Inkjet composition set

Abstract

Provided is an inkjet composition set having excellent wet rubbing fastness. The inkjet composition set includes a colored ink composition containing a pigment, resin particles, an alkali compound B, and water, and a treatment liquid composition containing an acid compound and water, or optionally containing an alkali compound A, the molar concentration Ca1 (mol / kg) of an acidic group based on the acid compound, the molar concentration Cb1 (mol / kg) of a basic group based on the alkali compound A, and the molar concentration Cb2 (mol / kg) of a basic group based on the alkali compound B satisfy the relationship Ca1-(Cb1 + 1.5 Cb2) > = 0.10 (mol / kg).

Description

Technical Field

[0001] This invention relates to an inkjet composition assembly. Background Technology

[0002] Inkjet recording methods have achieved rapid development in various aspects, enabling the recording of high-resolution images with relatively simple devices. Various studies have been conducted on aspects such as 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 relative to the total processing solution.

[0003] Patent Document 1: WO2023 / 042761

[0004] However, if a treatment liquid composition obtained by conventional configuration as in Patent Document 1 is used, there is room for improvement in the wet rubbing fastness of the resulting printed and dyed fabric. Summary of the Invention

[0005] The inkjet composition of the present invention comprises a processing liquid composition and a coloring ink composition. The processing liquid composition contains an acid compound and water, and the processing liquid composition contains an alkali compound A or does not contain an alkali compound A. The coloring ink composition contains pigment, resin particles, an alkali compound B and water. The molar concentrations of the acidic groups of the acid compound Ca1 (mol / kg), the molar concentrations of the basic groups of the alkali compound A Cb1 (mol / kg), and the molar concentrations of the basic groups of the alkali compound B Cb2 (mol / kg) satisfy the following formula (1).

[0006] Ca1-(Cb1+1.5Cb2)≥0.10(mol / kg)……Equation (1)

[0007] (In formula (1), Ca1>0, Cb1≥0, Cb2>0.) Attached Figure Description

[0008] Figure 1 Table 1 shows the composition of the groups of compositions used in the examples and their evaluation results.

[0009] Figure 2 Table 2 shows the composition of the groups of compositions used in the examples and their evaluation results.

[0010] Figure 3 Table 3 shows the composition of the groups of compositions used in the examples and their evaluation results.

[0011] Figure 4Table 4 shows the composition of the groups of compositions used in the examples and their evaluation results.

[0012] Figure 5 Table 5 shows the composition of the groups of compositions used in the examples and their evaluation results.

[0013] Figure 6 Table 6 shows the composition of the groups of compositions used in the comparative examples and their evaluation results.

[0014] Figure 7 Table 7 shows the composition of the coloring ink composition.

[0015] Figure 8 Table 8 shows the composition of the transparent ink composition. Detailed Implementation

[0016] Hereinafter, embodiments of the present invention (hereinafter referred to as "this embodiment") will be described in detail with reference to the accompanying drawings as needed. However, the present invention is not limited thereto and various modifications can be made without departing from its spirit.

[0017] Previously, organic acids or polyvalent metal salts were used as coagulants in the processing solution to cause ink agglomeration. While polyvalent metal salts have strong coagulant power and tend to produce recordings with suppressed color development and bleed-through, they also tend to form easily water-soluble aggregates near the surface of the recording, thus reducing the wet rubbing fastness of the resulting recording. On the other hand, it is known that organic acids neutralize the anionic components in the ink, thereby reducing the hydrophilicity of the anionic components and thus obtaining recordings with good wet rubbing fastness.

[0018] However, even when using organic acids, sufficient wet rubbing adhesion is sometimes not achieved when the treatment liquid composition and ink composition are mixed, depending on the concentration relationship between the organic acid and alkali compounds undergoing the neutralization reaction. Detailed research is needed to determine the optimal conditions for the neutralization reaction.

[0019] In this invention, it was discovered that in an inkjet composition comprising a coloring ink composition and a processing liquid composition, a record with excellent wet rubbing fastness is obtained under the condition that the molar concentration Ca1 of the acidic group of the acid compound contained in the processing liquid composition, the molar concentration Cb2 of the alkali compound B contained in the coloring ink composition, and the molar concentration Cb1 of the alkali group of the alkali compound A contained in the processing liquid composition satisfy the following formula (1).

[0020] Ca1-(Cb1+1.5Cb2)≥0.10(mol / kg)……Equation (1)

[0021] This is because the acid compounds in the treatment liquid composition cause dispersion disruption of the resin particles in the coloring ink composition, easily forming aggregates with low solubility in water. It is speculated that by increasing the amount of acidic groups beyond the specified limit, dispersion disruption is promoted, reducing the ink components dissolved from the printed material during wet rubbing, thereby improving wet rubbing adhesion.

[0022] However, on the other hand, alkali compounds are sometimes included in coloring ink compositions for purposes such as reducing skin irritation and improving storage stability. Furthermore, from the same perspective, alkali compounds are sometimes included in processing liquid compositions as needed. Because such alkali compounds react with acid compounds, they tend to compete with the reaction between acid compounds and resin particles. Alkali compounds, especially those included in ink compositions, tend to have a strong effect in inhibiting the action of acid compounds.

[0023] Therefore, in this embodiment, as shown in formula (1) above, the amount of acidic groups is specified to be greater than the specified amount. Thus, the amount of acidic compound contained in the treatment liquid composition and the ink composition is specified to a degree that does not hinder the dispersion-destructive effect. Furthermore, as mentioned above, the alkali compound contained in the ink composition has a strong effect in hindering the action of the acidic compound, therefore this aspect is corrected using a coefficient relative to the molar concentration Cb2. Therefore, it can be considered that if formula (1) above is satisfied, the wet rubbing adhesion of the recorded material is particularly excellent.

[0024] In this specification, "acid" and "acid compound" refer to substances with a pH less than 7 when prepared as a 0.1% by mass aqueous solution at 25°C. Furthermore, "base" and "base compound" refer to substances with a pH greater than 7 when prepared as a 0.1% by mass aqueous solution at 25°C. Moreover, in the ink composition, compounds included as "chelating agents" are not treated as acid compounds in this embodiment.

[0025] The following is a detailed description of the components contained in the inkjet composition.

[0026] <Inkjet Composition Kit>

[0027] The inkjet composition group (hereinafter also referred to as the "composition group") involved in this embodiment includes a processing liquid composition and a coloring ink composition. The processing liquid composition contains an acid compound and water. The processing liquid composition contains an alkali compound A or does not contain an alkali compound A. The coloring ink composition contains pigment, resin particles, an alkali compound B and water. The molar concentrations of the acidic groups of the acid compound Ca1 (mol / kg), the basic groups of the alkali compound A Cb1 (mol / kg), and the basic groups of the alkali compound B Cb2 (mol / kg) satisfy the following formula (1).

