Processing liquid composition and ink set

Abstract

The present invention provides a processing liquid composition that produces recorded materials with excellent color development and friction resistance, while also suppressing corrosion of internal components of the recording device. [Solution] A processing liquid composition used by ejection by an inkjet method, containing an acid compound, water, and a rust inhibitor, having a pH of 6.5 or less at 25°C, and having a molal concentration of acidic groups derived from the acid compound C A (mol / kg) and the molal concentration C of the basic group derived from the basic compound B The difference from (mol / kg) (C A -C B ) is 0.1 mol / kg or more (however, 0 <C A , 0≦C B ), processing liquid composition.

Description

[Technical Field]

[0001] This invention relates to a processing liquid composition and an ink set. [Background technology]

[0002] Inkjet recording methods are rapidly developing in various fields because they enable the recording of high-resolution images with relatively simple equipment. In this context, various studies have been conducted on color development and wash fastness. For example, Patent Document 1 discloses an inkjet processing solution containing a cationic polymer and lactic acid, with a halogen ion concentration of 5 g / L or less and a pH of 7 to 9.5. Also, for example, Patent Document 2 discloses an inkjet processing solution containing a water-soluble cationic polymer and an organic acid salt, in which the content of the water-soluble cationic polymer is 0.1% by weight or more and less than 10% by weight of the total processing solution. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] WO2022 / 131245 [Patent Document 2] WO2023 / 042761 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] However, when using processing liquid compositions obtained by conventional configurations such as those described in Patent Documents 1 and 2, there was room for improvement in the color development, friction fastness, and corrosiveness of the resulting printed materials. [Means for solving the problem]

[0005] The treatment liquid composition of the present invention is a treatment liquid composition that is ejected and used by an inkjet method, contains an acid compound, water, and a rust inhibitor, has a pH of 6.5 or less at 25°C, and has a molal concentration C of acidic groups derived from the acid compound A (mol / kg) and a molal concentration C of basic groups derived from a base compound B (mol / kg), the difference (C A -C B ) is 0.1 mol / kg or more (provided that 0<C A , 0≦C B ).

[0006] The ink set of the present invention includes the treatment liquid composition of the present invention and an inkjet ink composition containing resin particles and water. [Brief Description of the Drawings]

[0007] [Figure 1] This is Table 1 showing the compositions of the composition sets used in the examples and their evaluation results. [Figure 2] This is Table 2 showing the compositions of the composition sets used in the examples and their evaluation results. [Figure 3] This is Table 3 showing the compositions of the composition sets used in the examples and their evaluation results. [Figure 4] This is Table 4 showing the compositions of the inks used in the examples. [Mode for Carrying Out the Invention]

[0008] Hereinafter, embodiments of the present invention (hereinafter referred to as "the present embodiment") will be described in detail with reference to the drawings as necessary, but the present invention is not limited thereto, and various modifications are possible without departing from the gist of the present invention.

[0009] Conventionally, acid compounds used as flocculants in treatment liquids are important components that affect the color developability and wet rub fastness of recorded matter. In particular, the type and concentration of the acid compound, as well as the interaction with the base component, require careful consideration for forming an optimal flocculation state. On the other hand, since treatment liquids containing acid compounds exhibit corrosiveness to metal components of recording apparatuses, recording media, and the like, detailed studies have been demanded from the viewpoint of suppressing corrosion of the recording apparatus in addition to improving the color developability and wet rub fastness of recorded matter.

[0010] In the present invention, a treatment liquid composition to be used by being discharged by an inkjet method contains an acid compound, water, and a rust inhibitor, has a pH of 6.5 or less at 25°C, and has a molal concentration C of acidic groups derived from the acid compound A (mol / kg) and a molal concentration C of basic groups derived from the base compound B (mol / kg) (C A -C B ) of 0.1 mol / kg or more (provided that 0<C A and 0≦C B ), it has been found that the recorded matter is excellent in color developability and wet rub properties, and corrosion of members inside the recording apparatus can also be suppressed.

[0011] This is considered to be because setting the difference in concentration between the acid compound and the base compound to a predetermined amount or more promotes the flocculation reaction by the acid compound, thereby improving the color developability. In addition, in the treatment liquid composition containing an acid compound, the acid compound can undergo a neutralization reaction with an anionic component contained in the ink on the recording medium to reduce the hydrophilicity of the anionic component, and thus it is considered that the wet rub fastness of the recorded matter is improved. On the other hand, the use of an excessive acid compound increases the risk of corrosion, but simply adding a rust inhibitor may degrade print quality such as color developability and bleeding. Therefore, it is presumed that color developability, rub fastness, and corrosion resistance can be achieved at the same time by adding the rust inhibitor after controlling the pH at 25°C. However, the factor is not limited to those described above.

[0012] The following details each component of the processing solution composition and the composition included in the ink set.

[0013] 1. Processing liquid composition The processing liquid composition according to this embodiment (hereinafter also simply referred to as "processing liquid composition") is used by ejection by an inkjet method, contains an acid compound, water, and a rust inhibitor, has a pH of 6.5 or less at 25°C, and the molal concentration of the acidic group derived from the acid compound is C A (mol / kg) and the molal concentration C of the basic group derived from the basic compound B The difference from (mol / kg) (C A -C B ) is 0.1 mol / kg or more (however, 0 <C A , 0≦C B The treatment solution composition may or may not contain a basic compound.

