / sulfur dioxide copolymer, and diallyldimethylammonium chloride / acrylamide copolymer.

[0033] In the treatment solution composition, the molal concentration Cb1 (mol / kg) of the basic group derived from base compound A is preferably 0.00 or more and 3.00 or less. By keeping Cb1 within the above range, the effect of improving wet frictional fastness according to the present invention tends to be more effective and reliable. From a similar viewpoint, Cb1 (mol / kg) is more preferably 0.01 or more and 2.50 or less, even more preferably 0.05 or more and 2.00 or less, even more preferably 0.05 or more and 1.50 or less, even more preferably 0.10 or more and 1.75 or less, and even more preferably 0.10 or more and 1.00 or less.

[0034] The mass content of basic compound A is preferably 0.0 to 40% by mass, 0.1 to 30% by mass, 0.5 to 20% by mass, 0.5 to 10% by mass, 1.0 to 10% by mass, and 1.0 to 5% by mass, relative to the total amount of the treatment solution composition. By keeping the content of basic compound A within the above range, the effect of improving wet friction fastness according to the present invention tends to be more effective and reliable.

[0035] 1.3. Water-soluble organic solvents The processing solution composition may contain a water-soluble organic solvent. The organic solvent is not limited as long as it is water-soluble, but examples include polyhydric alcohols, glycol ethers, nitrogen-containing solvents, esters, and cyclic esters. Among these, polyhydric alcohols are preferred from the viewpoint of more effectively and reliably improving the wet friction fastness of the recorded material. Note that the water-soluble organic solvent may be used alone or in combination of two or more.

[0036] Polyhydric alcohols can be classified into, for example, polyols and diol compounds. 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 to include one or more selected from the group consisting of glycerin, propylene glycol, and triethylene glycol, from the viewpoint of further effectively and reliably improving the wet friction fastness of the recording material.

[0037] Specific diol compounds include, for example, 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. Among these, 1,2-hexanediol is preferred from the viewpoint of more effectively and reliably improving the wet friction fastness of the recorded material.

[0038] Furthermore, specific compounds of glycol ethers include, for example, 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. Among these, triethylene glycol monobutyl ether is preferred from the viewpoint of more effectively and reliably improving the wet friction fastness of the recorded material.

[0039] The content of the water-soluble organic solvent is preferably 5 to 50% by mass, 10 to 40% by mass, or 12 to 30% by mass, relative to the total amount of the treatment liquid composition. By keeping the content of the water-soluble organic solvent within the above range, the wet friction fastness tends to be further improved. From a similar viewpoint, it is preferable that the content of polyhydric alcohols or glycol ethers is 5 to 50% by mass, 10 to 40% by mass, or 12 to 30% by mass, relative to the total amount of the treatment solution composition.

[0040] 1.4. Surfactants The processing solution composition may contain a surfactant. Examples of surfactants include nonionic surfactants, anionic surfactants, and amphoteric surfactants. From the viewpoint of more effectively and reliably improving the ejection stability when the processing solution composition is ejected by the inkjet method, nonionic surfactants are preferred. Nonionic surfactants are also preferred because they tend to be stable even in processing solution compositions containing acid compounds and base compounds. One type of surfactant may be used alone, or two or more types may be used in combination.

[0041] Examples of nonionic surfactants include acetylene glycol-based surfactants, alcohol ethoxylate-based surfactants, fluorine-based surfactants, and silicone-based surfactants.

[0042] The acetylene glycol-based surfactant is not particularly limited, but examples include one or more selected from 2,4,7,9-tetramethyl-5-decine-4,7-diol and alkylene oxide adducts of 2,4,7,9-tetramethyl-5-decine-4,7-diol, and 2,4-dimethyl-5-decine-4-ol and alkylene oxide adducts of 2,4-dimethyl-5-decine-4-ol.

[0043] Examples of commercially available acetylene glycol-based surfactants include the E series (product names of Air Products Co., Ltd.), such as the Olfin 104 series and Olfin E1010, and Surfinol 61, 104, and 465 (product names of Nisshin Chemical Industry Co., Ltd.). Among these, Surfinol 465 is preferred from the viewpoint of achieving the wet friction fastness effect according to the present invention more effectively and reliably.

[0044] Alcohol ethoxylate surfactants are compounds in which a polyoxyethylene chain and an alkyl group are linked by an ether bond, and "R A -O-(CH2CH2O) d It can be represented by the molecular formula "-H" and is sometimes called a poly(oxyethylene) alkyl ether.

[0045] Examples of alcohol ethoxylate surfactants include CL-40, CL-50, CL-70, CL-85, CL-95, CL-100, CL-120, CL-140, CL-160, CL-200, and CL-400 (product names manufactured by Sanyo Chemical Industries, Ltd.).

[0046] Examples of fluorinated surfactants include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphate esters, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines, and perfluoroalkylamine oxide compounds.

[0047] Examples of silicone-based surfactants include polysiloxane compounds and polyether-modified organosiloxanes. Commercially available examples include BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349 (all product names, manufactured by BIC Chemie Japan Co., Ltd.), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017 (all product names, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0048] The surfactant content is preferably 0.01 to 3.0% by mass, 0.03 to 1.0% by mass, or 0.05 to 0.1% by mass, relative to the total amount of the treatment solution composition. By setting the surfactant content within the above range, the wet friction fastness effect according to the present invention can be achieved more effectively and reliably.