[0028] Ca1-(Cb1+1.5Cb2)≥0.10(mol / kg)……Equation (1)

[0029] (In formula (1), Ca1>0, Cb1≥0, Cb2>0.)

[0030] In formula (1), the value of Ca1-(Cb1+1.5Cb2) is preferably 0.10 or more and 8.0 or less. By keeping the value of Ca1-(Cb1+1.5Cb2) within the above range, the basic groups are not excessively reduced, and the effect of wet friction fastness based on the present invention is more effective and reliable. From the same point of view, the value of Ca1-(Cb1+1.5Cb2) is more preferably 0.15 or more and 7.0 or less, further preferably 0.15 or more and 6.0 or less, even more preferably 0.15 or more and 5.0 or less, and even more preferably 0.40 or more and 3.0 or less.

[0031] 1. Treatment liquid composition

[0032] The processing liquid composition included in the composition group is a composition used to adhere to a recording medium, containing an acid compound and water, and may also contain an alkaline compound A if necessary. The processing liquid composition in the composition group can be one or more types. Additionally, a portion of the acid compound and alkaline compound A may form a neutralizing salt in the processing liquid composition.

[0033] The pH of the treatment solution composition is preferably 1.5 or higher and 7.0 or lower. By keeping the pH of the treatment solution composition within the above range, it tends to more effectively and reliably exert the wet friction adhesion effect based on the present invention. From the same viewpoint, the pH of the treatment solution composition is more preferably 2.0 or higher and 6.5 or lower, further preferably 2.5 or higher and 6.5 or lower, and even more preferably 2.5 or higher and 5.5 or lower.

[0034] 1.1. Acid compounds

[0035] Examples of acid compounds include organic acids and inorganic acids. From the viewpoint of improving the wet rubbing fastness of printed and dyed materials, and thus enhancing the mildness of irritation, organic acids are preferred. Acid compounds can be used alone or in combination of two or more.

[0036] The pKa of the acid compound in water at 25°C is preferably 2.0 or higher and 7.0 or lower. With the pKa of the acid compound in water at 25°C within the above-mentioned range, it can exert buffering capacity within the pH range of 2.5 to 6.5. Furthermore, the neutralization rate with alkali compound A can be suppressed to be even lower, resulting in excellent wet friction resistance and thus improved irritation mitigation. From the same viewpoint, the pKa of the acid compound at 25°C is more preferably 2.2 or higher and 6.5 or lower, further preferably 2.5 or higher and 6.0 or lower, and even more preferably 2.8 or higher and 5.8 or lower.

[0037] In this specification, the pKa of a compound being in a certain range means that, in the case of a single pKa, the pKa is within a specified range, and in the case of multiple pKas, any one or more pKas are within the corresponding range.

[0038] Examples of preferred 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, pyranone carboxylic acid, pyrrolic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophenic acid, nicotinic acid, or derivatives of these compounds or their salts. Preferably, one or more compounds 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 compounds 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 compounds are selected from the group consisting of lactic acid, levulinic acid, malic acid, malonic acid, citric acid, glutaric acid, phosphoric acid, and dimethylolpropionic acid. By including such acid compounds, there is a tendency to more effectively and reliably exert the effect of improving wet friction adhesion based on the present invention.

[0039] In the treatment liquid composition, the molar concentration of the acidic group from the acid compound, Ca1 (mol / kg), is preferably 0.20 or more and 5.00 or less. By keeping Ca1 within the above range, the effect of improving wet friction adhesion based on the present invention tends to be more effective and reliable. From the same viewpoint, Ca1 (mol / kg) is more preferably 0.30 or more and 4.75 or less, further preferably 0.35 or more and 4.75 or less, even more preferably 0.40 or more and 3.50 or less, and still more preferably 0.50 or more and 3.50 or less.

[0040] The mass percentage of the acid compound is preferably 1.0–50% by mass, 2.0–40% by mass, 3.5–30% by mass, or 4.0–15% by mass relative to the total amount of the treatment liquid composition. By keeping the mass percentage of the acid compound within the above range, the effect of improving wet friction adhesion based on the present invention tends to be more effective and reliable.

[0041] 1.2. Alkali compound A

[0042] The treatment liquid composition may or may not contain alkali compound A. Examples of alkali compound A include organic and inorganic bases. Among organic and inorganic bases, metal hydroxides or amine compounds are preferred. By using such an alkali compound A, the effect of improving wet friction adhesion based on the present invention tends to be more effective and reliable. Furthermore, by using such an alkali compound A, the solubility of alkali compound A relative to water tends to be better. From the same 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. Additionally, alkali compound A can be used alone or in combination with two or more.

[0043] Alkali compound A preferably comprises a hydroxide of one or more metals selected from the group consisting of Li, Na, and K, or an amine compound containing 1 to 10 nitrogen atoms within its molecule. In particular, by using such an alkali compound, there is a tendency to further improve wet rubbing fastness, especially in the form of cotton fabrics.

[0044] The metal constituting the metal hydroxide is preferably one or more selected from the group consisting of Li, Na, K, Ca, Mg, and Al, and more preferably at least one selected from Na and K. Using such a metal hydroxide, the recording material tends to have superior wet rubbing fastness. From the same viewpoint, the metal hydroxide is preferably one or more selected from the group consisting of LiOH, NaOH, KOH, Ca(OH)2, Mg(OH)2, and Al(OH)3, or one or more selected from the group consisting of NaOH, KOH, Ca(OH)2, Mg(OH)2, and Al(OH)3. Using such a metal hydroxide, the recording material tends to have superior wet rubbing fastness.

[0045] The preferred amine compound is one or more selected from the group consisting of alkanolamine compounds, polyamine compounds, and polyamine compounds. By using such amine compounds, the recorded material tends to exhibit superior wet rubbing adhesion.

[0046] Examples of alkanolamine compounds include triethanolamine, tripropanolamine, triisopropanolamine, and tributanolamine. Among these, triisopropanolamine is preferred from the viewpoint of more effectively and reliably improving the wet rubbing adhesion of the recorded material.

[0047] Examples of polyamine compounds include diethylenetriamine, dipropyltriamine, dihexyltriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and hexadecimalylheptamine. Among these, dipropyltriamine is preferred from the same perspective as described above.

[0048] As a polyamine compound, any polyamine compound having an amino group in its structure is acceptable, such as polyamine resins, polyamide resins, and polyallylamine resins.

