Treatment liquid composition for inkjet and ink set

Abstract

To provide a treatment liquid composition for inkjet which is excellent in stimulation alleviation and friction fastness.SOLUTION: A treatment liquid composition for inkjet is used while being attached to a recording medium, and contains an acid compound, a basic compound and water, wherein the acid compound has a pKa in the water at 25°C of at least 2.5 or more and 7.0 or less. In the treatment liquid composition for the inkjet, a difference (CA-CB) between a mass molar concentration CA (mol / kg) of the acidic group derived from the acid compound and a mass molar concentration CB of the basic group derived from the basic compound is 0.01 or more, and a pH at 25°C is 2.5 or more and 6.5 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an inkjet treatment liquid composition and an ink set. [Background technology]

[0002] The inkjet recording method is capable of recording high-resolution images using a relatively simple device and has been rapidly developing in various fields. Various studies have been conducted on color development, washing fastness, etc. For example, Patent Document 1 discloses an inkjet treatment liquid containing a water-soluble cationic polymer and an organic acid salt, in which the content of the water-soluble cationic polymer is 0.1 wt % or more and less than 10 wt % of the total treatment liquid. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2023-042761 Summary of the Invention [Problem to be solved by the invention]

[0004] However, when a treatment liquid composition obtained by a conventional method such as that described in Patent Document 1 is used, there is room for improvement in the rub fastness of the resulting printed textile. There has been a demand for a treatment liquid composition for inkjet printing that has good rub fastness and also excellent irritation mitigation properties. [Means for solving the problem]

[0005] The inkjet treatment liquid composition of the present invention is used by being attached to a recording medium, and contains an acid compound, a base compound, and water, wherein the acid compound has a pKa in water at 25°C of at least 2.5 to 7.0, and in the inkjet treatment liquid composition, the molar concentration C of the acid group derived from the acid compound is A(mol / kg) and the molar mass concentration C of the basic group derived from the above basic compound B (mol / kg) (C A -C B ) is 0.01 or more, and the pH at 25°C is 2.5 or more and 6.5 or less.

[0006] The ink set of the present invention comprises the inkjet treatment liquid composition described above, and a water-based pigment ink composition containing an anionic dispersed pigment and anionic resin particles. [Brief explanation of the drawings]

[0007] [Figure 1] Table 1 shows the compositions of the treatment solutions used in the examples and the evaluation results thereof. [Figure 2] Table 2 shows the compositions of the treatment solutions used in the examples and the evaluation results thereof. [Figure 3] Table 3 shows the compositions of the treatment solutions used in the examples and the evaluation results thereof. [Figure 4] Table 4 shows the compositions of the treatment solutions used in the examples and the evaluation results thereof. [Figure 5] Table 5 shows the compositions of the treatment solutions used in the examples and the evaluation results thereof. [Figure 6] Table 6 shows the compositions of the water-based pigment ink and coating liquid used in the examples. DETAILED DESCRIPTION OF THE INVENTION

[0008] Below, we will explain in detail an embodiment of the present invention (hereinafter referred to as the "present embodiment"), referring to the drawings as necessary, but the present invention is not limited to this and various modifications are possible within the scope of the gist of the present invention.

[0009] 1. Inkjet treatment liquid composition The inkjet treatment liquid composition of the present invention (hereinafter also referred to as the treatment liquid composition) is used by being attached to a recording medium, and contains an acid compound, a base compound, and water, wherein the acid compound has a pKa in water at 25°C of at least 2.5 or more and 7.0 or less, and in the inkjet treatment liquid composition, the molar concentration C of the acidic groups derived from the acid compound is A (mol / kg) and the molar mass concentration C of the basic group derived from the above basic compound B (mol / kg) (C A -C B ) is 0.01 or more, and the pH at 25°C is 2.5 or more and 6.5 or less.

[0010] Conventionally, organic acids and polyvalent metal salts have been used in treatment liquids as aggregating agents for aggregating ink, but polyvalent metal salts have strong coagulation power and tend to produce recorded matter with good color development and reduced strike-through, but the wet rub fastness of the resulting recorded matter tends to be reduced. On the other hand, organic acids undergo a neutralization reaction with the anionic components of the ink, thereby reducing the hydrophilicity of the anionic components, and therefore, recorded matter with excellent wet rub fastness can be obtained.

[0011] Printed materials are often intended for use in products that come into direct contact with the skin of humans and animals, and when printed materials are pretreated with organic acids, they can be highly irritating to the skin. Therefore, the challenge is to mitigate skin irritation while maintaining rubfastness.

[0012] In this respect, the present invention provides a method for producing a sol-gel electrolytic solution containing an acid compound and a base compound, each of which has a pKa in water at 25°C of at least 2.5 to 7.0, and further having a molar concentration C of the acidic group derived from the acid compound. A (mol / kg) and the molar mass concentration C of the basic group derived from the base compound B (mol / kg) (C A -C B ) to be 0.01 or more, and the pH of the treatment liquid at 25°C to be 2.5 or more and 6.5 or less, it was possible to obtain a printed matter that was excellent in irritation mitigation properties and abrasion fastness.

[0013] Thus, among acid compounds, the use of those having a pKa in the range of 2.5 to 7.0 can improve wet rubbing fastness, while the use of a base compound can reduce irritation caused by the acid compound. Regarding the point that the reactivity of the acid compound is reduced by using a base compound, the use of an acid compound having a pKa of 2.5 or more in the pH range of 2.5 to 6.5 and the difference in mass molar concentration (C A -C B By making the ratio of the acid compound to the base in the treatment liquid to form a neutralized salt can be reduced by making the ratio 0.01 or more. Therefore, it is thought that the irritation caused by the acid compound can be suppressed while the action of the acid compound is maintained, allowing a sufficient neutralization reaction to proceed with the ink, reducing the hydrophilicity of the components in the ink, resulting in excellent rub fastness.

[0014] In this specification, "acid" and "acid compound" refer to a compound having a pH of less than 7 when made into a 0.1% by mass aqueous solution at 25°C. Furthermore, a compound having at least a pKa of 2.5 or more and 7.0 or less is considered an acid compound. Furthermore, "base" and "basic compound" refer to a compound having a pH of more than 7 when made into a 0.1% by mass aqueous solution at 25°C. Furthermore, it is preferable that the pKa of the conjugate acid of the base is 12 or less.

[0015] Each component contained in the treatment liquid composition will be described in detail below.

[0016] 1.1. Acid compounds Examples of the acid compound include organic acids and inorganic acids. From the viewpoint of providing printed materials with even better irritation mitigation properties and rubbing fastness, organic acids are preferred. One acid compound may be used alone, or two or more acid compounds may be used in combination. The acid compound and the base compound may partially form neutralized salts in the treatment liquid composition.