[0049] 1.5.Water The processing liquid composition contains water. Preferably, the water is one from which ionic impurities have been removed as much as possible. Examples of such water include pure water such as ion-exchanged water, reverse osmosis water, and distilled water, as well as ultrapure water.

[0050] 1.6. Other ingredients The processing solution composition may contain, as necessary, various additives other than those mentioned above, such as pH adjusters, chelating agents, softeners, solubilizers, viscosity modifiers, UV absorbers, antioxidants, and corrosion inhibitors. Furthermore, the processing solution composition is not an ink and is not intended to color itself.

[0051] 2. Colored ink composition The colored ink composition included in the composition set contains a pigment, resin particles, basic compound B, and water. The colored ink composition may be applied to a recording medium to which the processing liquid composition is attached, applied to the recording medium simultaneously with the processing liquid composition, or applied to a recording medium to which the processing liquid composition is attached. From the viewpoint of achieving the wet friction fastness effect of the present invention more effectively and reliably, it is preferable to apply the colored ink composition to the recording medium simultaneously with the processing liquid composition.

[0052] The pH of the colored ink composition is preferably greater than 6.5. By keeping the pH of the colored ink composition within the above range, the storage stability of the colored ink composition is good, and the wet friction fastness effect according to the present invention tends to be more effective and reliable. Furthermore, there is no particular upper limit to the pH of the colored ink composition, but it may be 13 or less, 12.5 or less, or 12 or less.

[0053] 2.1. Pigments The pigment preferably includes anionic dispersion pigments. Anionic phosphorus-containing pigments are dispersed by neutralizing the acidic groups with a base. The acidic compounds in the treatment solution composition cause the acidic groups of the dispersion pigment, which are relatively weak acids, to be released, reducing their solubility and tending to improve wet friction fastness.

[0054] In a colored ink composition, examples of the dispersed pigment include self-dispersing pigments and resin-dispersing pigments. From the viewpoint of facilitating the reaction with the processing liquid composition, it is preferable to use a self-dispersing pigment.

[0055] More specifically, examples of pigments include inorganic pigments and organic pigments. As inorganic pigments, in addition to titanium dioxide and iron oxide, carbon black produced by known methods such as the contact method, furnace method, and thermal method can be used. On the other hand, as organic pigments, examples include azo pigments, polycyclic pigments, nitro pigments, nitroso pigments, and aniline black. Examples of azo pigments include azo lakes, insoluble azo pigments, condensed azo pigments, and chelated azo pigments.

[0056] Examples of carbon black pigments include CI (Colour Index Generic Name) Pigment Black 1, 7, and 11. Commercially available carbon blacks may also be used, such as Mitsubishi Chemical'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® 35, U, V, 140U, and SpecialBlack 6, 5, 4A, 4. Pigments obtained by the preparation method described in the examples below may also be used.

[0057] The pigment content in the colored ink is preferably 1 to 10% by mass, 2 to 8% by mass, or 3 to 7% by 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 achieved more effectively and reliably. The pigment content in the colored ink is based on the mass percentage of the pigment solids.

[0058] 2.2. Resin particles Examples of resin particles include anionic resin particles, nonionic resin particles, and cationic resin particles. Among the resin particles, anionic resin particles are preferred from the viewpoint of more effectively and reliably achieving the wet friction fastness effect of the present invention. Examples of anionic groups contained in anionic resin particles include sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, and hydroxyl groups, but acidic groups are preferred. Using resin particles having acidic groups tends to more effectively and reliably achieve the effect of the present invention. The resin particles are particles containing resin, and can be used in either an emulsion state or a solution state, but from the viewpoint of suppressing an increase in ink viscosity, it is preferable to use them in an emulsion state.

[0059] The anionic resin particles are not limited as long as they have anionic groups, but more specifically, examples 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, styrene-acrylic resins or urethane resins are preferred, and urethane resins are more preferred, from the viewpoint of achieving the effects of the present invention more effectively and reliably.

[0060] The content of resin particles in the colored ink composition is preferably 1 to 10% by mass, 2 to 8% by mass, and 3 to 7% by mass, relative to the total amount of the colored ink composition. By keeping the resin particle content within the above range, the effects of the present invention can be achieved more effectively and reliably. From a similar viewpoint, the content of anionic resin particles in the colored ink composition is preferably 1 to 10% by mass, 2 to 8% by mass, and 3 to 7% by mass, relative to the total amount of the colored ink composition. The above content is based on the mass percentage of the solid content of the resin particles.

[0061] 2.3. Basic Compound B Examples of base compound B include organic bases and inorganic bases. Among organic and inorganic bases, metal hydroxides and amine compounds are preferred. Using metal hydrides or amine compounds tends to improve the wet friction fastness of the recorded material. Base compound B may be used alone or in combination of two or more types.

[0062] Specific examples of base compound B include compounds similar to the metal hydroxide and amine compounds in base compound A described above. Among these, from the viewpoint of achieving the wet friction fastness effect of the present invention more effectively and reliably, it is preferable that it contains at least one of potassium hydroxide and triethanolamine.