[0014] The treatment liquid composition has a pH of 6.5 or less at 25°C, which prevents a decrease in color development due to the addition of rust inhibitors and allows for a balance of corrosion resistance, color development, and friction fastness in recorded materials. From a similar viewpoint, the pH of the treatment liquid composition at 25°C is preferably 6.0 or less, more preferably 5.0 or less, even more preferably 4.0 or less, and even more preferably 3.0 or less.

[0015] The processing solution composition is for use in textile printing, and it is preferable to use it by attaching it to a fabric as a recording medium. The processing solution composition for textile printing provides excellent color development and friction fastness for the recorded material, while also ensuring corrosion resistance for the components of the recording device. Examples of fabrics 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. Blends of these fibers may also be used. In this embodiment, the fabric includes not only woven fabrics but also knitted fabrics.

[0016] 1.1. Acid compounds Examples of acid compounds include organic acids and inorganic acids. From the viewpoint of further improving the wet friction fastness of the printed material, it is preferable to use organic acids. One acid compound may be used alone, or two or more may be used in combination.

[0017] The acid compound preferably has a pKa in water at 25°C between 2.0 and 7.0. Having the pKa of the acid compound in water at 25°C within the above range allows it to exhibit buffering capacity in the pH range of 2.5 to 6.5, and also allows for a lower neutralization rate with base compound A, resulting in excellent wet friction fastness and a tendency for improved irritation mitigation. From a similar viewpoint, the pKa of the acid compound at 25°C is more preferably between 2.2 and 6.5, even more preferably between 2.5 and 6.0, and even more preferably between 2.8 and 5.8. When a compound has its pKa within a certain range, if it has a single pKa, it means that the pKa is within the specified range, and if it has multiple pKas, it means that one or more of the pKas are within the relevant range.

[0018] Suitable acid compounds include, for example, lactic acid, malonic acid, citric acid, adipic acid, succinic acid, malic acid, levulinic acid, phosphoric acid, glutaric acid, polyacrylic acid, acetic acid, glycolic acid, maleic acid, ascorbic acid, fumaric acid, tartaric acid, sulfonic acid, orthophosphoric acid, pyrrolidone carboxylic acid, pyrrone carboxylic acid, pyrrole carboxylic acid, furanic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, or derivatives of these compounds, or salts thereof. Among these, the acid compound preferably contains one or more selected from the group consisting of lactic acid, acetic acid, levulinic acid, malic acid, malonic acid, glutaric acid, citric acid, phosphoric acid, succinic acid, adipic acid, and dimethylolpropionic acid; more preferably contains one or more selected from the group consisting of lactic acid, acetic acid, levulinic acid, malic acid, malonic acid, glutaric acid, and citric acid; and even more preferably contains one or more selected from the group consisting of lactic acid, acetic acid, and levulinic acid. The inclusion of such acid compounds tends to make the effects of the present invention on improving color development and friction fastness even more effective and reliable.

[0019] In the treatment solution composition, the molal concentration C of the acidic group derived from the acid compound A The mol / kg is preferably 0.05 or more and 4.0 or less. A By keeping it within the above range, the effects of color development, friction fastness, and corrosion resistance according to the present invention tend to be achieved more effectively and reliably. From a similar viewpoint, molal concentration C A The (mol / kg) is more preferably 0.10 to 3.0, even more preferably 0.20 to 2.5, and even more preferably 0.30 to 2.4.

[0020] The content of the acid compound is preferably 0.1% by mass or more and 50% by mass or less based on the total amount of the treatment liquid composition. By keeping the content of the acid compound within the above range, the effects of color development, friction fastness, and corrosion resistance according to the present invention tend to be more effective and reliable. From a similar viewpoint, the content of the acid compound is more preferably 0.5% by mass or more and 40% by mass or less, even more preferably 1.0% by mass or more and 30% by mass or less, and still more preferably 2.0% by mass or more and 20% by mass or less, based on the total amount of the treatment liquid composition.

[0021] 1.2. Basic Compounds The treatment solution composition may contain a base compound. Examples of base compounds include organic bases and inorganic bases. Among organic and inorganic bases, metal hydroxides or amine compounds are preferred. Using such base compounds tends to make the effects of improving color development and friction fastness according to the present invention more effective and reliable. From a similar viewpoint, alkali metal hydroxides, alkaline earth metal hydroxides, or amine compounds are more preferred, and alkali metal hydroxides are even more preferred. Note that one type of base compound may be used alone, or two or more types may be used in combination.

[0022] The metal constituting the metal hydroxide is preferably one or more selected from the group consisting of Li, Na, K, Ca, Mg, and Al. Using such a metal hydroxide tends to make the effects of improving color development and friction fastness according to the present invention more effective and reliable. From a similar viewpoint, the metal constituting the metal hydroxide is more preferably one or more selected from the group consisting of Na, K, Ca, Mg, and Al, more preferably Na or K, and even more preferably K.

[0023] The amine compound is one or more selected from the group consisting of alkanolamine compounds, polyhydric amine compounds, and polyamine compounds. Examples of alkanolamine compounds include triethanolamine, trippropanolamine, triisopropanolamine, and triputanolamine. Examples of polyhydric amine compounds include diethylenetriamine, dipropylenetriamine, dihexylentriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and hexaethyleneheptamine.