[0049] As polyamine compounds, commercially available polyamine compounds equivalent to the basic compounds described in this specification may also 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 (these are trade names, Nittobo). Medical Company manufactures), FL-14 (SNF Company manufactures), Arafix100, 251S, 255, 255LOX (Arakawa Chemical Company manufactures), DK-6810, 6853, 6885; WS-4010, 4011, 4020, 4024, 4027, 4030 (Starlight PMC Company manufactures), Papyogen P-105 (Senka Company manufactures), Sumirez Resin650 (30), 675A, 6615, SLX-1 (Taoka Chemical Industry Company manufactures), Catiomaster (registered trademark) PD-1, 7, 30, A, PDT-2, PE-10, PE-30, DT-EH, EPA-SK01, TMHMDA-E (Yokichi Synthetic Company manufactures), JetFix36N, 38A, N700, 5052 (Satoda Chemical Company manufactures). From the viewpoint of more effectively and reliably improving the wet friction adhesion of the recorded material, PAA-03 is preferred.

[0050] Examples of polyallylamine resins include polyallylamine hydrochloride, polyallylamine amide 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, polymethyldiallylamine amide sulfate, polymethyldiallylamine acetate, polydiallyldimethylammonium chloride, diallylamine acetate-sulfur dioxide copolymer, diallyl methyl ethyl ammonium sulfate-sulfur dioxide copolymer, methyldiallylamine hydrochloride-sulfur dioxide copolymer, diallyldimethylammonium chloride-sulfur dioxide copolymer, and diallyldimethylammonium chloride-acrylamide copolymer.

[0051] In the treatment liquid composition, the molar concentration Cb1 (mol / kg) of the basic group from the alkali compound A is preferably 0.00 or more and 3.00 or less. With Cb1 within the above range, the effect of improving wet friction adhesion based on the present invention tends to be more effective and reliable. From the same viewpoint, Cb1 (mol / kg) is more preferably 0.01 or more and 2.50 or less, further preferably 0.05 or more and 2.00 or less, even more preferably 0.05 or more and 1.50 or less, still more preferably 0.10 or more and 1.75 or less, and still more preferably 0.10 or more and 1.00 or less.

[0052] The content of alkali compound A, based on its mass, is preferably 0.0–40% by mass, 0.1–30% by mass, 0.5–20% by mass, 0.5–10% by mass, 1.0–10% by mass, and 1.0–5% by mass relative to the total amount of the treatment liquid composition. By keeping the content of alkali compound A within the above range, the effect of improving wet friction adhesion based on the present invention tends to be more effective and reliable.

[0053] 1.3. Water-soluble organic solvents

[0054] The processing liquid composition may also contain a water-soluble organic solvent. There are no limitations on the type of organic solvent, as long as it is water-soluble; examples include polyols, glycol ethers, nitrogen-containing solvents, ethers, and cyclic esters. Among these, polyols are preferred from the viewpoint of more effectively and reliably improving the wettability and rubbing strength of the recorded material. Furthermore, one type of water-soluble organic solvent may be used alone, or two or more may be used in combination.

[0055] Polyols can be classified, for example, as polyols and diol compounds. Specific compounds that are polyols include, for example, glycerol, ethylene glycol, propylene glycol, 1,2-propanediol, 1,2-butanediol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, dipropylene glycol, and trimethylolpropane. From the viewpoint of more effectively and reliably improving the wet rubbing adhesion of the recorded material, it is preferable to include one or more compounds selected from the group consisting of glycerol, propylene glycol, and triethylene glycol.

[0056] Furthermore, specific examples of diol 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. Among these, 1,2-hexanediol is preferred from the viewpoint of more effectively and reliably improving the wet rubbing adhesion of the recording.

[0057] Furthermore, specific compounds that fall into the glycol ether class 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-n-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. From the viewpoint of more effectively and reliably improving the wet friction adhesion of the recorded material, triethylene glycol monobutyl ether is preferred.

[0058] The content of water-soluble organic solvent is preferably 5-50% by mass, 10-40% by mass, or 12-30% by mass relative to the total amount of the treatment liquid composition. By keeping the content of water-soluble organic solvent within the above range, there is a tendency for better wet friction fastness.

[0059] From the same point of view, the content of polyols or glycol ethers relative to the total amount of the treatment liquid composition is preferably 5-50% by mass, 10-40% by mass, or 12-30% by mass.

[0060] 1.4. Surfactants

[0061] The processing liquid composition may also 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 of the processing liquid composition when ejected by inkjet printing, nonionic surfactants are preferred. Nonionic surfactants are preferred because they tend to be stable even in processing liquid compositions containing acidic and alkaline compounds. Furthermore, one surfactant may be used alone, or two or more may be used in combination.

[0062] Examples of nonionic surfactants include alkynyl glycol surfactants, alcohol ethoxylate surfactants, fluorinated surfactants, and organosilicon surfactants.

[0063] As an alkynyl diol surfactant, there is no particular limitation, for example, one or more of the following can be cited: epoxide alkane adducts selected from 2,4,7,9-tetramethyl-5-decyn-4,7-diol and 2,4,7,9-tetramethyl-5-decyn-4,7-diol, and epoxide alkane adducts selected from 2,4-dimethyl-5-decyn-4-ol and 2,4-dimethyl-5-decyn-4-ol.

[0064] Commercially available surfactants based on acetylacetonate diols include, for example, the Olfine 104 series, the Olfine E1010 and other E-series surfactants (trade names manufactured by Air Products), and Surfynol 61, 104, and 465 (trade names manufactured by Nissin Chemical Industries). Among these, Surfynol 465 is preferred from the viewpoint of more effectively and reliably exerting the wetted friction adhesion effect based on the present invention.

[0065] As an alcohol ethoxylated surfactant, it is a compound in which polyoxyethylene chains and alkyl groups are linked through ether bonds, and it can be converted from "R" to "Ethylene oxide". A -O-(CH2CH2O) d The molecular formula "-H" is sometimes referred to as poly(oxyethylene) alkyl ether.

[0066] Examples of alcohol ethoxylated 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 (trade names manufactured by Sanyo Chemical Industries, Ltd.).

[0067] As a fluorinated surfactant, there are no particular limitations; examples include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines, and perfluoroalkyl amine oxides.

[0068] Examples of organosilicon surfactants include polysiloxane compounds and polyether-modified organosilicones. Commercially available examples include BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK-348, and BYK-349 (trade names, manufactured by BYK Chemical Co., Ltd.), and 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 (the above are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0069] The surfactant content is preferably 0.01 to 3.0% by mass, 0.03 to 1.0% by mass, and 0.05 to 0.1% by mass relative to the total amount of the treatment liquid composition. By keeping the surfactant content within the above range, the wet friction adhesion effect based on the present invention can be performed more effectively and reliably.

[0070] 1.5. Water

[0071] The treatment solution composition contains water. Preferably, the water has been thoroughly cleaned of ionic impurities, and examples of such water include pure water such as ion-exchange water, reverse osmosis water, and distilled water, as well as ultrapure water.

[0072] 1.6. Other ingredients

[0073] In addition to the components mentioned above, the treatment liquid composition may also contain various additives such as pH adjusters, chelating agents, softeners, solubilizers, viscosity modifiers, UV absorbers, antioxidants, and corrosion inhibitors, as needed. Furthermore, the treatment liquid composition is not an ink and is not intended for coloring.