[0017] As used herein, the expression "a compound has a pKa within a certain range" means that if the compound has a single pKa, the pKa is within a predetermined range, and if the compound has multiple pKas, any one or more of the pKas is within a predetermined range.

[0018] The acid compound is not particularly limited as long as it has a pKa in water at 25°C of at least 2.5 or more and 7.0 or less, but preferably has a pKa of 3.0 or more and 6.8 or less, 4.0 or more and 6.7 or more, or 4.5 or more and 6.5 or less. By having the pKa of the acid compound in water at 25°C within the above range, it is possible to exhibit buffering ability in the pH range of 2.5 to 6.5 and to further reduce the neutralization rate with the base compound. Therefore, while irritation is reduced, a large amount of unneutralized acid compound remains in the treatment liquid composition, which tends to further improve rub fastness.

[0019] The normal boiling point or thermal decomposition point at atmospheric pressure of the acid compound is preferably 350°C or lower, 300°C or lower, 250°C or lower, 200°C or lower, 170°C or lower, or 150°C or lower. The lower limit of the normal boiling point or thermal decomposition point at atmospheric pressure of the acid compound may be 100°C or higher. By setting the normal boiling point or thermal decomposition point at atmospheric pressure of the acid compound within the above range, the acid compound derived from the processing liquid composition tends to volatilize or decompose easily when the recorded material is dried. By volatilizing or decomposing the acid compound in this way, the acid compound is removed from the recorded material, and the resulting recorded material tends to have even better irritation mitigation properties and abrasion fastness.

[0020] Suitable examples of organic acid compounds include 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, pyrrolidonecarboxylic acid, pyrronecarboxylic acid, pyrrolecarboxylic acid, furancarboxylic acid, pyridinecarboxylic acid, coumaric acid, thiophenecarboxylic acid, nicotinic acid, derivatives of these compounds, and salts thereof. Among these, at least one selected from the group consisting of lactic acid, levulinic acid, malic acid, malonic acid, citric acid, phosphoric acid, succinic acid, glutaric acid, and adipic acid is preferred, and at least one selected from the group consisting of lactic acid, malonic acid, citric acid, adipic acid, succinic acid, malic acid, levulinic acid, glutaric acid, and phosphoric acid is more preferred. By including such an acid compound, the resulting printed item tends to be more excellent in irritation relief and rub fastness.

[0021] The content of the acid compound is preferably 1.0 to 50 mass%, 2.0 to 40 mass%, 3.5 to 30 mass%, or 4.0 to 15 mass%, relative to the total amount of the treatment liquid composition. By setting the content of the acid compound within the above range, the printed product tends to have even better irritation relief and rub fastness.

[0022] 1.2. Basic Compounds Examples of the basic compound include organic bases and inorganic bases. Among the organic bases and inorganic bases, metal hydroxides and amine compounds are preferred. By using a metal hydride or an amine compound, the printed material tends to have better irritation relief and rub fastness.

[0023] As the basic compound, one type may be used alone, or two or more types may be used in combination. From the viewpoint of further improving the irritation mitigation property and rub fastness of the printed textile, it is preferable to use two or more types of basic compounds. While a basic compound with low water solubility contributes to improving wet rub fastness, its low water solubility tends to limit the amount added to the treatment liquid composition, and adjustment of the pH tends to be difficult. In this regard, by using other bases of different types in combination, the flexibility of pH adjustment is further improved, and the pH of the extract tends to be more suitable.

[0024] The metal constituting the metal hydroxide is preferably at least one selected from the group consisting of Li, Na, K, Ca, Mg, and Al, and more preferably at least one selected from the group consisting of Na, K, Ca, Mg, and Al. By using such metal hydroxides and amine compounds, the printed material tends to have even better irritation mitigation properties and rub fastness. Furthermore, Li, Na, K, and monoamines have high solubility in water and are less likely to form precipitates in the reaction solution, resulting in excellent storage stability. Ca, Mg, Al, and polyamines tend to further improve wet rub fastness, particularly wet rub fastness on polyester fabrics.

[0025] From a similar perspective, the basic compound preferably includes a hydroxide of one or more metals selected from the group consisting of Ca, Mg, and Al, or an amine compound containing 2 to 10 nitrogen atoms in the molecule, and more preferably includes a hydroxide of one or more metals selected from the group consisting of Ca, Mg, and Al, or an amine compound containing 2 to 6 nitrogen atoms in the molecule. In particular, the use of such a basic compound tends to further improve wet rub fastness, particularly wet rub fastness on polyester fabrics. Furthermore, in printed materials, the basic compound can bond (neutralize) with the anionic groups of the anionic dispersed pigment or anionic resin particles in the ink composition described below to form a neutralized salt with relatively low solubility in water. Furthermore, because the basic compound is a polyvalent base, its molecular weight can be increased, making it less likely to leach out of the ink film on printed materials during wet rub, resulting in good wet rub fastness.

[0026] The metal hydroxide is preferably at least one selected from the group consisting of LiOH, NaOH, KOH, Ca(OH)2, Mg(OH)2, and Al(OH)3, and more preferably at least one selected from the group consisting of NaOH, KOH, Ca(OH)2, Mg(OH)2, and Al(OH)3. By using such a metal hydroxide, the printed item tends to have even better irritation relief and rub fastness.

[0027] The amine compound is preferably at least one selected from the group consisting of alkanolamine compounds, polyamine compounds, and polyamine compounds. By using such an amine compound, the printed material tends to have even better irritation relief and rub fastness.

[0028] Examples of alkanolamine compounds include triethanolamine, tripropanolamine, triisopropanolamine, and tributanolamine. Among these, triisopropanolamine is preferred from the viewpoint of further improving the irritation mitigation and rub fastness of printed textiles. Examples of polyvalent amine compounds include diethylenetriamine, dipropylenetriamine, dihexylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and hexaethyleneheptamine. Among these, dipropylenetriamine is preferred from the same viewpoint as above.

[0029] The polyamine compound may be any compound having an amino group in its structure, for example, Examples of the resin include polyamine resins, polyamide resins, and polyallylamine resins. The polyamine compound may be a commercially available product corresponding to the basic compound in the present specification. 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 Nittobo Medical Co., Ltd.), FL-14 (manufactured by SNF Co., Ltd.), Arafix 100, 251S, 255, 255LOX (manufactured by Arakawa Chemical Co., Ltd.), and DK-6 810, 6853, 6885; WS-4010, 4011, 4020, 4024, 4027, 4030 (manufactured by Seiko PMC Co., Ltd.), Papiogen P-105 (manufactured by Senka Co., Ltd.), Sumirez Resin 650(30), 675A, 6615, SLX-1 (manufactured by Taoka Chemical Co., Ltd.), Catiomaster (registered trademark) PD-1, 7, 30, A, PDT-2, PE-10, PE-30, DT-EH, EPA-SK01, TMHMDA-E (manufactured by Yokkaichi Synthetic Co., Ltd.), Jetfix 36N, 38A, N700, 5052 (manufactured by Satoda Chemical Co., Ltd.). Of these, PAA-03 is preferred from the viewpoint of further improving the irritation mitigation properties and rub fastness of printed textiles.