[0024] In the treatment solution composition, the molal concentration C of the basic group derived from the basic compound B The mol / kg is preferably between 0.0 and 3.0. B By keeping it within the above range, the effects of color development, friction fastness, and corrosion resistance according to the present invention tend to be achieved more effectively and reliably. From a similar viewpoint, molal concentration C B The (mol / kg) is more preferably 0.0 to 2.0, even more preferably 0.0 to 1.6, and even more preferably 0.0 to 1.0.

[0025] In the treatment solution composition, the molal concentration C of the acidic group derived from the acid compound A (mol / kg) and the molal concentration C of the basic group derived from the basic compound B The difference from (mol / kg) (C A -C B By setting the concentration to 0.1 mol / kg or higher, the resulting recording will have excellent color development and friction fastness. From a similar viewpoint, the above difference (C A -C B The ratio is preferably 0.11 mol / kg or more, and more preferably 0.3 mol / kg or more. Also, the above difference (C A -C B The concentration of ) may be 2.0 mol / kg or less, 1.5 mol / kg or less, or 1.2 mol / kg or less.

[0026] The content of the basic compound is preferably 0.0% by mass or more and 20% by mass or less based on the total amount of the treatment solution composition. By keeping the content of the basic compound within the above range, the effects of color development, friction fastness, and corrosion resistance according to the present invention tend to be more effective and reliable. From a similar viewpoint, the content of the basic compound is more preferably 0.0% by mass or more and 10% by mass or less based on the total amount of the treatment solution composition, and even more preferably 0.0% by mass or more and 5.0% by mass or less.

[0027] 1.3. Rust Inhibitor Examples of rust inhibitors include water-soluble rust inhibitors and oil-soluble rust inhibitors. From the viewpoint of achieving the corrosion resistance effect according to the present invention more effectively and reliably, water-soluble rust inhibitors are preferred. Note that one type of rust inhibitor may be used alone, or two or more types may be used in combination.

[0028] The rust inhibitor preferably contains one or more selected from the group consisting of amino acids, carboxylates, aliphatic carboxylic acids, triazoles, thiazoles, imidazoles, phosphates, borates, sulfonates, and phosphonates. Including such a rust inhibitor tends to make the corrosion resistance effect of the present invention more effective and reliable. From a similar viewpoint, it is more preferable to include one or more selected from the group consisting of amino acids, carboxylates, aliphatic carboxylic acids, triazoles, thiazoles, imidazoles, and phosphates, and even more preferable to include one or more selected from the group consisting of amino acids, carboxylates, aliphatic carboxylic acids, and triazoles.

[0029] The rust inhibitor content is preferably 0.01% by mass or more and 8.0% by mass or less based on the total amount of the treatment liquid composition. By keeping the rust inhibitor content within the above range, the color development, friction fastness, and corrosion resistance effects of the present invention tend to be more effective and reliable. From a similar viewpoint, the rust inhibitor content is more preferably 0.03% by mass or more and 5.0% by mass or less based on the total amount of the treatment liquid composition, and even more preferably 0.05% by mass or more and 3.0% by mass or less. Furthermore, from a similar viewpoint, the content of triazoles is preferably 0.01% by mass or more and 1.0% by mass or less relative to the total amount of the treatment solution composition, the content of amines is preferably 0.5% by mass or more and 1.0% by mass or less and 2.0% by mass or less, and the content of carboxylates is preferably 0.25% by mass or more and 3.0% by mass or less.

[0030] 1.4. Resin The treatment liquid composition may contain a resin. Preferably, the resin is a cationic polymer having cationic properties. The inclusion of a cationic polymer tends to make the effects of improving friction resistance and corrosion resistance more effective and reliable. Examples of cationic polymers include cationic acrylic resins, cationic urethane resins, cationic olefin resins, and cationic amine resins. Among these cationic polymers, cationic acrylic resins and cationic amine resins are preferred, and cationic acrylic resins are more preferred.

[0031] Cationic amine resins can be any resin containing amino groups, such as allylamine resins, polyamine resins, quaternary ammonium salt polymers, and polyamide resins. Polyamine resins include those having amino groups in the main skeleton of the resin. Allylamine resins include those having a structure derived from allyl groups in the main skeleton of the resin. As for cationic acrylic resins, commercially available examples include the Movinyl series manufactured by Japan Coating Resin Co., Ltd.

[0032] The treatment solution composition, by containing a cationic polymer resin, tends to improve the adhesion between the fabric and the ink layer, resulting in a more effective and reliable improvement in friction fastness. Cationic polymers may contain halide ions as counterions, and halide ions tend to accelerate corrosion. However, according to the treatment solution composition of this embodiment, corrosion resistance can be improved by including a rust inhibitor, so even if the treatment solution composition contains halide ions, good corrosion resistance can be achieved. From this perspective, the halide ion content may be 1 ppm or more, 2 ppm or more, or 5 ppm or more relative to the total amount of the treatment solution composition. Furthermore, the halide ion content is preferably 300 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less, relative to the total amount of the treatment solution composition.