[0063] In the colored ink composition, the molal concentration Cb2 (mol / kg) of the basic group derived from base compound B is preferably 0.00 or more and 3.00 or less. By keeping Cb2 within the above range, the effect of improving wet friction fastness according to the present invention tends to be more effective and reliable. From a similar viewpoint, Cb2 (mol / kg) is more preferably 0.001 or more and 2.50 or less, and even more preferably 0.005 or more and 2.00 or less.

[0064] The mass content of basic compound B is preferably 0.0 to 10% by mass, 0.05 to 5% by mass, 0.1 to 3.5% by mass, or 0.5 to 3.0% by mass, relative to the total amount of the colored ink composition. By keeping the content of basic compound B within the above range, the effect of improving wet friction fastness according to the present invention tends to be more effective and reliable.

[0065] 2.4. Water-soluble organic solvents The colored ink composition may contain a water-soluble organic solvent. The organic solvent used in the colored ink composition is not limited as long as it is water-soluble, and examples include those exemplified in the processing liquid composition described above. Among these, polyhydric alcohols are preferred from the viewpoint of further effectively and reliably improving the wet friction fastness of the recorded material, and it is more preferable to use at least one of glycerin and 1,2-hexanediol. Note that the organic solvent may be used alone or in combination of two or more.

[0066] The organic solvent content in the colored ink is preferably 5-40% by mass, 10-30% by mass, or 12-25% by mass, relative to the total amount of the colored ink composition. Keeping the organic solvent content within these ranges tends to further improve wet friction fastness.

[0067] 2.5. Surfactants The colored ink composition may contain a surfactant. Examples of surfactants used in the colored ink composition include those exemplified in the processing liquid composition described above. Among such surfactants, acetylene glycol-based surfactants are preferred from the viewpoint of achieving the wet friction fastness effect according to the present invention more effectively and reliably, and Surfinol 465 is a preferred commercially available product thereof. One surfactant may be used alone, or two or more may be used in combination.

[0068] The surfactant content is preferably 0.1 to 3.0% by mass, 0.2 to 2.0% by mass, and 0.3 to 1.0% by mass, relative to the total amount of the colored ink composition. By setting the surfactant content within the above range, the wet friction fastness effect according to the present invention can be achieved more effectively and reliably.

[0069] 2.6. Chelating agents The colored ink composition may contain a chelating agent. Examples of chelating agents used in the colored ink composition include ethylenediaminetetraacetate disodium salt (EDTA2Na), ethylenediaminetetraacetate (EDTA), ethylenediamine nitrilotriacetate, hexametaphosphate, pyrophosphate, and metaphosphate. From the viewpoint of achieving the wet friction fastness effect of the present invention more effectively and reliably, ethylenediaminetetraacetate disodium salt (EDTA2Na) is preferred.

[0070] The chelating agent content is preferably 0.001 to 0.5% by mass, 0.005 to 0.3% by mass, or 0.01 to 0.1% by mass, relative to the total amount of the colored ink composition. By setting the chelating agent content within the above range, the wet friction fastness effect according to the present invention can be achieved more effectively and reliably.

[0071] 2.7.Water As for the water, it is preferable to use water from which ionic impurities have been removed as much as possible. Examples of such water include pure water such as ion-exchanged water, reverse osmosis water, and distilled water, as well as ultrapure water.

[0072] 2.8. Other Ingredients In addition to the above-mentioned components, various additives such as pH adjusters, softeners, solubilizers, viscosity modifiers, UV absorbers, antioxidants, and corrosion inhibitors may be included as needed.

[0073] 3. Clear ink composition The composition set may further contain a clear ink composition. The clear ink composition is a composition containing resin particles, a basic compound C, and water, and substantially free of colorants. The inclusion of a clear ink composition in the composition set tends to further improve the wet abrasion fastness of the recorded material.

[0074] Furthermore, the clear ink composition is not an ink used for coloring, but rather for purposes such as improving the scratch resistance of the recorded material, adjusting the gloss level, and improving the fixation and color development of the color ink. Here, "substantially free of colorants" means that the colorant content is preferably 0.1% by mass or less, 0.05% by mass or less, and 0.01% by mass or less, relative to the total amount of the clear ink composition.

[0075] When the composition set includes a clear ink composition, preferably, the above Ca1, above Cb1, above Cb2, and the molar concentration Cb3 (mol / kg) of the basic group due to the above base compound C satisfy the following formula (2). By satisfying the relationship of formula (2), the effect of the aggregation reaction between the acid compound and the base compound in each composition can be optimized, resulting in a tendency for the wet friction fastness of the recording material, especially the wet friction fastness when polyester fabric is used as the recording medium, to be further improved. In formula (2), the value of Ca1-(Cb1+1.5Cb2+1.5Cb3) is preferably 0.10 or more and 8.0 or less, more preferably 0.10 or more and 7.0 or less, and even more preferably 0.10 or more and 6.0 or less. Ca1-(Cb1+1.5Cb2+1.5Cb3)≧0.10(mol / kg)...Formula (2)