[0030] Examples of polyallylamine resins include polyallylamine hydrochloride, polyallylamine amidosulfate, 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 amidosulfate, 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, diallyldimethylammonium chloride-acrylamide copolymer, and the like.

[0031] The content of the basic compound is preferably 0.1 to 30 mass%, 0.2 to 20 mass%, 0.25 to 15 mass%, or 0.4 to 13 mass%, relative to the total amount of the treatment liquid composition. By setting the content of the basic compound within the above range, the printed product tends to have even better irritation relief and rub fastness.

[0032] 1.3. Acidic and basic groups In the processing liquid composition, the molar concentration C of the acidic group derived from the acid compound A (mol / kg) and the molar mass concentration C of the basic group derived from the base compound B (mol / kg) (C A -C B The difference in the molar concentration (C A -C B By making the difference in the molar concentrations (C ) in the processing solution 0.01 or more, the obtained printed textile will have excellent rub fastness and irritation relief. A -C B) is 0.01 or more and 5.0 or less, 0.1 or more and 4.8 or less, 0.2 or more and 4.5 or less, 0.5 or more and 4.0 or less, 0.5 or more and 2.0 or less, and 0.5 or more and 1.2 or less. The acidic group and the basic group may each be contained alone or in combination of two or more types.

[0033] The acidic group is not particularly limited as long as it is one that the above-mentioned acid compound has, and examples thereof include a carboxyl group, a sulfo group, a phosphate group, a phenol group, and a sulfite group. Among these, from the viewpoint of further improving the irritation relief and rub fastness of the printed textile, one or more selected from the group consisting of a carboxyl group, a sulfo group, and a phosphate group are preferred, and a carboxyl group is more preferred.

[0034] The basic group is not particularly limited as long as it is one that the above-mentioned basic compound has, and examples thereof include a hydroxyl group, an amino group, and an imidazole group. Among these, from the above-mentioned viewpoint, a hydroxyl group and an amino group are preferred, and an amino group is more preferred.

[0035] Molarity of acidic groups C A (mol / kg) is preferably 0.30 or more, 0.30 or more and 7.0 or less, 0.30 or more and 6.5 or less, or 0.50 or more and 5.0 or less. A By setting the molar concentration C (mol / kg) within the above range, the irritation mitigation property and the friction resistance tend to be more excellent. Note that the acid compound may also have a basic group. In this case, in this embodiment, the molar concentration C A (mol / kg), and the basic groups of the acid compound are not taken into account when calculating the concentration.

[0036] Molar concentration of basic groups C B (mol / kg) is preferably 0.01 or more and 5.0 or less, 0.03 or more and 3.0 or less, or 0.05 or more and 2.5 or less. BBy setting the molar concentration C (mol / kg) within the above range, the effects of irritation relief and friction fastness according to the present invention can be more effectively and reliably achieved. Note that the basic compound may also have an acidic group. In this case, in this embodiment, the molar concentration C B (mol / kg), and the acidic groups of basic compounds are not taken into account when calculating the concentration.

[0037] Polyvalent metal salts are divided into the acid and base (hydroxide of the polyvalent metal) that make up the salt, and the molar concentration of the acidic group, C A (mol / kg), the molar concentration of basic groups, C B For example, for a fully neutralized compound such as calcium lactate, the difference in molar concentration (C A -C B ) is 0 and does not exceed 0.01. On the other hand, in monocalcium hydrogen citrate and disodium hydrogen citrate, two of the three acidic groups of citric acid are neutralized and one remains as an acidic group, and the difference in molar concentration (C A -C B ) is a positive value.

[0038] 1.4. Water-soluble organic solvents The treatment liquid composition may contain a water-soluble organic solvent. The organic solvent is not limited as long as it is water-soluble, and examples thereof include polyhydric alcohols, glycol ethers, nitrogen-containing solvents, esters, and cyclic esters. Among these, polyhydric alcohols are preferred from the viewpoint of further improving the irritation mitigation properties and friction fastness of printed textiles. The organic solvent may be used alone or in combination of two or more.

[0039] 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, from the viewpoint of further improving the irritation mitigation properties and rub fastness of printed textiles, it is preferable to include one or more selected from the group consisting of glycerin, propylene glycol, and triethylene glycol.

[0040] Specific examples of the diol compound 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, 2-methylpentane-2,4-diol, etc. Among these, 1,2-hexanediol is preferred from the viewpoint of further improving the irritation mitigation properties and rub fastness of printed textiles.

[0041] Furthermore, specific examples of glycol ether compounds include triethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, 3-methoxy-3-methyl-1-butanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether. Among these, it is preferable to use triethylene glycol monobutyl ether from the viewpoint of further improving the irritation mitigation property and the rub fastness of the printed textile.

[0042] The content of the organic solvent is preferably 5 to 50 mass %, 10 to 40 mass %, or 12 to 30 mass %, relative to the total amount of the treatment liquid composition. By setting the content of the organic solvent within the above range, irritation mitigation properties and rub fastness tend to be even more excellent. From the same viewpoint, the content of the polyhydric alcohols or polyols is preferably 5 to 50 mass %, 10 to 40 mass %, or 12 to 30 mass % relative to the total amount of the treatment liquid composition.

[0043] The treatment liquid composition preferably contains 5.0% by mass or more of a water-soluble organic solvent having a normal boiling point of 280°C or higher, relative to the total amount of the treatment liquid composition. By setting the content of the organic solvent having a normal boiling point of 280°C or higher within this range, irritation mitigation properties and rub fastness tend to be even more excellent. Furthermore, the discharge stability when the treatment liquid composition is discharged by an inkjet method tends to be even more improved. From the same viewpoint, the water-soluble organic solvent having a normal boiling point of 280°C or higher is more preferably contained in an amount of 5.0 to 30% by mass, or 7.0 to 25% by mass, relative to the total amount of the treatment liquid composition.

[0044] 1.5.Surfactants The treatment liquid composition may contain a surfactant. Examples of surfactants include nonionic surfactants, anionic surfactants, and amphoteric surfactants. From the viewpoint of further improving the ejection stability when the treatment liquid composition is ejected by an inkjet method, nonionic surfactants are preferred. Nonionic surfactants are also preferred because they tend to be stable even in treatment liquid compositions containing an acid compound and a base compound. Note that one type of surfactant may be used alone, or two or more types may be used in combination.