[0033] 1.5. Organic Solvents The processing liquid composition preferably contains an organic solvent. The inclusion of an organic solvent tends to improve ejection stability when ejected by the inkjet method. Examples of organic solvents include polyhydric alcohols, glycol ethers, nitrogen-containing solvents, esters, and cyclic esters. Among these, from the viewpoint of more effectively and reliably achieving corrosion resistance and ejection stability, an organic solvent with moisturizing properties is preferred, and a composition containing at least one of polyhydric alcohols and glycol ethers is more preferable. Note that the organic solvent may be used alone or in combination of two or more.

[0034] 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 achieving a more effective and reliable discharge stability, it is preferable to include one or more selected from the group consisting of glycerin, propylene glycol, and triethylene glycol, and it is even more preferable to include propylene glycol.

[0035] 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.

[0036] The content of the organic solvent is preferably 5.0% by mass or more and 50% by mass or less based on the total amount of the treatment liquid composition. By keeping the content of the organic solvent within the above range, the discharge stability and corrosion resistance effects of the present invention tend to be more effective and reliable. From a similar viewpoint, the content of the organic solvent is more preferably 10% by mass or more and 40% by mass or less based on the total amount of the treatment liquid composition, and even more preferably 15% by mass or more and 30% by mass or less. From a similar viewpoint, the content of polyhydric alcohols is also preferably 5.0% by mass or more and 50% by mass or less, 10% by mass or more and 40% by mass or less, and 15% by mass or more and 30% by mass or less based on the total amount of the treatment liquid composition.

[0037] 1.6. Surfactants The processing solution 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 processing solution composition is ejected by the inkjet method, nonionic surfactants are preferred. Nonionic surfactants are also preferred because they tend to be stable even in processing solution compositions containing acid compounds and base compounds. One type of surfactant may be used alone, or two or more types may be used in combination.

[0038] Examples of nonionic surfactants include acetylene glycol-based surfactants, alcohol ethoxylate-based surfactants, fluorine-based surfactants, and silicone-based surfactants. Examples of acetylene glycol-based surfactants are not particularly limited, but include one or more selected from 2,4,7,9-tetramethyl-5-decine-4,7-diol and alkylene oxide adducts of 2,4,7,9-tetramethyl-5-decine-4,7-diol, and 2,4-dimethyl-5-decine-4-ol and alkylene oxide adducts of 2,4-dimethyl-5-decine-4-ol.

[0039] Examples of commercially available acetylene glycol-based surfactants include the E series (product names of Air Products Co., Ltd.), such as the Olfin 104 series and Olfin E1010, and Surfinol 61, 104, and 465 (product names of Nisshin Chemical Industry Co., Ltd.). Among these, Olfin E1010 is preferred from the viewpoint of achieving a more effective and reliable discharge stability effect.

[0040] Alcohol ethoxylate surfactants are compounds in which a polyoxyethylene chain and an alkyl group are linked by an ether bond, and "R A -O-(CH2CH2O) d It can be represented by the molecular formula "-H" and is sometimes called a poly(oxyethylene) alkyl ether.

[0041] Examples of silicone-based surfactants include polysiloxane compounds and polyether-modified organosiloxanes. Examples of commercially available silicone-based surfactants include BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK-348, BYK-349 (all product names, manufactured by Bic Chemie Japan Co., Ltd.), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017 (all product names, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0042] Examples of fluorinated surfactants include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphate esters, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines, and perfluoroalkylamine oxide compounds.

[0043] The surfactant content is preferably 0.01 to 3.0% by mass, 0.03 to 2.0% by mass, or 0.05 to 1.0% by mass, relative to the total amount of the treatment liquid composition. By keeping the surfactant content within the above range, the discharge stability and corrosion resistance effects of the present invention tend to be achieved more effectively and reliably.

[0044] 1.7.Water The processing liquid composition contains water. Preferably, the water is one from which ionic impurities have been removed as much as possible. Examples of such water include pure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water, as well as ultrapure water.

[0045] The water content is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and even more preferably 50 to 75% by 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 achieved more effectively and reliably.

[0046] 1.8. Other Ingredients The processing liquid composition may contain, as necessary, various additives other than those mentioned above, such as softeners, solubilizers, viscosity modifiers, ultraviolet absorbers, antioxidants, and corrosion inhibitors. Furthermore, the processing liquid composition is not an ink and is not intended to color itself. Therefore, it substantially does not contain colorants. The colorant content may be 0.5% by mass or less, 0.1% by mass or less, and preferably 0.0% by mass, relative to the total amount of the processing liquid composition.

[0047] 2. Ink Set The ink set of this embodiment (hereinafter also referred to as "this ink set") comprises the above-described processing liquid composition and an inkjet ink composition containing resin particles and water. Because the above-described processing liquid composition is used, the resulting recorded material has excellent color development and friction fastness, and corrosion of recording device components during recording can also be suppressed. One type of inkjet ink composition may be used alone, or two or more types may be used in combination.

[0048] 2.1. Clear Ink Composition This ink set preferably includes a clear ink composition that does not contain pigment as an inkjet ink composition. Including a clear ink composition tends to further improve the friction fastness of the recorded material. The clear ink composition may be applied, for example, to a recording medium to which another inkjet ink composition is attached.