[0074] 2. Coloring ink composition

[0075] The coloring ink composition included in the composition group contains pigments, resin particles, alkali compound B, and water. The coloring ink composition can adhere to a recording medium on which the processing liquid composition is attached, or it can adhere simultaneously with the processing liquid composition to the recording medium, or the processing liquid composition can adhere to the recording medium on which the coloring ink composition is attached. From the viewpoint of more effectively and reliably utilizing the wet rubbing adhesion effect based on the present invention, it is preferable to adhere simultaneously with the processing liquid composition to the recording medium.

[0076] The pH of the coloring ink composition is preferably greater than 6.5. By keeping the pH of the coloring ink composition within the above range, the coloring ink composition exhibits good storage stability and tends to more effectively and reliably exert the wet rubbing adhesion effect based on the present invention. Furthermore, the upper limit of the pH of the coloring ink composition is not particularly limited and can be 13 or less, 12.5 or less, or 12 or less.

[0077] 2.1. Pigments

[0078] As a pigment, anionic dispersed pigments are preferred. Anionic dispersed pigments are dispersed by neutralizing acidic groups with alkali. Through the treatment of the acidic compounds in the liquid composition, the acidic groups of the dispersed pigment, being relatively weak acids, become free, resulting in reduced solubility and a tendency to improve wet rubbing adhesion.

[0079] In coloring ink compositions, dispersed pigments can be, for example, self-dispersible pigments and resin-dispersible pigments. From the viewpoint of facilitating reaction with the processing liquid composition, self-dispersible pigments are preferred.

[0080] More specifically, as pigments, examples include inorganic pigments and organic pigments. As inorganic pigments, carbon black manufactured by known methods such as the contact process, furnace process, and thermal process can be used, in addition to titanium dioxide and iron oxide. 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.

[0081] Examples of carbon black pigments include CI (Colour Index Generic Name) Pigment Black 1, 7, and 11. Commercially available carbon black products are also available, 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; Monarch (registered trademark) 700, 800, 880, 900, 1000, 1100, 1300, and 1400; and Degussa's Color Black. FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Printex (registered trademark) 35, U, V, 140U, SpecialBlack 6, 5, 4A, 4, etc. Alternatively, pigments obtained by the preparation methods described in the examples below may also be used.

[0082] The pigment content in the coloring ink is preferably 1-10% by mass, 2-8% by mass, or 3-7% by mass relative to the total amount of the coloring ink composition. By keeping the pigment content within the above range, the effects based on the present invention can be achieved more effectively and reliably. Furthermore, the pigment content in the above-mentioned coloring ink is based on the mass of the pigment solid component.

[0083] 2.2. Resin particles

[0084] Examples of resin particles include anionic resin particles, nonionic resin particles, and cationic resin particles. Among these, anionic resin particles are preferred from the viewpoint of more effectively and reliably achieving the wetting and rubbing adhesion effect based on the present invention. Examples of anionic groups included in anionic resin particles include sulfonic acid groups, carboxylic acid groups, phosphate groups, and hydroxyl groups, but acidic groups are preferred. By producing resin particles containing acidic groups, it is preferable to achieve the effects based on the present invention more effectively and reliably. Furthermore, the resin particles are particles containing resin, and either emulsion or solution states can be used, but from the viewpoint of suppressing the increase in ink viscosity, emulsion-state resin particles are preferred.

[0085] As anionic resin particles, there are no limitations as long as they are anionic resin particles having anionic groups. More specifically, examples include polyurethane 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, from the viewpoint of more effectively and reliably exerting the effects based on the present invention, styrene-acrylic resins or polyurethane resins are preferred, and polyurethane resins are more preferred.

[0086] The content of resin particles in the coloring ink composition is preferably 1-10% by mass, 2-8% by mass, or 3-7% by mass relative to the total amount of the coloring ink composition. By keeping the content of resin particles within the above range, the effects based on the present invention can be achieved more effectively and reliably. From the same point of view, the content of anionic resin particles in the coloring ink composition is preferably 1-10% by mass, 2-8% by mass, or 3-7% by mass relative to the total amount of the coloring ink composition. Furthermore, the above contents are based on the mass of the solid component of the resin particles.

[0087] 2.3. Alkali compound B

[0088] Examples of alkali compounds B include organic and inorganic bases. Among organic and inorganic bases, metal hydroxides and amine compounds are preferred. By using metal hydroxides or amine compounds, the recorded material tends to have better wet friction fastness. As alkali compound B, one can be used alone, or two or more can be used in combination.

[0089] Specific compounds for alkali compound B can be the same as the metal hydroxides and amine compounds in alkali compound A described above. From the viewpoint of more effectively and reliably achieving the wet friction adhesion effect based on the present invention, it is preferable to include at least one of potassium hydroxide and triethanolamine.

[0090] In the coloring ink composition, the molar concentration Cb2 (mol / kg) of the basic group from the alkali 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 rubbing adhesion based on the present invention tends to be more effective and reliable. From the same point of view, 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.

[0091] The content of alkali compound B, based on its mass, is preferably 0.0 to 10% by mass, 0.05 to 5% by mass, 0.1 to 3.5% by mass, and 0.5 to 3.0% by mass relative to the total amount of the coloring ink composition. By keeping the content of alkali compound B within the above range, the effect of improving wet rubbing adhesion based on the present invention tends to be more effective and reliable.

[0092] 2.4. Water-soluble organic solvents

[0093] The coloring ink composition may also contain a water-soluble organic solvent. There is no limitation on the organic solvent used in the coloring ink composition, as long as it is water-soluble; examples include the organic solvents described in the above-described processing liquid composition. From the viewpoint of more effectively and reliably improving the wet rubbing adhesion of the recorded material, polyols are preferred, and at least one of glycerol and 1,2-hexanediol is more preferred. Furthermore, one organic solvent may be used alone, or two or more may be used in combination.

[0094] The content of organic solvent in the coloring ink is preferably 5-40% by mass, 10-30% by mass, or 12-25% by mass relative to the total amount of the coloring ink composition. By keeping the content of organic solvent within the above range, there is a tendency for better wet rubbing adhesion.

[0095] 2.5. Surfactants

[0096] The coloring ink composition may also contain a surfactant. Examples of surfactants used in the coloring ink composition include those described in the above-described treatment liquid composition. Among such surfactants, from the viewpoint of more effectively and reliably achieving the wetting rubbing adhesion effect based on the present invention, acetylenol-based surfactants are preferred, and Surfynol 465 is a preferred commercially available example. Furthermore, one surfactant may be used alone, or two or more may be used in combination.

[0097] 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 coloring ink composition. By keeping the surfactant content within the above range, the wetting rubbing adhesion effect based on the present invention can be achieved more effectively and reliably.