[0045] The treatment liquid composition preferably contains a nonionic surfactant and a water-soluble organic solvent, and the water-soluble organic solvent further preferably contains one or more of a diol compound having 4 or more carbon atoms and a glycol ether having 4 or more carbon atoms. When the concentration of neutralized salts formed by an acid compound and a base compound in the treatment liquid composition increases, the water solubility of the nonionic surfactant tends to decrease. In this regard, the inclusion of a combination of the diol compound and the glycol ether can improve the solubility of the nonionic surfactant. By including such compounds in the treatment liquid, the effects of irritation mitigation and abrasion fastness according to the present invention can be more effectively and reliably achieved.

[0046] Examples of nonionic surfactants include acetylene glycol surfactants, alcohol ethoxylate surfactants, fluorine-based surfactants, and silicone-based surfactants. The acetylene glycol surfactant is not particularly limited, but examples thereof include one or more selected from 2,4,7,9-tetramethyl-5-decyne-4,7-diol, alkylene oxide adducts of 2,4,7,9-tetramethyl-5-decyne-4,7-diol, and alkylene oxide adducts of 2,4-dimethyl-5-decyne-4-ol and alkylene oxide adducts of 2,4-dimethyl-5-decyne-4-ol.

[0047] Commercially available acetylene glycol surfactants include, for example, the E series (product names of Air Products Co., Ltd.) such as the Olfin 104 series and Olfin E1010, and Surfynol 61, 104, and 465 (product names of Nissin Chemical Industry Co., Ltd.). Of these, Surfynol 465 is preferred from the viewpoint of more effectively and reliably achieving the effects of irritation relief and friction fastness according to the present invention.

[0048] Alcohol ethoxylate surfactants are compounds in which a polyoxyethylene chain and an alkyl group are bonded by an ether bond. A -O-(CH2CH2O) d It can be represented by the molecular formula "-H" and is sometimes called poly(oxyethylene) alkyl ether.

[0049] In alcohol ethoxylate surfactants, the alkyl group (R A There are no limitations on the number of carbon atoms in the alkyl group (R ) and the average number of moles of ethyleneoxy chains (d) added. A ) preferably has about 11 to 15 carbon atoms, more preferably about 12 to 13 carbon atoms; and the average number of moles of added ethyleneoxy chains (d) is preferably about 3 to 15, more preferably about 5 to 10.

[0050] 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 (trade names manufactured by Sanyo Chemical Industries, Ltd.).

[0051] Examples of silicone surfactants include polysiloxane compounds and polyether-modified organosiloxanes. Commercially available silicone surfactants include, for example, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK-348, and BYK-349 (all trade names, manufactured by BYK Japan KK), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, and KF-6017 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.). Among these, BYK-348 is preferred from the viewpoint of more effectively and reliably achieving the effects of irritation relief and friction fastness according to the present invention.

[0052] The fluorine-based surfactant is not particularly limited, but examples thereof include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines, and perfluoroalkyl amine oxide compounds.

[0053] Commercially available fluorine-based surfactants include, but are not limited to, S-144 and S-145 (manufactured by Asahi Glass Co., Ltd.); FC-170C, FC-430, and Fluorad-FC4430 (manufactured by Sumitomo 3M Limited); FSO, FSO-100, FSN, FSN-100, and FS-300 (manufactured by DuPont); and FT-250 and 251 (manufactured by Neos Corporation).

[0054] The content of the surfactant is preferably 0.01 to 3.0 mass %, 0.03 to 2.0 mass %, or 0.05 to 1.0 mass %, relative to the total amount of the treatment liquid composition. By keeping the content of the surfactant within the above range, the effects of irritation relief and rub fastness according to the present invention can be more effectively and reliably achieved.

[0055] 1.6.Water The treatment liquid contains water. The water is preferably water from which ionic impurities have been removed as much as possible, and examples of such water include pure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water, as well as ultrapure water.

[0056] The water content is preferably 30 to 90 mass %, more preferably 40 to 80 mass %, and even more preferably 50 to 75 mass %, relative to the total amount of the treatment liquid composition. By keeping the water content in the treatment liquid within the above range, the effects of the present invention can be more effectively and reliably achieved.

[0057] 1.7.Other Ingredients The treatment liquid may contain various additives as needed, such as pH adjusters, metal sealants, softeners, solubilizers, viscosity adjusters, UV absorbers, antioxidants, and corrosion inhibitors, in addition to the components described above. Furthermore, the treatment liquid composition is not an ink and is not intended for coloring purposes. Therefore, it does not substantially contain coloring materials. The coloring material content may be 0.5% by mass or less, or 0.1% by mass or less, and is preferably 0.0% by mass, relative to the total amount of the treatment liquid composition.

[0058] 1.8. Method for preparing processing liquid composition The treatment liquid composition can be prepared, for example, by mixing the components in any order and, if necessary, filtering or the like to remove impurities and foreign matter. The components can be mixed by sequentially adding the components to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer, followed by stirring and mixing. Examples of filtration methods include centrifugal filtration and filter filtration. Alternatively, the method used in the examples described below may be used.

[0059] 2. Ink set The ink set of this embodiment (hereinafter also referred to as the present ink set) includes the inkjet treatment liquid composition described above and a water-based pigment ink composition containing an anionic dispersed pigment and anionic resin particles. Use of an ink set having such a configuration improves the irritation mitigation and rub fastness of printed textiles.

[0060] Each of the compositions that can be included in the ink set is described in detail below.

[0061] 2.1. Water-based pigment ink composition The water-based pigment ink composition of the present ink set contains an anionic dispersed pigment and anionic resin particles. While not particularly limited, for example, the water-based pigment ink composition may be applied to a recording medium to which the treatment liquid composition has been applied, or may be applied to the recording medium simultaneously with the treatment liquid composition, or the water-based pigment ink composition may be applied first and then the treatment liquid composition may be applied. Among these, it is preferable to apply the water-based pigment ink composition to the recording medium simultaneously with the treatment liquid composition.

[0062] 2.1.1. Anionic pigment dispersions The water-based pigment ink composition of this ink set contains an anionic dispersed pigment. The anionic dispersed pigment is dispersed by neutralizing its acidic groups with a base, and the acid in the treatment liquid composition liberates the acidic groups of the dispersed pigment, which are weaker acids, reducing solubility and tending to further improve rub fastness.

[0063] In the water-based pigment ink, the dispersed pigment is preferably a self-dispersing pigment. By including a self-dispersing pigment, the neutralization reaction with the organic acid in the treatment liquid tends to proceed more easily, and the ink tends to have excellent abrasion fastness and irritation mitigation properties.