[0049] 2.1.1. Resin particles Anionic resin particles are preferred as the resin particles. Including anionic resin tends to make the color development, friction fastness, and corrosion resistance effects of the present invention more effective and reliable. Examples of anionic resin particles include those in which the resin constituting the resin has anionic groups. Examples of anionic groups include sulfonic acid groups, carboxyl groups, phosphoric acid groups, and hydroxyl groups, but acidic groups are preferred. Using resin particles with acidic groups tends to make the effects of the present invention more effective and reliable. The resin particles are particles containing resin, and can be used in either an emulsion state or a solution state, but from the viewpoint of suppressing an increase in ink viscosity, it is preferable to use them in an emulsion state.

[0050] More specifically, examples of anionic resin particles include urethane resin, polycarbonate resin, (meth)acrylic resin, styrene resin, silicone resin, styrene-acrylic resin, fluorene resin, polyolefin resin, rosin-modified resin, terpene resin, polyester resin, polyamide resin, epoxy resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, and ethylene vinyl acetate resin. Among these, styrene-acrylic resin or urethane resin is preferred, and urethane resin is more preferred, from the viewpoint of achieving the effects of the present invention more effectively and reliably.

[0051] The resin particle (solid content) content is preferably 2.0% by mass or more and 30% by mass or less based on the total amount of the clear ink composition. When the resin particle content is within the above range, the effects of color development, friction fastness, and corrosion resistance according to the present invention tend to be more effective and reliable. From a similar viewpoint, the resin particle content is more preferably 5.0% by mass or more and 25% by mass or less based on the total amount of the clear ink composition, and even more preferably 12% by mass or more and 20% by mass or less.

[0052] 2.1.2. Organic Solvents The clear ink composition may contain an organic solvent. The organic solvent is not particularly limited as long as it is water-soluble, and the same type as that used in the processing solution may be used. Preferably, it is a polyhydric alcohol and a glycol ether. Among the polyhydric alcohol and glycol ether organic solvents, it is preferable to include one or more selected from the group consisting of triethylene glycol, triethylene glycol monobutyl ether, and propylene glycol.

[0053] The content of the organic solvent in the clear ink composition is preferably 10% by mass or more and 50% by mass or less based on the total amount of the clear ink composition. When the content of the organic solvent is within the above range, the effects of color development, friction fastness, and corrosion resistance according to the present invention tend to be more effective and reliable. From a similar viewpoint, the content of the organic solvent is more preferably 20% by mass or more and 40% by mass or less based on the total amount of the clear ink composition, and even more preferably 25% by mass or more and 35% by mass or less.

[0054] 2.1.3. Surfactants The clear ink composition may contain a surfactant. Examples of surfactants include acetylene glycol-based surfactants, fluorine-based surfactants, and silicone-based surfactants, with silicone-based surfactants being preferred. By using a silicone-based surfactant, the effects of the present invention can be achieved more effectively and reliably.

[0055] Examples of commercially available silicone-based surfactants include those exemplified in section 1.6 above. Among these, BYK-348 is preferred from the viewpoint of more effectively and reliably achieving the color development, friction fastness, and corrosion resistance effects of the present invention.

[0056] The surfactant content in the clear ink composition is preferably 0.1 to 5% by mass, 0.2 to 3% by mass, or 0.3 to 1% by mass, relative to the total amount of the clear ink composition. By keeping the surfactant content within the above range, the effects of the present invention can be achieved more effectively and reliably.

[0057] 2.1.4.Water The clear ink composition contains water. Preferably, the water is free of ionic impurities as much as possible. 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.

[0058] The water content is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and even more preferably 45 to 70% by mass, relative to the total amount of the clear ink composition. By keeping the water content in the processing solution within the above range, the effects of the present invention can be achieved more effectively and reliably.

[0059] In addition to the above-mentioned components, the clear ink composition may optionally contain various additives such as metal sealants, softeners, solubilizers, viscosity modifiers, ultraviolet absorbers, antioxidants, and corrosion inhibitors.

[0060] 2.2. Colored Ink Compositions This ink set preferably includes a colored ink composition containing a pigment as an inkjet ink composition. Including a colored ink composition tends to further improve the color development of the recorded material.

[0061] 2.2.1. Pigments The pigment preferably includes a pigment dispersed with an anionic dispersant. Including a pigment dispersed with an anionic dispersant tends to make the friction fastness effect of the present invention more effective and reliable. The pigment may be used alone or in combination of two or more types.

[0062] More specifically, examples of pigments include inorganic pigments and organic pigments. As inorganic pigments, in addition to titanium dioxide and iron oxide, carbon black produced by known methods such as the contact method, furnace method, and thermal method can be used. On the other hand, as organic pigments, examples include azo pigments, polycyclic pigments, nitro pigments, nitroso pigments, and aniline black. Examples of azo pigments include azo lakes, insoluble azo pigments, condensed azo pigments, and chelated azo pigments.

[0063] The pigment (solid content) content is preferably 1.0% by mass or more and 30% by mass or less based on the total amount of the colored ink composition. By keeping the pigment content within the above range, the effects of color development and friction fastness in the present invention tend to be more effective and reliable. From a similar viewpoint, the pigment content is more preferably 2.0% by mass or more and 20% by mass or less, more preferably 5.0% by mass or more and 20% by mass or less, and even more preferably 6.0% by mass or more and 15% by mass or less, based on the total amount of the colored ink composition.