[0076] When the composition set includes a clear ink composition, preferably, Ca1, Cb1, Cb2, and Cb3 satisfy the following formula (4). By satisfying the relationship of formula (4), the effect of the aggregation reaction between the acid compound and the base compound in each composition can be optimized, resulting in a tendency for the wet friction fastness of the recording material, particularly the wet friction fastness when polyester fabric is used as the recording medium, to be further improved. In formula (4), the value of Ca1-(Cb1+1.5Cb2+1.5Cb3) is preferably 0.15 or more and 8.0 or less, more preferably 0.15 or more and 7.0 or less, and even more preferably 0.15 or more and 6.0 or less. Ca1-(Cb1+1.5Cb2+1.5Cb3)≧0.15(mol / kg)...Formula (4)

[0077] When the composition set includes a clear ink composition, preferably, the above Ca1, Cb1, Cb2, and Cb3 satisfy the following formula (3). By satisfying the relationship of formula (3), the excessive generation of neutralization salts is suppressed, and the wet friction fastness of the recorded material to the polyester cloth tends to be further improved. In formula (3), the value of {Ca1-(Cb1+1.5Cb2+1.5Cb3)} / 1.5(Cb1+1.5Cb2+1.5Cb3) is preferably 0.01 or more and 150 or less, more preferably 0.01 or more and 130 or less, and even more preferably 0.01 or more and 10 or less. {Ca1-(Cb1+1.5Cb2+1.5Cb3)} / 1.5(Cb1+1.5Cb2+1.5Cb3)≧0.01...Equation (3)

[0078] When the composition set includes a clear ink composition, preferably, Ca1, Cb1, Cb2, and Cb3 satisfy the following formula (5). Satisfying the relationship of formula (5) suppresses the excessive generation of neutralization salts, and tends to further improve the wet friction fastness of the recorded material to the polyester cloth. In formula (5), the value of {Ca1-(Cb1+1.5Cb2+1.5Cb3)} / 1.5(Cb1+1.5Cb2+1.5Cb3) is preferably 0.20 or more and 150 or less, more preferably 0.20 or more and 130 or less, and even more preferably 0.20 or more and 10 or less. {Ca1-(Cb1+1.5Cb2+1.5Cb3)} / 1.5(Cb1+1.5Cb2+1.5Cb3)≧0.20...Equation (5)

[0079] 3.1. Resin particles As resin particles, those similar to those used in the colored ink composition described above can also be preferably used.

[0080] The content of resin particles in the clear ink composition is preferably 1 to 20% by mass, 5 to 15% by mass, and 8 to 12% by mass, relative to the total amount of the clear ink composition. By keeping the resin particle content within the above range, the effects of the present invention can be achieved more effectively and reliably. From a similar viewpoint, the content of anionic resin particles in the clear ink composition is preferably 1 to 20% by mass, 5 to 15% by mass, and 8 to 12% by mass, relative to the total amount of the clear ink composition. The above content is based on the mass percentage of the solid content of the resin particles.

[0081] 3.2. Basic Compound C Examples of base compound C include organic bases and inorganic bases. Among organic and inorganic bases, metal hydroxides and amine compounds are preferred. Using metal hydrides or amine compounds tends to improve the wet friction fastness of the recorded material. Base compound C may be used alone or in combination of two or more types.

[0082] The above-mentioned base compound A, base compound B, and base compound C preferably contain one or more selected from alkali metal hydroxides, alkaline earth metal hydroxides, and amine compounds. By using a set of compositions containing such base compounds, the wet friction fastness effect of the present invention tends to be achieved more effectively and reliably.

[0083] As a specific compound for base compound C, compounds similar to the metal hydroxide and amine compounds in base compound A described above can be used. Among these, from the viewpoint of achieving the wet friction fastness effect of the present invention more effectively and reliably, it is preferable to include at least one of potassium hydroxide and triethanolamine.

[0084] In the clear ink composition, the molal concentration Cb3 (mol / kg) of the basic group derived from the base compound C is preferably 0.000 or more and 3.00 or less. By keeping Cb3 within the above range, the effect of improving wet friction fastness according to the present invention tends to be more effective and reliable. From a similar viewpoint, Cb3 (mol / kg) is more preferably 0.001 or more and 2.50 or less, and even more preferably 0.005 or more and 2.00 or less.

[0085] When the composition set includes a clear ink composition, it is preferable that Cb2 and Cb3 are each 0.35 mol / kg or less. By keeping Cb2 and Cb3 within the above range, the wet friction fastness of the recorded material tends to improve further. From a similar viewpoint, it is more preferable that Cb2 and Cb3 are each 0.30 mol / kg or less, and even more preferable that they are 0.25 mol / kg or less.

[0086] The mass-based content of basic compound C is preferably 0.0 to 10% by mass, 0.01 to 5% by mass, and 0.011 to 3.7% by mass, relative to the total amount of the clear ink composition. By keeping the content of basic compound C within the above range, the effect of improving wet friction fastness according to the present invention tends to be more effective and reliable.

[0087] 3.3. Water-soluble organic solvents The clear ink composition may contain a water-soluble organic solvent. The organic solvent used in the clear ink composition is not limited as long as it is water-soluble, and examples include those exemplified in the processing liquid composition described above. Among these, polyhydric alcohols are preferred from the viewpoint of further effectively and reliably improving the wet friction fastness of the recorded material, and it is more preferable to use at least one of glycerin and 1,2-hexanediol. The organic solvent may be used alone or in combination of two or more.