[0064] Examples of carbon blacks include CI (Colour Index Generic Name) Pigment Black 1, 7, and 11. Commercially available carbon blacks may be used, such as Mitsubishi Chemical Corporation's No. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, and No. 2200B, Columbia Carbon's Raven (registered trademark) 5750, 5250, 5000, 3500, 1255, and 700, CABOT's Rega1 (registered trademark) 400R, 330R, and 660R, Mogul (registered trademark) L, and Monarch (registered trademark) 700, 800, 880, 900, 1000, 1100, 1300, and 1400, and Degussa's Color Black Examples include FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Printex (registered trademark) 35, U, V, 140U, and Special Black 6, 5, 4A, and 4. Pigments obtained by the preparation methods described in the examples below may also be used.

[0065] The pigment content in the water-based pigment ink is preferably 1 to 10 mass %, 2 to 8 mass %, or 3 to 7 mass % relative to the total amount of the water-based pigment ink composition. By keeping the pigment content within the above range, the effects of the present invention can be more effectively and reliably achieved. The pigment content in the water-based pigment ink is based on the mass % of the pigment solid content.

[0066] 2.1.2. Anionic resin particles Examples of anionic resin particles include those in which the resin constituting the resin particles has anionic groups. Examples of anionic groups include sulfonic acid groups, carboxyl groups, phosphate groups, and hydroxyl groups, with acidic groups being preferred. By using resin particles with acidic groups, the effects of the present invention tend to be more effective and reliable. The resin particles are particles containing a resin, and can be used in either an emulsion state or a solution state, but from the viewpoint of suppressing an increase in the viscosity of the ink, it is preferable to use those in an emulsion state.

[0067] More specifically, examples of the anionic resin particles include urethane resins, polycarbonate resins, (meth)acrylic resins, styrene resins, silicone resins, styrene-acrylic resins, fluorene resins, polyolefin resins, rosin-modified resins, terpene resins, polyester resins, polyamide resins, epoxy resins, vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, and ethylene-vinyl acetate resins. Among these, from the viewpoint of more effectively and reliably achieving the effects of the present invention, styrene-acrylic resins or urethane resins are preferred, and urethane resins are more preferred.

[0068] The content of the anionic resin particles in the aqueous pigment 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 aqueous pigment ink composition. By keeping the content of the anionic resin particles within the above range, the effects of the present invention can be more effectively and reliably achieved. The above content is based on the mass % of the solid content of the anionic resin particles.

[0069] 2.1.3. Organic Solvents The water-based pigment ink may contain an organic solvent. The organic solvent is not particularly limited as long as it is water-soluble, and the same types as those used in the treatment liquid may be used. Polyhydric alcohols are preferred.

[0070] The water-based pigment ink preferably contains glycerin or 1,2-hexanediol as an organic solvent of polyhydric alcohols, because the inclusion of these compounds makes it possible to more effectively and reliably achieve the effects of the present invention.

[0071] The content of the organic solvent in the water-based pigment ink is preferably 5 to 30 mass %, 10 to 25 mass %, or 15 to 20 mass %, relative to the total amount of the water-based pigment ink composition. By keeping the content of the organic solvent within the above range, irritation mitigation properties and rub fastness tend to be even better. From the same viewpoint, the content of the polyhydric alcohols is 5 to 30% by mass, and preferably 10 to 25% by mass, relative to the total amount of the water-based pigment ink composition.

[0072] Surfactants The aqueous pigment ink composition may contain a surfactant. Examples of surfactants include acetylene glycol surfactants, fluorine-based surfactants, and silicone-based surfactants, and preferably, acetylene glycol surfactants are used. By using an acetylene glycol surfactant, the effects of the present invention can be more effectively and reliably achieved.

[0073] As a commercially available acetylene glycol surfactant, Surfynol 465 (trade name, manufactured by Nissin Chemical Industry Co., Ltd.) is preferably used from the viewpoint of more effectively and reliably achieving the effects of irritation relief and friction fastness according to the present invention.

[0074] The content of the surfactant in the water-based pigment ink is preferably 0.1 to 5 mass %, 0.2 to 3 mass %, or 0.3 to 1 mass %, relative to the total amount of the water-based pigment ink composition. By keeping the content of the surfactant within the above range, the effects of the present invention can be more effectively and reliably achieved.

[0075] 2.1.5. pH adjusters The aqueous pigment ink composition may contain a pH adjuster. The pH adjuster is not particularly limited, but may include an appropriate combination of an acid, a base, a weak acid, and a weak base. Examples of such acids and bases include inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, and inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium dihydrogen phosphate, disodium hydrogen phosphate, potassium carbonate, sodium carbonate, sodium bicarbonate, and ammonia. Examples of organic bases include triethanolamine (TEA), diethanolamine, monoethanolamine, tripropanolamine, triisopropanolamine, diisopropanolamine, and trishydroxymethylaminomethane (THAM). Examples of organic acids include adipic acid, citric acid, succinic acid, lactic acid, N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES), and 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPE). Other examples of suitable buffers include Good's buffers such as acetamidoglycine, tricine, glycineamide, bicine, phosphate buffer, citrate buffer, and Tris buffer. Among these, triethanolamine is preferred from the viewpoint of achieving the effects of the present invention more effectively and reliably.

[0076] The content of the pH adjuster in the water-based pigment ink is preferably 0.1 to 5 mass %, 0.2 to 3 mass %, or 0.3 to 1 mass %, relative to the total amount of the water-based pigment ink composition. By keeping the content of the pH adjuster within the above range, the effects of the present invention can be more effectively and reliably achieved.

[0077] In addition to the above components, the water-based pigment ink may contain various additives as needed, such as a metal sealant, a softener, a dissolution aid, a viscosity adjuster, an ultraviolet absorber, an antioxidant, and a corrosion inhibitor.

[0078] 2.2. Coating liquid composition The ink set preferably includes a water-based coating liquid composition, which contains anionic resin particles and is substantially free of pigments. The inclusion of such a coating liquid composition tends to further improve the abrasion fastness of the printed textile. While not particularly limited, for example, the coating liquid composition may be applied to a recording medium to which the ink composition has been applied.

[0079] 2.2.1. Anionic resin particles The anionic resin particles contained in the coating liquid composition are not particularly limited as long as they are usable in an aqueous pigment ink composition. The anionic resin particles may react with an acid compound in the treatment liquid composition to aggregate, thereby forming a coating layer on the ink composition adhered to the recording medium.

[0080] The content of the anionic resin particles in the coating liquid composition is preferably 3 to 30 mass %, 5 to 20 mass %, or 7 to 15 mass %, relative to the total amount of the coating liquid composition. By setting the content of the anionic resin particles within the above range, the effects of the present invention can be more effectively and reliably achieved.