[0064] 2.2.2. Resin particles As resin particles, those similar to those used in the clear ink composition described above can also be preferably used.

[0065] The resin particle content in the colored ink composition is preferably 2.0% by mass or more and 30% by mass or less, relative to the total amount of the colored ink composition. When the resin particle content is within the above range, the effects of color development, friction fastness, and corrosion resistance according to the present invention tend to be more effective and reliable. From a similar viewpoint, the resin particle content is more preferably 3.0% by mass or more and 20% by mass or less, and even more preferably 4.0% by mass or more and 15% by mass or less, relative to the total amount of the colored ink composition.

[0066] 2.2.3. Organic Solvents The colored ink composition may contain an organic solvent. The organic solvent is not particularly limited as long as it is water-soluble, and the same type as that used in the processing solution may be used. Preferably, polyhydric alcohols and glycol ethers are used. Among the polyhydric alcohols and glycol ethers, it is preferable to include one or more selected from the group consisting of glycerin, triethylene glycol, triethylene glycol monobutyl ether, and propylene glycol.

[0067] The content of the organic solvent in the colored ink composition is preferably 5.0% by mass or more and 40% by mass or less, relative to the total amount of the colored ink composition. When the content of the organic solvent is within the above range, the effects of color development, friction fastness, and corrosion resistance according to the present invention tend to be more effective and reliable. From a similar viewpoint, the content of the organic solvent is more preferably 8.0% by mass or more and 30% by mass or less, and even more preferably 12% by mass or more and 20% by mass or less, relative to the total amount of the colored ink composition.

[0068] 2.2.4. Surfactants The colored ink composition may contain a surfactant. Examples of surfactants include acetylene glycol-based surfactants, fluorine-based surfactants, and silicone-based surfactants, with silicone-based surfactants or acetylene glycol-based surfactants being preferred. Using a silicone-based surfactant allows the effects of the present invention to be achieved more effectively and reliably. From a similar viewpoint, BYK-348 is preferred as a commercially available silicone-based surfactant.

[0069] The surfactant content in the colored ink composition is preferably 0.1 to 5% by mass, 0.2 to 3% by mass, or 0.3 to 1% by mass, relative to the total amount of the colored ink composition. By keeping the surfactant content within the above range, the effects of the present invention can be achieved more effectively and reliably.

[0070] 2.2.5.Water As for the water, it is preferable to use water from which ionic impurities have been removed as much as possible. Examples of such water include pure water such as ion-exchanged water, reverse osmosis water, and distilled water, as well as ultrapure water.

[0071] The water content is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and even more preferably 45 to 75% by mass, relative to the total amount of the colored ink composition. By keeping the water content in the processing solution within the above range, the effects of the present invention can be achieved more effectively and reliably.

[0072] In addition to the above-mentioned components, the colored ink composition may optionally contain various additives such as metal sealants, softeners, solubilizers, viscosity modifiers, ultraviolet absorbers, antioxidants, and corrosion inhibitors.

[0073] 3. Preparation methods for each composition Each composition can be prepared, for example, by mixing the components in any order and removing impurities and foreign matter by filtration or other methods as needed. A method for mixing the components is to sequentially add each component to a container equipped with a stirring device such as a mechanical stirrer or magnetic stirrer, and then stir and mix them. Filtration methods include centrifugal filtration and filter filtration. Alternatively, the methods used in the examples described later may also be employed. [Examples]

[0074] The present invention will be described more specifically below using examples and comparative examples. The present invention is not limited in any way by the following examples.

[0075] Figures 1 to 4 show the compositions of each example and comparative example composition, as well as Tables 1 to 4 illustrating their evaluation results.

[0076] 1. Preparation of the ink composition Each component was placed in a mixing tank to obtain the composition shown in Tables 1 to 4, mixed and stirred, and then filtered through a membrane filter to obtain the treatment solution composition, colored ink composition, and clear ink composition for each example. Unless otherwise specified, the numerical values ​​for each component in the tables represent mass percent. Furthermore, in the tables, the numerical values ​​for each content represent the mass percent of the solid content of the active ingredient.

[0077] The abbreviations used in each composition and details of the product ingredients are as follows. Furthermore, the treatment solution compositions of Example 5 and Comparative Example 4 contained halide ions, and the halide ion concentration in the treatment solution composition was 1 ppm or higher (on the order of 1000 ppm).

[0078] 1.1. Processing liquid composition [Acid compound] Lactic acid (pKa=3.9, carboxyl group, monovalent) • Citric acid (pKa = 3.1, 4.8, 5.4, carboxyl group, trivalent) Levulinic acid (pKa=4.6, carboxyl group, monovalent) [Rust inhibitor] • Rust inhibitor 1 (benzotriazole, water-soluble triazoles) • Rust inhibitor 2 (Product name "Sunhibitor No. 50", water-soluble, amine-based nonionic surfactant, manufactured by Sanyo Chemical Industries, Ltd.) • Rust inhibitor 3 (Product name "Sanhibitor OMA-10", water-soluble, carboxylic acid-type anionic surfactant, manufactured by Sanyo Chemical Industries, Ltd.) [resin] • Resin 1 (Product name "Movinyl 6940", cationic acrylic resin, manufactured by Japan Coating Resin Co., Ltd., contains halide ions as counterions) [Basic compounds] ·KOH [Auxiliary drugs] NaCl [Organic solvents] Propylene glycol [Surfactants] • Orphine E1010 (product name, acetylene-based surfactant, manufactured by Nisshin Chemical Industry Co., Ltd.) [water] Ion-exchanged water