[0088] The organic solvent content in the clear ink is preferably 5-40% by mass, 10-30% by mass, or 15-25% by mass, relative to the total amount of the clear ink composition. Keeping the organic solvent content within these ranges tends to further improve wet friction fastness.

[0089] 3.4. Surfactants The clear ink composition may contain a surfactant. Examples of surfactants include those used in the processing liquid composition described above. Among such surfactants, acetylene glycol-based surfactants are preferred from the viewpoint of more effectively and reliably achieving the wet friction fastness effect according to the present invention, and Surfinol 465 is a preferred commercially available product. One surfactant may be used alone, or two or more may be used in combination.

[0090] The surfactant content is preferably 0.1 to 3.0% by mass, 0.2 to 2.0% by mass, or 0.3 to 1.0% by mass, relative to the total amount of the clear ink composition. By setting the surfactant content within the above range, the wet friction fastness effect according to the present invention can be achieved more effectively and reliably.

[0091] 3.5. Chelating agents The clear ink composition may contain a chelating agent. Examples of chelating agents used in the clear ink composition include ethylenediaminetetraacetate disodium salt (EDTA2Na), ethylenediaminetetraacetate (EDTA), ethylenediamine nitrilotriacetate, hexametaphosphate, pyrophosphate, and metaphosphate. From the viewpoint of achieving the wet friction fastness effect of the present invention more effectively and reliably, ethylenediaminetetraacetate disodium salt (EDTA2Na) is preferred.

[0092] The chelating agent content is preferably 0.001 to 0.5% by mass, 0.005 to 0.3% by mass, or 0.01 to 0.1% by mass, relative to the total amount of the clear ink composition. By setting the chelating agent content within the above range, the wet friction fastness effect according to the present invention can be achieved more effectively and reliably.

[0093] 3.6.Water As for the water, it is preferable to use water from which ionic impurities have been removed as much as possible. Examples of such water include pure water such as ion-exchanged water, reverse osmosis water, and distilled water, as well as ultrapure water.

[0094] 3.7. Other ingredients In addition to the above-mentioned components, various additives such as pH adjusters, softeners, solubilizers, viscosity modifiers, UV absorbers, antioxidants, and corrosion inhibitors may be included as needed.

[0095] 4. Preparation methods for each composition Each composition can be prepared, for example, by mixing the components in any order and removing impurities and foreign matter by filtration or other methods as needed. A method for mixing the components is to sequentially add each component to a container equipped with a stirring device such as a mechanical stirrer or magnetic stirrer, and then stir and mix them. Filtration methods include centrifugal filtration and filter filtration. Alternatively, the methods used in the examples described later may also be employed. [Examples]

[0096] The present invention will be described more specifically below with reference to examples and comparative examples. The present invention is not limited in any way by the following examples.

[0097] Figures 1 to 8 show Tables 1 to 8 illustrating the composition of each composition set in the examples and comparative examples, and / or their evaluation results.

[0098] 1. Preparation of each composition Each component was placed in a mixing tank to obtain the composition shown in Tables 1 to 8, mixed and stirred, and then filtered through a membrane filter to obtain the treatment solution composition, colored ink composition, and clear ink composition for each example. Unless otherwise specified, the numerical values ​​for each component shown in the examples in the tables represent mass percent. In addition, in the tables, the numerical values ​​for each content represent the mass percent of the solid content of the active ingredient.

[0099] The abbreviations used in each composition and details of the product ingredients are as follows.

[0100] 1.1. Preparation of the treatment solution composition [Acid compound] Lactic acid (pKa=3.9, carboxyl group, monovalent) • Malonic acid (pKa=2.8, 5.7, carboxyl group, divalent) • Citric acid (pKa = 3.1, 4.8, 5.4, carboxyl group, trivalent) • Adipic acid (pKa=4.4, 5.4, carboxyl group, divalent) Succinic acid (pKa=4.2, 5.5, carboxyl group, divalent) Malic acid (pKa=3.4, 5.1, carboxyl group, divalent) Levulinic acid (pKa=4.6, carboxyl group, monovalent) • Glutaric acid (pKa = 4.1, 5.0, carboxyl group, divalent) • Dimethylolpropionic acid (pKa=4.7, carboxyl group, monovalent) • Propionic acid (pKa=4.7, carboxyl group, monovalent) Sulfuric acid (pKa = -2.0, 1.9, sulfo group, divalent) • Phosphate (pKa = 2.0, 6.8, 12.5, phosphate group, divalent) • Hydrochloric acid (pKa < 0, monovalent) [Basic compound A] KOH (monovalent) • NaOH (monovalent) • Ca(OH)2 (divalent) Mg(OH)2 (divalent) Al(OH)3 (trivalent) Triisopropanolamine (amino group, monovalent) • Dipropylenetriamine (amino group, trivalent) • PAA-03 (cationic polymer) (polyallylamine, amino group, pH=11, manufactured by Nitto Boseki Medical Co., Ltd., molecular weight per basic group calculated by the method described below: 61.385 g / mol) [Organic solvents] Glycerin Propylene glycol Triethylene glycol · 1,2-Hexanediol Triethylene glycol monobutyl ether ·3-Methoxy-1-butanol • ε-caprolactam [Surfactants] • Surfinol 465 (acetylene glycol, manufactured by Nisshin Chemical Industry Co., Ltd.) [water] ·Pure water