[0081] 2.2.2. Crosslinking Agents The coating liquid composition may contain a crosslinking agent, preferably an anionic crosslinking agent. By containing an anionic crosslinking agent, the aggregation reaction tends to proceed more easily, and the abrasion resistance tends to be further improved. The crosslinking agent may be used alone or in combination of two or more.

[0082] Among the anionic crosslinking agents, for example, oxazoline-based crosslinking agents, isocyanate-based crosslinking agents, carbodiimide-based crosslinking agents, and epoxy-based crosslinking agents can be mentioned, and from the viewpoint of more effectively and reliably exhibiting the effects of the present invention, oxazoline-based crosslinking agents are preferred.

[0083] The oxazoline-based crosslinking agent is not particularly limited, but examples thereof include polymers obtained by homopolymerizing oxazoline-group-containing ethylenically unsaturated monomers such as 2-isopropenyl-2-oxazoline and 2-vinyl-2-oxazoline, or copolymerizing them with other unsaturated monomers. Commercially available oxazoline-based crosslinking agents include EPOCROS (registered trademark) K-2010, K-2020, K-2030, K-2035E, WS-300, WS-500, and WS-700 (all trade names, Nippon Shokubai Co., Ltd.). Among these, EPOCROS WS-700 is preferred from the viewpoint of more effectively and reliably achieving the effects of the present invention.

[0084] The content of the crosslinking agent is preferably 1.0 to 8.0 mass %, 1.5 to 6.0 mass %, or 2.0 to 4.0 mass %, relative to the total amount of the coating liquid. By keeping the content of the crosslinking agent within this range, the effects of the present invention can be more effectively and reliably achieved.

[0085]

[0042] With regard to components other than those mentioned above that may be contained in the coating liquid, such as surfactants, pH adjusters, and organic solvents, the types used in the aqueous pigment ink composition can be used within the same content ranges. Furthermore, as other components, various additives such as metal sealants, softeners, solubilizers, viscosity adjusters, UV absorbers, antioxidants, and corrosion inhibitors may also be contained as needed.

[0086] The inkjet treatment liquid composition and ink set of this embodiment are applied to fabric for recording. Examples of the fabric material include natural fibers such as cotton, linen, wool, and silk, synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, and polyurethane, and biodegradable fibers such as polylactic acid, and blends of these fibers are also acceptable.

[0087] The fabric preferably has a hydroxyl group. Examples of such fabrics include fabrics containing cellulose such as cotton and linen, and fabrics containing polyurethane. When the fabric has a hydroxyl group, a crosslinking reaction can occur between the acidic component contained in the processing liquid composition and the hydroxyl groups of the fabric, which tends to improve color development due to thickening and aggregation, and improve friction fastness due to improved adhesion between the fabric and the recording layer. [Example]

[0088] The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited to the following examples.

[0089] 1 to 6, Tables 1 to 6 are provided showing the constitution of each composition of the examples and comparative examples.

[0090] 1. Preparation of each composition Each component was placed in a mixing tank, mixed and stirred, and filtered through a membrane filter to obtain the treatment liquid composition and inkjet ink composition shown in Tables 1 to 6. The numerical values ​​for each component shown in the tables represent % by mass unless otherwise specified. Furthermore, the numerical values ​​for each content in the tables represent % by mass of the solid content of the active ingredient.

[0091] The abbreviations used for each composition and details of the product ingredients are as follows:

[0092] 1.1. Preparation of treatment liquid composition [Acid compound] Lactic acid (pKa=3.9, carboxyl group, monovalent, boiling point 122°C) Malonic acid (pKa=2.8, 5.7, carboxyl group, divalent, decomposition point 135°C) Citric acid (pKa = 3.1, 4.8, 5.4, carboxyl group, trivalent, decomposition point 175°C) Adipic acid (pKa=4.4, 5.4, carboxyl group, divalent, boiling point 338°C) Succinic acid (pKa=4.2, 5.5, carboxyl group, divalent, boiling point 235°C) Malic acid (pKa=3.4, 5.1, carboxyl group, divalent, decomposition point 150°C) Levulinic acid (pKa=4.6, carboxyl group, monovalent, boiling point 246°C) Propionic acid (pKa=4.7, carboxyl group, monovalent, boiling point 141°C) Sulfuric acid (pKa = -2.0, 1.9, sulfo group, divalent, boiling point 290°C) Phosphoric acid (pKa = 2.0, 6.8, 12.5, phosphate group, divalent, decomposition point 213°C) Hydrochloric acid (pKa<0, monovalent) Glutaric acid (pKa=4.1, 5.0, carboxyl group, divalent, boiling point 200°C) [Basic compounds] 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 Nittobo Medical Co., Ltd.) [Organic solvents] Glycerin (boiling point 290°C) Propylene glycol (boiling point 188°C) Triethylene glycol (boiling point 285°C) 1,2-Hexanediol (boiling point 223°C) Triethylene glycol monobutyl ether (boiling point 278°C) 3-Methoxy-1-butanol (boiling point 158°C) ε-caprolactam (boiling point 270°C) [Surfactants] Surfynol 465 (acetylene glycol, manufactured by Nissin Chemical Industry Co., Ltd.) Naroacty CL-200 (polyoxyethylene alkyl ether, manufactured by Sanyo Chemical Industries, Ltd.) BYK348 (polyether-modified siloxane, manufactured by BYK Japan Co., Ltd.) [water] ·Pure water

[0093] 1.2. Preparation of water-based pigment ink [Pigment] Self-dispersing pigment: The pigment was prepared by the following method. 500 g of carbon black powder (primary particle diameter = 18 nm, BET specific surface area = 180 m) prepared by the furnace method 2 3750 g of ion-exchanged water (100 g / g, DBP absorption = 186 mL / 100 g) was added and heated to 45°C while stirring with a dissolver. Subsequently, the mixture was ground using a sand mill with 0.8 mm diameter zirconia beads, and 30,000 g of an aqueous solution of sodium hypochlorite (available chlorine concentration = 12%) was added dropwise at 45°C over 3.5 hours. Grinding was continued for 30 minutes using the sand mill to obtain a treatment solution containing self-dispersible carbon black. This treatment solution was filtered through a 400-mesh wire screen to separate the zirconia beads, unreacted carbon black, and 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 desalted and purified using an ultrafiltration membrane until the liquid's conductivity reached 1.5 mS / cm. Further desalting and purification were performed using an electrodialysis device until the liquid's conductivity reached 1.0 mS / cm. The liquid was concentrated until the concentration of self-dispersible carbon black reached 17% by mass. The concentrated liquid was centrifuged to remove coarse particles and then filtered through a 0.6 μm filter. Ion-exchanged water was added to the resulting filtrate, and the self-dispersible carbon black was diluted to a concentration of 15% by mass. The resulting mixture was dispersed to obtain a self-dispersible pigment dispersion.