[0098] 2.6. Chelating agents

[0099] The coloring ink composition may also contain a chelating agent. Examples of chelating agents used in the coloring ink composition include disodium ethylenediaminetetraacetate (EDTA2Na), ethylenediaminetetraacetate (EDTA), hypozonotriacetate of ethylenediamine, hexametaphosphate, pyrophosphate, metaphosphate, etc. From the viewpoint of more effectively and reliably exerting the wet rubbing adhesion effect based on the present invention, disodium ethylenediaminetetraacetate (EDTA2Na) is preferred.

[0100] 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 coloring ink composition. By keeping the chelating agent content within the above range, the wet friction adhesion effect based on the present invention can be achieved more effectively and reliably.

[0101] 2.7. Water

[0102] As water, water in which ionic impurities have been removed to the greatest extent possible is preferred. Examples of such water include pure water such as ion-exchange water, reverse osmosis water, and distilled water, as well as ultrapure water.

[0103] 2.8. Other ingredients

[0104] In addition to the above-mentioned components, various additives such as pH adjusters, softeners, solvents, viscosity modifiers, UV absorbers, antioxidants, and corrosion inhibitors may also be included as needed.

[0105] 3. Transparent ink composition

[0106] The composition group may also include a transparent ink composition. A transparent ink composition is a composition containing resin particles, alkali compound C, and water, and substantially free of pigments. The inclusion of a transparent ink composition in the composition group tends to further improve the wet rubbing adhesion of the recorded material.

[0107] Furthermore, the transparent ink composition is not an ink used for coloring, but rather an ink used to improve the abrasion resistance of the recorded material, adjust its gloss, and enhance the fixing and color development properties of colored inks. Here, "substantially free of pigment" means that the content of pigment relative to the total amount of the transparent ink composition is preferably 0.1% by mass or less, 0.05% by mass or less, or 0.01% by mass or less.

[0108] When the composition group includes a transparent ink composition, it is preferable that the molar concentration (mol / kg) of Ca1, Cb1, Cb2, and Cb3 based on the basic group of the alkali compound C satisfies the following formula (2). By satisfying the relationship of formula (2), the effect of the aggregation reaction based on the acid and alkali compounds in each composition can be optimized, resulting in a tendency to further improve the wet rubbing fastness of the recorded material, especially when polyester fabric is used as the recording medium. In addition, 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.

[0109] Ca1-(Cb1+1.5Cb2+1.5Cb3)≥0.10(mol / kg)……Equation (2)

[0110] When the composition group includes a transparent ink composition, it is preferable that the above-mentioned Ca1, Cb1, Cb2, and Cb3 satisfy the following formula (4). By satisfying the relationship of formula (4), the effect of the aggregation reaction based on the acid and alkali compounds in each composition can be optimized, resulting in a tendency to further improve the wet rubbing fastness of the recorded material, especially when polyester fabric is used as the recording medium. In addition, 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.

[0111] Ca1-(Cb1+1.5Cb2+1.5Cb3)≥0.15(mol / kg)……Equation (4)

[0112] When the composition group includes a transparent ink composition, it is preferable that the above-mentioned Ca1, Cb1, Cb2, and Cb3 satisfy the following formula (3). By satisfying the relationship of formula (3), there is a tendency to suppress the excessive formation of neutralizing salt and further improve the wet rubbing adhesion of the recording material to the polyester fabric. In addition, 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.

[0113] {Ca1-(Cb1+1.5Cb2+1.5Cb3)} / 1.5(Cb1+1.5Cb2+1.5Cb3)≥0.01……Equation (3)

[0114] When the composition group includes a transparent ink composition, it is preferable that Ca1, Cb1, Cb2, and Cb3 satisfy the following formula (5). By satisfying the relationship of formula (5), there is a tendency to suppress the excessive formation of neutralizing salts and further improve the wet rubbing adhesion of the recording material to the polyester fabric. In addition, 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.

[0115] {Ca1-(Cb1+1.5Cb2+1.5Cb3)} / 1.5(Cb1+1.5Cb2+1.5Cb3)≥0.20……Equation (5)

[0116] 3.1. Resin particles

[0117] As resin particles, it is equally preferable to use the same resin particles as those used in the above-described coloring ink compositions.

[0118] The content of resin particles in the transparent ink composition is preferably 1-20% by mass, 5-15% by mass, or 8-12% by mass relative to the total amount of the transparent ink composition. By keeping the content of resin particles within the above range, the effects based on the present invention can be achieved more effectively and reliably. From the same viewpoint, the content of anionic resin particles in the transparent ink composition is preferably 1-20% by mass, 5-15% by mass, or 8-12% by mass relative to the total amount of the transparent ink composition. Furthermore, the above contents are based on the mass of the solid component of the resin particles.

[0119] 3.2. Alkali compound C

[0120] Examples of alkali compounds C include organic and inorganic bases. Among organic and inorganic bases, metal hydroxides and amine compounds are preferred. By using metal hydroxides or amine compounds, the recorded material tends to have better wet friction fastness. As alkali compound C, one type can be used alone, or two or more types can be used in combination.

[0121] The aforementioned alkali compounds A, B, and C preferably contain one or more compounds selected from alkali metal hydroxides, alkaline earth metal hydroxides, and amine compounds. Compositions containing such alkali compounds tend to exhibit more effective and reliable wet friction adhesion based on the present invention.

[0122] As a specific compound for alkali compound C, the same compound as the metal hydroxide and amine compound in alkali compound A described above can be used. From the viewpoint of more effectively and reliably achieving the wet friction adhesion effect based on the present invention, it is preferable to include at least one of potassium hydroxide and triethanolamine.

[0123] In the transparent ink composition, the molar concentration of the basic group from the alkali compound C, Cb3 (mol / kg), is preferably 0.000 or more and 3.00 or less. By keeping Cb3 within the above range, the effect of improving wet rubbing adhesion based on the present invention tends to be more effective and reliable. From the same 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.

[0124] When the composition group includes a transparent ink composition, the Cb2 and Cb3 mentioned above are preferably 0.35 mol / kg or less. By keeping Cb2 and Cb3 within the above range, there is a tendency to further improve the wet rubbing adhesion of the recorded material. From the same point of view, Cb2 and Cb3 are more preferably 0.30 mol / kg or less, and even more preferably 0.25 mol / kg or less.

[0125] The content of alkali compound C, based on its mass, is preferably 0.0 to 10% by mass, 0.01 to 5% by mass, or 0.011 to 3.7% by mass relative to the total amount of the transparent ink composition. By keeping the content of alkali compound C within the above range, the effect of improving wet rubbing adhesion based on the present invention tends to be more effective and reliable.