[0101] 1.2. Preparation of colored ink composition The details of each component shown in Table 7 are as follows:

[0102] [Pigments] • Self-dispersing Bk pigment dispersion: The following method was used to prepare the dispersion. 500g of raw carbon black powder prepared by the furnace method (primary particle size = 18nm, BET specific surface area = 180m²) 2A solution containing self-dispersing carbon black was added to 3750g of deionized water (186mL / g, DBP absorption rate = 186mL / 100g) and heated to 45°C while stirring with a dissolver. Then, while grinding with a sand mill using 0.8mm diameter zirconia beads, 30000g of an aqueous solution of sodium hypochlorite (effective chlorine concentration = 12%) was added dropwise at 45°C for 3.5 hours. Grinding was continued with the sand mill for 30 minutes to obtain a treatment solution containing self-dispersing carbon black. This treatment solution was filtered through a 400-mesh wire mesh to separate the zirconia beads and unreacted carbon black from the treatment solution. A 5% aqueous solution of potassium hydroxide was added to the separated treatment solution to adjust the pH to 7.5. Desalting and purification were performed using an ultrafiltration membrane until the conductivity of the solution was 1.5mS / cm. Further desalting and purification were performed using an electrodialysis machine until the conductivity of the solution was 1.0mS / cm. The solution was concentrated until the concentration of self-dispersing carbon black reached 17% by mass. This concentrate was subjected to a centrifuge to remove coarse particles and filtered through a 0.6 μm filter. Deionized water was added to the resulting filtrate, and the solution was diluted and dispersed until the concentration of self-dispersing carbon black reached 15% by mass to obtain a self-dispersing Bk pigment dispersion.

[0103] • Resin-dispersed Bk pigment dispersion: The following method was used to prepare the dispersion. 20 parts by mass of methyl ethyl ketone, 0.03 parts by mass of 2-mercaptoethanol, polymerization initiator, 15 parts by mass of polypropylene glycol monomethacrylate (propylene oxide = 9), 15 parts by mass of poly(ethylene glycol-propylene glycol) monomethacrylate (propylene oxide group = 7, ethylene oxide group = 5), 12 parts by mass of methacrylic acid, 50 parts by mass of styrene monomer, 10 parts by mass of styrene macromer, and 10 parts by mass of benzyl methacrylate were placed in a reaction vessel that had been thoroughly purged with nitrogen gas and polymerized under stirring at 75°C. 0.9 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 40 parts by mass of methyl ethyl ketone was added to 100 parts by mass of monomer components, and the mixture was aged at 80°C for 1 hour to obtain a polymer solution. 7.5 parts by mass of the water-insoluble polymer obtained above was dissolved in 45 parts by mass of methyl ethyl ketone, and a predetermined amount of 20% aqueous sodium hydroxide solution (neutralizing agent) was added to neutralize the salt-forming groups. Then, 20 parts by mass of carbon glut was added as a pigment and the mixture was kneaded in a bead mill for 2 hours. After adding 120 parts by mass of ion-exchanged water to the resulting mixture and stirring, the methyl ethyl ketone was removed under reduced pressure at 6°C, and some of the water was removed to obtain a resin-dispersed pigment dispersion with a solid content of 20% by mass.

[0104] [resin] • Resin dispersion: The following method was used to prepare the resin dispersion. In a four-necked flask equipped with a stirrer, condenser, nitrogen inlet tube, and thermometer, 322.2 g of polytetramethylene ether glycol with a number-average molecular weight of 1000, 19.7 g of 2,2-dimethylolbutanoic acid, 16.9 g of 1,4-butanediol, 137.9 g of hexamethylene diisocyanate, and 344.0 g of methyl ethyl ketone were charged and reacted at 80°C for 6 hours under a nitrogen gas atmosphere. After cooling to 60°C, 12.5 g of triethylamine was added and mixed at this temperature for 30 minutes. The resulting prepolymer was mixed with 1146.7 g of deionized water and stirred for 2 hours. Methyl ethyl ketone was then removed under reduced pressure at 40°C to obtain a polyurethane resin dispersion having carboxyl groups as acidic groups.