[0094] Resin-dispersed pigment: The pigment was prepared by the following method. To 15 parts by mass of carbon black, 10 parts by mass of ammonium salt of styrene-acrylic acid copolymer (weight average molecular weight 10,000) as a dispersant polymer component and 55 parts by mass of ion-exchanged water were added and mixed thoroughly, and then this mixture was dispersed in a sand mill (manufactured by Yaskawa Corporation) together with glass beads (diameter 1.7 mm, 1.5 times the amount of the mixture) for 2 hours. After dispersion, the glass beads were removed to obtain a resin-dispersed pigment dispersion.

[0095] [resin] Resin dispersion: prepared by the following method. A four-neck flask equipped with a stirrer, condenser, nitrogen inlet, and thermometer was charged with 322.2 g of polytetramethylene ether glycol (number average molecular weight 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. The mixture was then reacted at 80°C for 6 hours under a nitrogen gas atmosphere. The mixture was then cooled to 60°C, and 12.5 g of triethylamine was added. The mixture was then mixed 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 removed under reduced pressure at 40°C to obtain a polyurethane resin dispersion containing carboxyl groups as acidic groups.

[0096] [Organic solvents] Glycerin 1,2-Hexanediol [Surfactants] Surfynol 465 (trade name, acetylene glycol surfactant, manufactured by Nissin Chemical Industry Co., Ltd.) [pH adjuster] Triethanolamine [water] ·Pure water

[0097] 1.3. Preparation of coating solution [resin] Resin dispersion: The resin dispersion used in preparing the water-based pigment ink was used. [Crosslinking agent] Epocross WS-700 (product name, oxazoline crosslinking agent, manufactured by Nippon Shokubai Co., Ltd.) [Organic solvents] Glycerin 1,2-Hexanediol [Surfactants] Surfynol 465 (trade name, acetylene glycol surfactant, manufactured by Nissin Chemical Industry Co., Ltd.) [pH adjuster] Triethanolamine [water] ·Pure water

[0098] 2.Calculation method

[0099] 2.1. Molar concentration of the acidic group of the compound, C A and the molar mass concentration of basic groups, C B How to calculate Molar concentration of the acidic group of the acid compound, C A was calculated using the following formula: C A = (amount of acid compound added [mass %]) × (number of acidic groups with pKa of 7 or less per acid molecule) × 10 / (molecular weight of acid compound [g / mol])

[0100] Molar concentration of the basic group of the basic compound, C B was calculated from the following formula: C B = (amount of basic compound added [mass %]) × (number of hydroxyl groups or amino groups in one base molecule) × 10 / (molecular weight of basic compound [g / mol])

[0101] 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 nature of the group with the larger number. For example, in the case of L-aspartic acid as an acidic amino acid, the concentration 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 acid compound, aspartic acid has a molar concentration of acidic groups, C, as shown in the following formula: Acan be calculated. Ca = (amount of acidic compound added [mass %]) × {(number of acidic groups with pKa of 7 or less per molecule of acidic compound) - (number of basic groups per molecule of acidic compound)} × 10 / (molecular weight of acidic compound [g / mol]) When the amount of aspartic acid added is 10% by mass, the results are as follows. Ca=10×(2-1)×10 / 133.10≒0.751

[0102] The molecular weight and valence of compounds whose molecular weight or the number of acidic groups (or basic groups) is unknown were calculated by the following method.

[0103] 2.2. Calculation method for molecular weight and valence of compounds whose molecular weight and number of acidic (or basic) groups are unknown 0.30 g of a compound with unknown molecular weight and number of acidic groups (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, and the solution was stirred with a magnetic stirrer. The pH of the solution was then measured using a pH meter (F-72, manufactured by HORIBA). The procedure was repeated until the pH of the solution reached 8.0 (or 6.0), at which point neutralization was determined, and the repetition process was terminated. From these results, the amount of acid compound (or basic compound) required to neutralize 1 g of 100 wt% sodium hydroxide (or 1 g of sulfuric acid) was calculated using the following formula: x (or b x )(g) was calculated. a x = 0.30g / (100wt% sodium hydroxide added amount g) b x = 0.30g / (100wt% sulfuric acid added amount g)

[0104] Here, (amount of 100 wt% sulfuric acid added in g) = (amount of 10 wt% sulfuric acid added in g) / 10, and (amount of 100 wt% sulfuric acid added in g) = (amount of 10 wt% sulfuric acid added in g) / 10. Next, the above operation is carried out on a 1 wt% aqueous sulfuric acid solution (or a 1 wt% aqueous sodium hydroxide solution), and the amount of sulfuric acid (or potassium hydroxide) required to neutralize 1 g of 100 wt% sodium hydroxide (or 100 wt% sulfuric acid) is calculated as follows: 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

[0105] 3.Printing method Using a modified ML-8000 (manufactured by Seiko Epson Corporation) device, printing was performed by ejecting the treatment liquid composition and water-based pigment ink from the head in the same pass onto 100% cotton white broadcloth (#4000, manufactured by Nisshinbo Co., Ltd.) or polyester cloth, and after main scanning was performed multiple times (2 times, 4 times, 8 times, 12 times, or 16 times) on the same scanning area, a coating liquid was then printed in the same manner, thereby forming a 20 cm x 5 cm solid pattern image on the fabric, which was the recording medium. The amount of adhesion of each liquid was 10 mg / inch for the treatment liquid composition. 2 , water-based pigment ink is 30mg / inch 2 , coating liquid is 20mg / inch 2 After image formation, the image was heated in an oven at 160°C for 5 minutes and dried to produce printed textiles for each example and comparative example. Note that "solid pattern image" refers to an image in which dots are formed uniformly over the entire surface of the recording area (main scanning direction x sub-scanning direction: 20 cm x 5 cm) so that the application amount of each liquid satisfies the above numerical values. The inkjet head used was a head unit with a nozzle distance of 600 dpi in the sub-scanning direction, two head chips arranged in the sub-scanning direction, and a nozzle length of 2 inches.