[0126] 3.3. Water-soluble organic solvents

[0127] The transparent ink composition preferably contains a water-soluble organic solvent. There is no limitation on the organic solvent used in the transparent ink composition, as long as it is water-soluble; examples include the organic solvents described in the above-described processing liquid composition. From the viewpoint of more effectively and reliably improving the wet rubbing adhesion of the recorded material, polyols are preferred, and at least one of glycerol and 1,2-hexanediol is more preferred. Furthermore, one organic solvent may be used alone, or two or more may be used in combination.

[0128] The content of organic solvent in the transparent ink is preferably 5-40% by mass, 10-30% by mass, or 15-25% by mass relative to the total amount of the transparent ink composition. By keeping the content of organic solvent within the above range, there is a tendency for better wet rubbing adhesion.

[0129] 3.4. Surfactants

[0130] The transparent ink composition may also contain a surfactant. Examples of surfactants include those used in the above-described treatment liquid composition. Among such surfactants, from the viewpoint of more effectively and reliably achieving the wet rubbing adhesion effect based on the present invention, acetylenol-based surfactants are preferred, and Surfynol 465 is a preferred commercially available example. Furthermore, one surfactant may be used alone, or two or more may be used in combination.

[0131] 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 transparent ink composition. By keeping the surfactant content within the above range, the wet friction adhesion effect based on the present invention can be achieved more effectively and reliably.

[0132] 3.5. Chelating agents

[0133] The transparent ink composition may also contain a chelating agent. Examples of chelating agents used in the transparent ink composition include disodium ethylenediaminetetraacetate (EDTA2Na), ethylenediaminetetraacetate (EDTA), hypozonotriacetate of ethylenediamine, hexametaphosphate, pyrophosphate, metaphosphate, etc. From the viewpoint of more effectively and reliably exerting the wet rubbing adhesion effect based on the present invention, disodium ethylenediaminetetraacetate (EDTA2Na) is preferred.

[0134] The chelating agent content is preferably 0.001 to 0.5% by mass, 0.005 to 0.3% by mass, and 0.01 to 0.1% by mass relative to the total amount of the transparent ink composition. By keeping the chelating agent content within the above range, the wet friction adhesion effect based on the present invention can be exerted more effectively and reliably.

[0135] 3.6. Water

[0136] As water, water in which ionic impurities have been removed to the greatest extent possible is preferred. Examples of such water include pure water such as ion-exchange water, reverse osmosis water, and distilled water, as well as ultrapure water.

[0137] 3.7. Other ingredients

[0138] In addition to the above-mentioned components, various additives such as pH adjusters, softeners, solvents, viscosity modifiers, UV absorbers, antioxidants, and corrosion inhibitors may also be included as needed.

[0139] 4. Preparation methods of each composition

[0140] As a method for preparing each composition, for example, it can be prepared by mixing the components in any order and removing impurities, foreign matter, etc., by performing filtration or other methods as needed. As a method for mixing the components, a method is used where the components are added sequentially to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer, and then stirred and mixed. As a filtration method, centrifugal filtration and filter filtration can be cited as examples. In addition, the methods used in the examples described later can also be used.

[0141] Example

[0142] The present invention will now be described in more detail using examples and comparative examples. The present invention is not limited to the following examples.

[0143] exist Figures 1 to 8 Tables 1 to 8 describe the composition of the compositions in each composition group of the Examples and Comparative Examples and / or their evaluation results.

[0144] 1. Preparation of each composition

[0145] Each component was added to a mixing tank in the manner described in Tables 1 to 8, mixed and stirred, and then filtered using a membrane filter to obtain the processing liquid composition, coloring ink composition, and transparent ink composition of each example. Unless otherwise specified, the values ​​of each component shown in the tables represent mass percentages. Furthermore, the content values ​​in the tables represent the mass percentage of the solid component of the active ingredient.

[0146] The abbreviations used in each composition and details of the product ingredients are as follows.

[0147] 1.1. Preparation of the treatment liquid composition

[0148] [Acid compounds]

[0149] • Lactic acid (pKa=3.9, carboxyl group, 1 valence)

[0150] • Malonic acid (pKa = 2.8, 5.7, carboxyl group, divalent)

[0151] • Citric acid (pKa = 3.1, 4.8, 5.4, carboxyl group, trivalent)

[0152] • Adipic acid (pKa = 4.4, 5.4, carboxyl group, divalent)

[0153] • Succinic acid (pKa = 4.2, 5.5, carboxyl group, divalent)

[0154] • Malic acid (pKa = 3.4, 5.1, carboxyl group, divalent)

[0155] • Vetylpropionic acid (pKa=4.6, carboxyl group, 1 valence)

[0156] • Glutaric acid (pKa = 4.1, 5.0, carboxyl group, divalent)

[0157] • Dimethylolpropionic acid (pKa=4.7, carboxyl group, 1 valence)

[0158] • Propionic acid (pKa=4.7, carboxyl group, monovalent)

[0159] • Sulfuric acid (pKa = -2.0, 1.9, sulfonyl, divalent)

[0160] • Phosphoric acid (pKa = 2.0, 6.8, 12.5, phosphate group, divalent)

[0161] • Hydrochloric acid (pKa < 0, valence 1)

[0162] [Base compound A]

[0163] •KOH (monovalent)

[0164] • NaOH (monovalent)

[0165] •Ca(OH)2 (divalent)

[0166] •Mg(OH)2 (divalent)

[0167] •Al(OH)3 (trivalent)

[0168] • Triisopropanolamine (amino, monovalent)

[0169] • Dipropyltriamine (amino, trivalent)

[0170] • PAA-03 (Cationic Polymer) (Polyallylamine, amino, pH=11, manufactured by Nittobo Medical Co., Ltd., molecular weight of each basic group calculated by the method described below: 61.385 g / mol)

[0171] [Organic solvents]

[0172] ·glycerin

[0173] ·Propylene glycol

[0174] Triethylene glycol

[0175] • 1,2-Hexanediol

[0176] • Triethylene glycol monobutyl ether

[0177] ・3-Methoxy-1-butanol

[0178] ε-caprolactam

[0179] [surfactant]

[0180] •Surfynol 465 (acetylenic diol, manufactured by Nissin Chemical Industries, Ltd.)

[0181] [water]

[0182] Pure water

[0183] 1.2. Preparation of Coloring Ink Composition

[0184] The details of each component shown in Table 7 are as follows.

[0185] [pigment]

[0186] • Self-dispersible Bk pigment dispersion: A self-dispersible Bk pigment dispersion prepared by the following method.