[0105] [Organic solvents] Glycerin · 1,2-Hexanediol [Basic compound B] KOH (monovalent) Triethanolamine [Surfactants] • Surfinol 465 (product name, acetylene glycol-based surfactant, manufactured by Nisshin Chemical Industry Co., Ltd.) [Chelating agent] • EDTA2Na (Ethylenediaminetetraacetate disodium salt) [water] ·Pure water

[0106] 1.3. Preparation of Clear Ink Composition The details of each component shown in Table 8 are as follows:

[0107] [resin] • Resin dispersion: The same resin dispersion used in the preparation of the colored ink composition described above was used. [Basic compound C] KOH (monovalent) Triethanolamine [Organic solvents] Glycerin · 1,2-Hexanediol [Surfactants] • Surfinol 465 (product name, acetylene glycol-based surfactant, manufactured by Nisshin Chemical Industry Co., Ltd.) [Chelating agent] • EDTA2Na (Ethylenediaminetetraacetate disodium salt) [water] ·Pure water

[0108] 2.Calculation method 2.1. Calculation method for Ca1, Cb1, Cb2, and Cb3 The molal concentration Ca1 of the acidic group in the acid compound was calculated using the following formula. Ca1 = (Amount of acid compound added [mass%]) × (Number of acidic groups with a pKa of 7 or less in one molecule of acid) × 10 / (Molecular weight of the acid compound [g / mol])

[0109] The molal concentrations Cb1, Cb2, and Cb3 of the basic groups in the basic compound were calculated using the following formula. Cb = (Amount of base compound added [mass%]) × (Number of hydroxyl groups or amino groups in one molecule of base) × 10 / (Molecular weight of base compound [g / mol])

[0110] In the case of amphoteric compounds such as amino acids, the concentration was calculated in the same manner as above, based on the difference in the number of acidic and basic groups, according to the properties of the more numerous group. For example, in the case of L-aspartic acid as an acidic amino acid, it can be calculated as follows. Aspartic acid has two carboxyl groups (pKa = 2.0, 3.9) as acidic groups and one amino group as a basic group in one molecule, and its aqueous solution has a pH of around 3. As an acidic compound, the molal concentration of the acidic groups of aspartic acid is calculated using the following formula C A It is possible to calculate this. Ca = (Amount of acidic compound added [mass%]) × {(Number of acidic groups with a pKa of 7 or less in one molecule of the acidic compound) - (Number of basic groups in one molecule of the acidic compound)} × 10 / (Molecular weight of the acidic compound [g / mol]) The following applies when the amount of aspartic acid added is 10% by mass. Ca=10×(2-1)×10 / 133.10≒0.751

[0111] In the case of amphoteric compounds such as amino acids, the concentration was calculated in the same manner as above, based on the difference in the number of acidic and basic groups, according to the properties of the group with the greater number.

[0112] 2.2. Method for calculating the molecular weight and valency of compounds whose molecular weight and number of acidic (or basic) groups are unknown. 0.30 g of a compound of unknown molecular weight and number of acidic (or basic) groups was dissolved in 29.70 g of pure water to make 30.00 g. 0.03 g of 10 wt% sodium hydroxide (or sulfuric acid) was added dropwise to the aqueous solution of the compound, stirred with a magnetic stirrer, and the pH of the solution was measured using a pH meter (F-72, HORIBA). This procedure was repeated until the pH of the solution reached 8.0 (or 6.0), at which point neutralization was determined, and the repeated operation was terminated. Based on these results, the amount of acidic (or basic) compound required to neutralize 1 g of 100 wt% sodium hydroxide (or sulfuric acid) is calculated using the following formula: a x (or b x (g) was calculated. a x = 0.30g / (amount of 100wt% sodium hydroxide added in grams) b x = 0.30g / (amount of 100wt% sulfuric acid added in grams)

[0113] Here, (amount of 100 wt% sulfuric acid added, g) = (amount of 10 wt% sulfuric acid added, g) / 10, and (amount of 100 wt% sulfuric acid added, g) = (amount of 10 wt% sulfuric acid added, g) / 10. Subsequently, the above operation was carried out on a 1 wt% sulfuric acid aqueous solution (or a 1 wt% sodium hydroxide aqueous solution), and the amount of sulfuric acid (or potassium hydroxide) added, a H2SO4 (g) (or b KOH (g)) was calculated, and the molecular weight (g / mol) per acidic group (or basic group) was calculated using the following formula. 98.08 × a x / a H2SO4 40.00 × b x / b KOH

[0114] 3. Printing method Using a modified device of ML-8000 (manufactured by Seiko Epson Corporation), for 100% cotton white broadcloth (#4000, manufactured by Nisshinbo Industries, Inc.) or polyester cloth, the treatment liquid composition and the coloring ink were discharged from the head within the same pass for printing. After performing main scanning a plurality of times (twice, four times, eight times, twelve times or sixteen times) on the same scanning area, subsequently, the clear ink composition was printed in the same manner, thereby forming a 20 cm × 5 cm solid pattern image on the cloth as the recording medium.

[0115] The adhesion amount of each composition to the cotton cloth was 15 mg / inch for the treatment liquid composition 2 , 30 mg / inch for the coloring ink composition 2 , and 15 mg / inch for the clear ink composition 2 . Also, the adhesion amount of each composition to the polyester cloth was 20 mg / inch for the treatment liquid composition 2 , 30 mg / inch for the coloring ink composition 2 , and 30 mg / inch for the clear ink composition 2The following steps were taken. After image formation, the printed materials for each example and comparative example were prepared by heating in an oven at 160°C for 5 minutes and drying. A "solid pattern image" refers to an image in which dots are uniformly formed across the entire recording area (main scanning direction × sub-scanning direction: 20 cm × 5 cm) so that the amount of each liquid applied matches the above values.