[0106] 4. Evaluation Method 4.1.Irritation alleviation A 15cm x 3.2cm area of ​​the printed image was cut out from cotton fabric using the above printing method, cut into 5mm-wide pieces, and placed in a glass bottle with 35mL of pure water. Extraction was then performed by stirring for 2 hours using a magnetic stirrer. The pH of the extract was then measured using a pH meter (F-72, manufactured by HORIBA). This procedure was repeated three times, and the average pH value was used to evaluate the results according to the following criteria. (Evaluation criteria) S: Average pH is 4.7 or higher A: The average pH is between 4.4 and 4.7. B: The average pH is 4.2 or more but less than 4.4 C: Average pH is less than 4.2

[0107] 4.2. Rubbing resistance (cotton fabric, polyester fabric) Printed textiles were produced on cotton and polyester fabrics using the above printing method. Using a crockmeter (FI-306, Tester Sangyo Co., Ltd.), a gold cloth (white cotton cloth) was rubbed 10 times on the image on the printed textile at a load of 9 N. The ink-stained area of ​​the rubbed gold cloth was then measured for black optical density (OD, Status E) of the printed image using a colorimeter (FD-7, Konica Minolta Inc.), and evaluated according to the following criteria: (Evaluation criteria) SS:OD is 0.22 or less S:OD is greater than 0.22 and less than 0.31 A: OD is over 0.31 and 0.4 or less B: OD is greater than 0.4 and less than 0.5 C:OD > 0.5

[0108] 4.3.Storage stability of processing solution Each treatment liquid composition obtained above was left to stand for 3 days in an environment at a temperature of 60°C. Then, after another day of standing at room temperature, the presence or absence of phase separation was confirmed. Furthermore, the composition was stirred, and the change in transparency was visually observed and evaluated according to the following criteria. (Evaluation criteria) A: No separation of the oil and water layers was observed, and no turbidity was observed even after stirring. C: Separation of the oil and water layers was observed, or the transparency decreased and the color became cloudy after stirring.

[0109] 4.4.Clogging recovery of processing liquid Each treatment liquid composition obtained above was filled into an ink cartridge of an inkjet printer PX-G930 (product name, manufactured by Seiko Epson Corporation), and continuous ejection was performed from all nozzles for 3 minutes. After ejection, the printer was left to stand for 2 weeks at a temperature of 40°C and a relative humidity of 20%. Thereafter, the head was cleaned by suctioning the treatment liquid from the nozzles once to check whether there were any nozzles that could not eject the treatment liquid, and then the cleaning operation was performed again to check whether all nozzles had recovered. Based on the results, evaluation was performed according to the following criteria. (Evaluation criteria) A: There is no clogging, or it was resolved with one cleaning. C: Clogging occurred and was resolved after two or more cleanings, or was not resolved at all.

[0110] The ejection reliability of all water-based pigment inks was good, but the ink of Example 25, which used Ink1-2 (resin-dispersed pigment), had slightly inferior ejection reliability (clogging) compared to the ink of Example 6, which used Ink1-1 (self-dispersed pigment).

[0111] 5. Evaluation Results From Tables 1 to 6, there are shown inkjet treatment liquid compositions that are used by being attached to a recording medium, and that contain an acid compound, a base compound, and water, and the acid compound has a pKa in water at 25°C of at least 2.5 or more and 7.0 or less, and in the inkjet treatment liquid composition, the molar concentration C A (mol / kg) and the molar mass concentration C of the basic group derived from the above basic compound B (mol / kg) (C A -C B) is 0.01 or more and the pH at 25°C is 2.5 to 6.5, the obtained printed textile is excellent in irritation relief and rub fastness.

Claims

1. A treatment liquid composition for inkjet use by being applied to a recording medium, comprising: Contains an acid compound, a base compound, and water, the acid compound has a pKa in water at 25°C of at least 2.5 or more and 7.0 or less; In the inkjet treatment liquid composition, the molar concentration C of the acidic group derived from the acid compound Ａ (mol / kg), and the molar mass concentration C of the basic group derived from the basic compound Ｂ (mol / kg) (C Ａ -C Ｂ ) is 0.01 or more, The pH at 25°C is 2.5 or more and 6.5 or less. An inkjet treatment liquid composition.

2. The mass molarity C Ａ (mol / kg) and the molar mass concentration C Ｂ (mol / kg) (C Ａ -C Ｂ ) is 5.0 or less; The inkjet treatment liquid composition according to claim 1 .

3. the basic compound includes a hydroxide of one or more metals selected from the group consisting of Li, Na, K, Ca, Mg, and Al, or an amine compound; The inkjet treatment liquid composition according to claim 1 .

4. the basic compound includes a hydroxide of one or more metals selected from the group consisting of Ca, Mg, and Al, or an amine compound containing 2 to 10 nitrogen atoms in the molecule; The inkjet treatment liquid composition according to claim 1 .

5. Contains two or more of the basic compounds, The inkjet treatment liquid composition according to claim 1 .

6. The normal boiling point or the thermal decomposition point at atmospheric pressure of the acid compound is 170°C or less. The inkjet treatment liquid composition according to claim 1 .

7. The acid compound includes at least one selected from the group consisting of lactic acid, levulinic acid, malic acid, malonic acid, citric acid, phosphoric acid, succinic acid, glutaric acid, and adipic acid. The inkjet treatment liquid composition according to claim 1 .

8. The acid compound has a pKa in water at 25°C of at least 4.5 or more and 6.5 or less. The inkjet treatment liquid composition according to claim 1 .

9. the acidic group includes one or more groups selected from the group consisting of a carboxyl group, a sulfo group, and a phosphate group, and the basic group includes one or more groups selected from the group consisting of a hydroxyl group and an amino group; The inkjet treatment liquid composition according to claim 1 .

10. the inkjet treatment liquid composition contains a nonionic surfactant and a water-soluble organic solvent, the water-soluble organic solvent contains one or more of a diol compound having 4 or more carbon atoms and a glycol ether having 4 or more carbon atoms; The inkjet treatment liquid composition according to claim 1 .

11. the content of the water-soluble organic solvent is 30% by mass or less relative to the total amount of the inkjet treatment liquid composition; The inkjet treatment liquid composition according to claim 10.

12. The molar concentration C of the acidic group Ａ (mol / kg) is 0.3 mol / kg or more with respect to the total amount of the inkjet treatment liquid composition, The inkjet treatment liquid composition according to claim 1 .

13. the inkjet treatment liquid composition contains a water-soluble organic solvent having a normal boiling point of 280°C or higher in an amount of 5.0% by mass or more relative to the total amount of the inkjet treatment liquid composition; The inkjet treatment liquid composition according to claim 1 .

14. The inkjet treatment liquid composition according to any one of claims 1 to 13, a water-based pigment ink composition containing an anionic dispersed pigment and anionic resin particles; Ink set.

15. The dispersed pigment is a self-dispersed pigment. The ink set according to claim 14.

16. The resin particles have acidic groups. The ink set according to claim 14.

17. The coating composition further includes an aqueous coating liquid composition, the aqueous coating liquid composition including anionic resin particles and being substantially free of pigments. The ink set according to claim 14.

18. the aqueous coating liquid composition contains an anionic crosslinking agent; The ink set according to claim 17.

Images