[0187] 500g of carbon black raw material powder (primary particle size = 18nm, BET specific surface area = 180m²) prepared by furnace method was used. 2 The solution (containing zirconia beads with a DBP absorption capacity of 186 mL / 100 g) was added to 3750 g of ion-exchanged water and heated to 45 °C while stirring in a dissolver. Then, using a sand mill with 0.8 mm diameter zirconia beads, 30000 g of an aqueous solution of sodium hypochlorite (available chlorine concentration = 12%) was added dropwise over 3.5 hours at 45 °C. The mixture was then further milled for 30 minutes to obtain a treatment solution containing self-dispersible carbon black. This treatment solution was filtered through a 400-mesh metal 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. The solution was then desalted and purified using an ultrafiltration membrane until the conductivity of the liquid was 1.5 mS / cm. Further desalting and purification were performed using an electrodialysis apparatus until the conductivity of the liquid was 1.0 mS / cm. The liquid was then concentrated to a self-dispersible carbon black concentration of 17% by mass. The concentrate was centrifuged to remove coarse particles and then filtered through a 0.6 μm filter. Ion-exchanged water was added to the filtrate to dilute it to a concentration of 15% by mass for the self-dispersible carbon black, thus dispersing it to obtain a self-dispersible Bk pigment dispersion.

[0188] Resin-dispersed Bk pigment dispersion: A resin-dispersed Bk pigment dispersion prepared by the following method.

[0189] 20 parts by weight of methyl ethyl ketone, 0.03 parts by weight of 2-mercaptoethanol, polymerization initiator, 15 parts by weight of polypropylene glycol monomethacrylate (propylene oxide = 9), 15 parts by weight of poly(ethylene glycol-propylene glycol) monomethacrylate (propylene oxide = 7, ethylene oxide = 5), 12 parts by weight of methacrylic acid, 50 parts by weight of styrene monomer, 10 parts by weight of styrene macromonomer, and 10 parts by weight of benzyl methacrylate were added to a reaction vessel that had been fully purged with nitrogen. Polymerization was carried out at 75°C with stirring. Relative to 100 parts by weight of monomer, 0.9 parts by weight of 2,2'-azobis(2,4-dimethylpentanonitrile) in 40 parts by weight of methyl ethyl ketone was added. The mixture was cured at 80°C for 1 hour to obtain a polymer solution.

[0190] 7.5 parts by mass of the water-insoluble polymer obtained above were dissolved in 45 parts by mass of methyl ethyl ketone. A specified amount of 20% sodium hydroxide aqueous solution (neutralizing agent) was added to neutralize it into a base. Then, 20 parts by mass of carbon black as a pigment were added, and the mixture was ball-milled for 2 hours. 120 parts by mass of deionized water were added to the resulting mixture and stirred. The methyl ethyl ketone was removed under reduced pressure at 6°C, and a portion of the water was also removed, thereby obtaining a resin-dispersed pigment dispersion with a solid content concentration of 20% by mass.

[0191] [Resin]

[0192] • Resin dispersion: A resin dispersion prepared by the following method is used.

[0193] In a four-necked flask equipped with a stirrer, cooling tube, nitrogen inlet tube, and thermometer, 322.2 g of polytetramethylene ether glycol, 19.7 g of 2,2-dimethylolbutyric acid, 16.9 g of 1,4-butanediol, 137.9 g of hexamethylene diisocyanate, and 344.0 g of methyl ethyl ketone (number average molecular weight 1000) were added. The mixture was reacted at 80°C for 6 hours under a nitrogen atmosphere. Then, the mixture was cooled to 60°C, and 12.5 g of triethylamine was added. The mixture was then stirred at this temperature for 30 minutes. The resulting prepolymer was mixed with 1146.7 g of deionized water and stirred for 2 hours. The methyl ethyl ketone was then desolvated under reduced pressure at 40°C to obtain a polyurethane resin dispersion with carboxyl groups as acidic groups.

[0194] [Organic solvents]

[0195] ·glycerin

[0196] • 1,2-Hexanediol

[0197] [Base compound B]

[0198] •KOH (monovalent)

[0199] Triethanolamine

[0200] [surfactant]

[0201] •Surfynol465 (trade name, acetylenol-based surfactant, manufactured by Nissin Chemical Industries, Ltd.)

[0202] [Chlorinating agents]

[0203] • EDTA2Na (Disodium dihydrogen ethylenediaminetetraacetate)

[0204] [water]

[0205] Pure water

[0206] 1.3. Preparation of transparent ink compositions

[0207] The details of each component shown in Table 8 are as follows.

[0208] [Resin]

[0209] • Resin dispersion: The same resin dispersion used in the preparation of the above-described coloring ink composition is used.

[0210] [Base compound C]

[0211] •KOH (monovalent)

[0212] Triethanolamine

[0213] [Organic solvents]

[0214] ·glycerin

[0215] • 1,2-Hexanediol

[0216] [surfactant]

[0217] •Surfynol465 (trade name, acetylenol-based surfactant, manufactured by Nissin Chemical Industries, Ltd.)

[0218] [Chlorinating agents]

[0219] • EDTA2Na (Disodium dihydrogen ethylenediaminetetraacetate)

[0220] [water]

[0221] Pure water

[0222] 2. Calculation Method

[0223] 2.1. Calculation methods for Ca1, Cb1, Cb2, and Cb3

[0224] The molar concentration Ca1 of the acidic group in an acid compound can be calculated using the following formula.

[0225] Ca1 = (Amount of acid compound added [mass%]) × (Number of acidic groups with pKa below 7 in one acid molecule) × 10 / (Molecular weight of acid compound [g / mol])

[0226] The molar concentrations of the basic groups in an alkali compound, Cb1, Cb2, and Cb3, are calculated using the following formula.

[0227] Cb = (Amount of alkali compound added [mass%]) × (Number of hydroxyl or amino groups in one molecule of alkali) × 10 / (Molecular weight of alkali compound [g / mol])

[0228] Furthermore, in the case of amphoteric compounds such as amino acids, the concentration is 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 of groups. For example, in the case of L-aspartic acid as an acidic amino acid, the concentration can be calculated as follows.

[0229] Aspartic acid has two carboxyl groups as acidic groups (pKa = 2.0, 3.9) and one amino group as a basic group in one molecule, and its aqueous solution has a pH of approximately 3. As an acidic compound, the molar concentration (Ca) of the acidic group can be calculated using the following formula.

[0230] Ca = (Amount of acidic compound added [mass%]) × {(Number of acidic groups with pKa below 7 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])

[0231] The following applies when the amount of aspartic acid added is 10% by mass.

[0232] Ca=10×(2-1)×10 / 133.10≈0.751

[0233] In addition, in the case of amphoteric compounds such as amino acids, the concentration is calculated in the same way as above, based on the difference in the number of acidic and basic groups, according to the properties of the group with more numbers.

[0234] 2.2. Methods for calculating the molecular weight and valence of compounds whose molecular weight and the number of acidic (or basic) groups are unclear.