[0116] The inkjet head used was a head unit with a nozzle distance of 600 dpi in the sub-scanning direction, and two head chips arranged in the sub-scanning direction with a nozzle length of 2 inches.

[0117] 4. Evaluation Method 4.1. Wet abrasion fastness (cotton fabric, polyester fabric) Printed materials were prepared on cotton and polyester fabrics using the printing method described above. These were then rubbed 10 times with a metal cloth (white cotton cloth) at a load of 9N using a clock meter (FI-306, manufactured by Tester Sangyo Co., Ltd.). Subsequently, the optical density (OD, Status E) of the black area of ​​the printed image was measured using a colorimeter (FD-7, manufactured by Konica Minolta Corporation) in the ink-contaminated areas of the rubbed metal cloth, and evaluated according to the following criteria. (Evaluation criteria for printing on cotton fabric) SS:OD is 0.22 or less. S:OD is greater than 0.22 and less than or equal to 0.31 A: OD is greater than 0.31 and less than or equal to 0.4 B:OD is greater than 0.4 and less than or equal to 0.5 C:OD is greater than 0.5 (Evaluation criteria for printing on polyester fabric) SS: The OD of black is 0.22 or less. S: The OD of black is greater than 0.22 and less than or equal to 0.29. A+: Black OD is greater than 0.29 and less than or equal to 0.36. A: The OD of black is greater than 0.36 and less than or equal to 0.40. B: The OD of the black is greater than 0.40 and less than or equal to 0.47. C+: Black OD is greater than 0.47 and less than or equal to 0.53. C: The OD of black is greater than 0.53.

[0118] 4.2.Irritation alleviation For printed materials made on cotton cloth using the above printing method, a 15cm x 3.2cm area of ​​the printed image was cut out, then cut into 5mm wide pieces and placed in a glass bottle with 35mL of pure water. Extraction was then performed by stirring with a magnetic stirrer for 2 hours. Afterward, the pH of the extract was measured using a pH meter (F-72, HORIBA). This procedure was repeated three times, and the average pH measurement was used for evaluation according to the following criteria. (Evaluation Criteria) S: The average pH value is 4.7 or higher. A: The average pH is between 4.4 and 4.7. B: The average pH value is between 4.2 and 4.4. C: The average pH value is less than 4.2.

Claims

1. An inkjet composition set comprising a processing liquid composition and a colored ink composition, The aforementioned processing liquid composition contains an acid compound and water. The aforementioned processing liquid composition contains or does not contain base compound A. The aforementioned colored ink composition contains a pigment, resin particles, basic compound B, and water. The molar concentration Ca1 (mol / kg) of the acidic group due to the acid compound, the molar concentration Cb1 (mol / kg) of the basic group due to the base compound A, and the molar concentration Cb2 (mol / kg) of the basic group due to the base compound B satisfy the following formula (1): Ca1-(Cb1+1.5Cb2)≧0.10 (mol / kg)...Formula (1) (In equation (1), Ca1 > 0, Cb1 ≥ 0, and Cb2 > 0.) Inkjet composition set.

2. The acid compound comprises one or more selected from the group consisting of lactic acid, acetic acid, levulinic acid, malic acid, malonic acid, citric acid, glutaric acid, phosphoric acid, and dimethylolpropionic acid. The inkjet composition set according to claim 1.

3. The pH of the aforementioned treatment liquid composition is 2.5 or higher and 6.5 or lower. The pH of the aforementioned colored ink composition is greater than 6.

5. The inkjet composition set according to claim 1.

4. The acid compound has a pKa of at least 2.2 or more and 6.5 or less in water at 25°C. The inkjet composition set according to claim 1.

5. The above Cb1 is 0.01 or greater. The inkjet composition set according to claim 1.

6. Further comprising a clear ink composition, The clear ink composition contains resin particles, a basic compound C, and water. The Ca1, Cb1, Cb2, and the molar concentration Cb3 (mol / kg) of the basic group due to the base compound C satisfy the following formula (2): Ca1-(Cb1+1.5Cb2+1.5Cb3)≧0.10 (mol / kg)...Formula (2) The inkjet composition set according to claim 1.

7. The Ca1, Cb1, Cb2, and Cb3 satisfy the following formula (3): {Ca1-(Cb1+1.5Cb2+1.5Cb3)} / 1.5(Cb1+1.5Cb2+1.5Cb3)≧0.01...Formula (3) The inkjet composition set according to claim 6.

8. The Cb2 and Cb3 concentrations are each 0.35 mol / kg or less. The inkjet composition set according to claim 6.

9. The Ca1, Cb1, Cb2, and Cb3 satisfy the following formula (4): Ca1-(Cb1+1.5Cb2+1.5Cb3)≧0.15 (mol / kg)...Formula (4) The inkjet composition set according to claim 6.

10. The Ca1, Cb1, Cb2, and Cb3 satisfy the following formula (5): {Ca1-(Cb1+1.5Cb2+1.5Cb3)} / 1.5(Cb1+1.5Cb2+1.5Cb3)≧0.20...Formula (5) The inkjet composition set according to claim 6.

11. The base compound A, the base compound B, and the base compound C each contain one or more selected from alkali metal hydroxides, alkaline earth metal hydroxides, and amine compounds. The inkjet composition set according to claim 6.

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