[0079] 1.2. Colored ink composition and clear ink composition The details of each component shown in Table 4 are as follows:

[0080] [Colorants] • Titanium dioxide dispersion: A pigment dispersion prepared by the following procedure was used. CI Pigment White 6 (specific gravity: 4.2 g / mL) was used as the pigment, and an anionic resin dispersant of styrene-acrylic resin synthesized using 55% by mass of styrene, 20% by mass of acrylic acid, and 30% by mass of methyl methacrylate was used as the pigment dispersant. 3 parts by mass of pigment were mixed with 1 part by mass of dispersant and 10 parts by mass of ion-exchanged water. The resulting mixture was premixed, and then dispersed using a bead mill disperser (product name "UAM-015", manufactured by Kotobuki Kogyo Co., Ltd.) with 0.03 mm diameter zirconia beads at a peripheral speed of 10 m / s and a liquid temperature of 30°C for 15 minutes. Coarse particles were then centrifuged using a centrifuge (product name "Model-3600", manufactured by Kuboyama Shoji Co., Ltd.) to obtain a titanium dioxide dispersion.

[0081] [Resin dispersion] • Urethane resin (product name "Takelac WS-6021", manufactured by Mitsui Chemicals, Inc.) [Organic solvents] Glycerin Triethylene glycol Triethylene glycol monobutyl ether Propylene glycol [Surfactants] • BYK-348 (Product name, silicone-based surfactant, HLB value: 11, manufactured by Bic Chemie Japan Co., Ltd.) [solvent] Ion-exchanged water

[0082] 2. Evaluation Method The printed materials obtained by the following method were tested for color development and friction fastness, and corrosion resistance was tested using the treatment solution composition for each example. A modified serial recording device (product name "SC-F2250", manufactured by Seiko Epson Corporation) was used to record a printed image pattern with an image resolution of 1200 x 600 dpi and a solid pattern (2 inches x 10 inches). The processing liquid composition and the colored ink composition were ejected from the head in the same pass to perform printing, and multiple main scans were performed on the same scanning area. In the example using clear ink (Example 6), the clear ink was then printed in the same manner. A 100% cotton black T-shirt (manufactured by Printstar) was used as the recording medium. After recording, the fabric with the processing liquid, colored ink, and / or clear ink attached was heated and dried in a belt conveyor oven (product name "Fusion R 36-6-4", manufactured by M&R) at 160°C for 6 minutes to obtain the printed material. The molal concentration Ca of the acidic group in acid compounds and the molal concentration Cb of the basic group in base compounds were calculated as follows.

[0083] 2.0.Calculation method 2.0.1. Method for calculating the molal concentration Ca of the acidic group in an acid compound and the molal concentration Cb of the basic group in a base compound. The molal concentration Ca of the acidic group in the acid compound was calculated using the following formula. Ca = (Amount of acid compound added [mass%]) × (Number of acidic groups with a pKa of 7 or less in one molecule of the acid compound) × 10 / (Molecular weight of the acid compound [g / mol])

[0084] The molal concentration Cb of the basic group in the basic compound was calculated using the following formula. Cb = (Amount of base compound added [mass%]) × (Number of hydroxyl groups or amino groups in one molecule of base) × 10 / (Molecular weight of base compound [g / mol])

[0085] In the case of amphoteric compounds such as amino acids, the concentration was calculated in the same manner as above, based on the difference in the number of acidic and basic groups, according to the properties of the more numerous group. For example, in the case of L-aspartic acid as an acidic amino acid, it can be calculated as follows. Aspartic acid has two carboxyl groups (pKa = 2.0, 3.9) as acidic groups and one amino group as a basic group in one molecule, and its aqueous solution has a pH of around 3. As an acidic compound, the molal concentration of the acidic groups of aspartic acid is calculated using the following formula C A It is possible to calculate this. Ca = (Amount of acid compound added [mass%]) × {(Number of acidic groups with a pKa of 7 or less in one molecule of the acid compound) - (Number of basic groups in one molecule of the acid compound)} × 10 / (Molecular weight of the acid compound [g / mol]) The following applies when the amount of aspartic acid added is 10% by mass. Ca=10×(2-1)×10 / 133.10≒0.751

[0086] For compounds where the molecular weight and the number of acidic (or basic) groups are unknown, the molecular weight and valency were calculated using the following method.