[0235] Dissolve 0.30 g of a compound with an unspecified molecular weight and number of acidic (or basic) groups in 29.70 g of pure water to prepare 30.00 g. Add 0.03 g of 10 wt% sodium hydroxide (or sulfuric acid) dropwise to the aqueous solution of this compound. After stirring with a magnetic stirrer, repeatedly measure the pH of the aqueous solution using a pH meter (F-72, HORIBA). Neutralization is considered complete when the pH of the aqueous solution reaches 8.0 (or 6.0), and the process is then stopped. Based on this result, calculate the amount of acid (or basic) compound (a) required to neutralize 1 g of 100 wt% sodium hydroxide (or 1 g of sulfuric acid) using the following formula. x (or b) x (g).

[0236] a x =0.30g / (amount of 100wt% sodium hydroxide added in g)

[0237] b x =0.30g / (amount of 100wt% sulfuric acid added in g)

[0238] Here, (the amount of 100wt% sodium hydroxide added in g) = (the amount of 10wt% sodium hydroxide added in g) / 10, and (the amount of 100wt% sulfuric acid added in g) = (the amount of 10wt% sulfuric acid added in g) / 10.

[0239] Next, perform the above operation on a 1 wt% sulfuric acid aqueous solution (or a 1 wt% sodium hydroxide aqueous solution), and calculate the amount of sulfuric acid (or potassium hydroxide) to be added, a, required to neutralize 1 g of 100 wt% sodium hydroxide (or 100 wt% sulfuric acid). H2SO4 (g) (or b) KOH (g)), use the following formula to calculate the molecular weight (g / mol) of each acidic group (or basic group).

[0240] 98.08×a x / a H2SO4

[0241] 40.00×b x / b KOH

[0242] 3. Printing Method

[0243] Using a modified ML-8000 (manufactured by Seiko Epson Corporation), a processing liquid composition and coloring ink are sprayed from the beginning in the same path to print on 100% white cotton wide-width fabric (#4000, manufactured by Nisshinbo Corporation) or polyester fabric. After multiple (2, 4, 8, 12 or 16) main scans of the same scanning area, a transparent ink composition is then printed in the same way, thereby forming a solid image of 20cm × 5cm on the fabric as the recording medium.

[0244] Regarding the adhesion amount of each composition to the cotton fabric, the treatment solution composition is 15 mg / inch. 2 The coloring ink composition is 30 mg / inch. 2 The transparent ink composition is 15 mg / inch. 2 Furthermore, regarding the adhesion amount of each composition to the polyester fabric, the treatment liquid composition is 20 mg / inch. 2 The coloring ink composition is 30 mg / inch. 2 The transparent ink composition is 30 mg / inch. 2 After image formation, the images are dried by heating in an oven at 160°C for 5 minutes, thereby producing the printed materials of each embodiment and comparative example. Furthermore, "solid image" refers to an image with dots uniformly formed across the entire surface of the recording area (main scanning direction × sub-scanning direction: 20cm × 5cm) with the amount of each liquid applied being the values ​​described above.

[0245] In addition, the inkjet head uses a head unit with a nozzle spacing of 600 dpi in the sub-scanning direction and two head chips arranged in the sub-scanning direction, resulting in a nozzle length of 2 inches.

[0246] 4. Evaluation Methods

[0247] 4.1. Wet rubbing adhesion (cotton fabric, polyester fabric)

[0248] Printed materials were produced using various printing methods described above on cotton and polyester fabrics. Conversely, using a clockwork counter (FI-306, manufactured by Tester Industries), the image on the printed material was rubbed 10 times with a load of 9N using a fine white cloth (cotton white cloth). Then, the optical density (OD, Status E) of the black in the rubbed fine white cloth, which was contaminated with ink, was measured using a colorimeter (FD-7, manufactured by Konica Minolta), and evaluated according to the following criteria.

[0249] (Evaluation criteria for printing on cotton fabric)

[0250] SS: OD below 0.22

[0251] S: OD greater than 0.22 and less than 0.31

[0252] A: OD greater than 0.31 and less than 0.4

[0253] B: OD greater than 0.4 and less than 0.5

[0254] C: OD exceeds 0.5

[0255] (Evaluation criteria for printing on polyester fabric)

[0256] SS: Black's OD is below 0.22

[0257] S: Black has an OD greater than 0.22 and less than 0.29.

[0258] A+: Black has an OD greater than 0.29 and less than 0.36.

[0259] A: Black has an OD greater than 0.36 and less than 0.40.

[0260] B: Black has an OD greater than 0.40 but less than 0.47.

[0261] C+: Black has an OD greater than 0.47 and less than 0.53.

[0262] C: The OD of black exceeds 0.53

[0263] 4.2. Stimulation soothing

[0264] For printed materials made using the above printing method on cotton fabric, a 15cm × 3.2cm area of ​​the printed image was cut into 5mm wide pieces and added to a glass bottle along with 35mL of pure water. The mixture was then stirred with a magnetic stirrer for 2 hours for extraction. The pH of the extract was then measured using a pH meter (F-72, manufactured by HORIBA). This process was repeated three times, and the average pH value was evaluated according to the following criteria.

[0265] (Evaluation Criteria)

[0266] S: The average pH value is above 4.7.

[0267] A: The average pH value is above 4.4 and below 4.7.

[0268] B: The average pH value is above 4.2 and below 4.4.

[0269] C: The average pH value is less than 4.2.

Claims

1. An inkjet composition set, characterized by, An inkjet composition set comprising a treatment liquid composition and a colored ink composition, the treatment liquid composition contains an acid compound and water, the treatment liquid composition contains an alkali compound A or does not contain the alkali compound A, the colored ink composition contains a pigment, a resin particle, an alkali compound B, and water, a molar concentration Cb1 mol / kg of a basic group based on the alkali compound A, a molar concentration Cb2 mol / kg of a basic group based on the alkali compound B satisfy the following formula (1) based on a molar concentration Cal mol / kg of an acidic group of the acid compound, Cal - (Cb1 + 1.5 Cb2) ≥ 0.10 mol / kg... Formula (1), in formula (1), Cal > 0, Cb1 ≥ 0, and Cb2 > 0.

2. The inkjet composition set according to claim 1, wherein the acid compound contains 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 dimethylol propionic acid.

3. The inkjet composition set according to claim 1, wherein a pH of the treatment liquid composition is 2.5 or more and 6.5 or less, a pH of the colored ink composition exceeds 6.

5.

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

5. The inkjet composition set according to claim 1, wherein the Cb1 is 0.01 or more.

6. The inkjet composition set according to claim 1, further comprising a clear ink composition, the clear ink composition contains a resin particle, an alkali compound C, and water, the Cal, the Cb1, the Cb2, and a molar concentration Cb3 mol / kg of a basic group based on the alkali compound C satisfy the following formula (2), Cal - (Cb1 + 1.5 Cb2 + 1.5 Cb3) ≥ 0.10 mol / kg... Formula (2).

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

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

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

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

11. The inkjet composition set of claim 6, wherein The base compound A, the base compound B, and the base compound C include one or more selected from an alkali metal hydroxide, an alkaline earth metal hydroxide, and an amine compound.

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