[0087] 2.0.2. Method for calculating the molecular weight and valency of compounds whose molecular weight and number of acidic (or basic) groups are unknown. 0.30 g of a compound of unknown molecular weight and number of acidic (or basic) groups was dissolved in 29.70 g of pure water to make 30.00 g. 0.03 g of 10 wt% sodium hydroxide (or sulfuric acid) was added dropwise to the aqueous solution of the compound, stirred with a magnetic stirrer, and the pH of the solution was measured using a pH meter (product name "F-72", HORIBA). This procedure was repeated until the pH of the solution reached 8.0 (or 6.0), at which point neutralization was determined, and the repeated operation was terminated. Based on these results, the amount of acidic (or basic) compound required to neutralize 1 g of 100 wt% sodium hydroxide (or 1 g of sulfuric acid) is calculated using the following formula: a x (or b x (g) was calculated. a x = 0.30g / (amount of 100wt% sodium hydroxide added in grams) b x = 0.30g / (amount of 100wt% sulfuric acid added in grams) 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% sodium hydroxide added in g) = (amount of 10 wt% sodium hydroxide added in g) / 10.

[0088] Next, the above procedure is performed on a 1 wt% sulfuric acid aqueous solution (or a 1 wt% sodium hydroxide aqueous solution), and the amount of sulfuric acid (or potassium hydroxide) required to neutralize 1 g of 100 wt% sodium hydroxide (or 100 wt% sulfuric acid) is a. H2SO4 (g) (or b) KOH (g)) was calculated, and the molecular weight (g / mol) per acidic group (or basic group) was calculated using the following formula. 98.08 × a x / a H2SO4 40.00 × b x / b KOH

[0089] 2.1. Color development For the printed materials obtained by the above method, the L* value (whiteness) of the recorded image was measured on the surface using a colorimeter (product name "FD-7", manufactured by Konica Minolta, Inc.), and the color development (whiteness) was determined according to the following criteria. (Evaluation Criteria) A: The L* value is 85 or higher. The B:L* value is between 80 and 85. The C:L* value is less than 80.

[0090] 2.2. Friction resistance The printed materials obtained by the above method were tested for friction fastness using a test method compliant with ISO 105-X12, and wet friction fastness was evaluated. For both the friction and non-friction areas, the L* (whiteness) of the recorded image was measured using a colorimeter (product name "FD-7", manufactured by Konica Minolta, Inc.), ΔL* was calculated, and friction fastness was determined according to the following criteria. (Evaluation Criteria) A: The L* value is less than 4. B:L* value is 4 or greater and less than 8. The C:L* value is 8 or higher.

[0091] 2.3. Corrosion resistance A SUS430 piece (approximately 25 mm square) was placed in a 60 ml PFA container containing 4 g of the treatment solution composition, and left in a 60°C constant temperature bath. The degree of corrosion on the surface of the SUS430 piece was visually observed, and the result was determined by the number of days on which corrosion was observed. (Evaluation Criteria) A: No corrosion was detected for a period of 40 days or more. B: Corrosion was observed during a period of 10 days or more but less than 40 days. C: Corrosion was observed within a period of less than 10 days.

[0092] 3. Evaluation Results Tables 1 to 4 show the composition of the inks used in each example and the evaluation results. From Tables 1 to 4, it can be seen that the treatment solution composition contains an acid compound, water, and a rust inhibitor, has a pH of 6.5 or less at 25°C, and the molal concentration of the acidic group derived from the acid compound is C A (mol / kg) and the molal concentration C of the basic group derived from the basic compound B The difference from (mol / kg) (C A -C B ) is 0.1 mol / kg or more (however, 0 <C A , 0≦C B It can be seen that by including ), the resulting recording material has excellent color development and friction fastness, and corrosion to the components of the recording device can also be suppressed.

Claims

1. A processing liquid composition used by ejection by an inkjet method, It contains an acid compound, water, and a rust inhibitor. The pH at 25°C is 6.5 or less. The molal concentration C of the acidic group derived from the aforementioned acid compound A (mol / kg) and the molal concentration C of the basic group derived from the base compound. B The difference from (mol / kg) (C A -C B ) but is 0.1 mol / kg or more (however, 0 < C A , 0 ≤ C B ), Processing liquid composition.

2. The pH at 25°C is 4.0 or less. The processing liquid composition according to claim 1.

3. The content of halide ions is 1 ppm or more relative to the total amount of the treatment solution composition. The processing liquid composition according to claim 1.

4. Contains a cationic polymer, The processing liquid composition according to claim 1.

5. Contains organic solvents, The processing liquid composition according to claim 1.

6. The acid compound contains one or more selected from the group consisting of lactic acid, acetic acid, levulinic acid, malic acid, malonic acid, glutaric acid, citric acid, phosphoric acid, succinic acid, adipic acid, and dimethylolpropionic acid. The processing liquid composition according to claim 1.

7. The aforementioned rust inhibitor is water-soluble. The processing liquid composition according to claim 1.

8. The rust inhibitor contains one or more selected from the group consisting of amino acids, carboxylates, aliphatic carboxylic acids, triazoles, thiazoles, imidazoles, phosphates, borates, sulfonates, and phosphonates. The processing liquid composition according to claim 1.

9. It is used by attaching it to the fabric. The processing liquid composition according to claim 1.

10. A processing liquid composition according to any one of claims 1 to 9, An inkjet ink composition containing resin particles and water, comprising: Ink set.

11. The aforementioned inkjet ink composition is a clear ink composition that does not contain pigment. The ink set according to claim 10.

12. The aforementioned inkjet ink composition is a colored ink composition containing a pigment. The ink set according to claim 10.

13. The content of the resin particles is 12% by mass or more relative to the total amount of the clear ink composition. The ink set according to claim 11.

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