Fabric processing solution, fabric processing solution and ink set, processing solution dispensing device, image forming apparatus, processing solution dispensing method, and image forming method

Abstract

To provide a treatment liquid for a fabric that achieves a high color development property in an image formed of ink while suppressing deterioration with time of the color development property as well as yellow discoloration.SOLUTION: A treatment liquid for a fabric imparted to a fabric contains an amino group-containing resin and a polyvalent metal salt, wherein an amine value of the amino group-containing resin is 200 mgKOH / g or more and 1,200 mgKOH / g or less, and a content of the amino group-containing resin is 0.01 mass% or more and 10 mass% or less with respect to the total amount of the treatment liquid for the fabric.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a processing solution for fabrics, a set of processing solution and ink for fabrics, a processing solution application device, an image forming apparatus, a method for applying a processing solution, and an image forming method. [Background technology]

[0002] Inkjet printers have advantages such as the ability to easily produce color prints on demand, and as a digital signal output device, they have become widely used in ordinary households. In recent years, there has been a growing demand for inkjet recording methods to achieve image quality comparable to conventional analog printing, not only for home use but also for slow-penetration media such as coated paper, non-absorbent media such as plastic film, and fabric media such as woven and knitted fabrics. For example, in the textile printing field, the market size for so-called DTG (Direct to Garment), which involves printing directly onto clothing such as T-shirts, is expanding year by year. Furthermore, with the recent rise of personal recommendation businesses in the apparel industry and the increased activity of collaborations with fine art recognized in the interior textile field, the demand for inkjet recording systems capable of forming images with excellent color reproduction on fabrics is steadily increasing. In inkjet printing, which uses ink containing pigments as colorants to directly create an image on fabric, the printing method differs from screen printing and other conventional printing methods in that it does not require the creation, storage, and cleaning of printing plates, making it suitable for small-batch, high-mix production. It also offers advantages such as shorter lead times because it does not involve processes such as transfer printing, and excellent lightfastness. Inks for this method have been developed.

[0003] In recent years, there has been a growing need for image creation on fabrics containing synthetic fibers such as polyester. Furthermore, there is a growing demand not only for plain fabrics, but also for fabrics that have already been colored through printing or other methods. Examples of image formation on a colored fabric include a method of coating the fabric with white ink and then landing color ink thereon. A layer of white ink can serve as a base for the color ink, enabling sufficient color development even on fabrics colored with dark colors such as black or navy. Therefore, in the above image formation method, it is important for the white ink to conceal the dark color of the fabric and it is required to have a high whiteness.

[0004] For example, in a printing method using a white pigment printing inkjet ink composition, a treatment liquid composition for improving color development, which contains a cationic compound such as a polyvalent metal salt, an organic acid, or a cationic resin, has been disclosed (see, for example, Patent Document 1).

Summary of the Invention

Problems to be Solved by the Invention

[0005] An object of the present invention is to provide a treatment liquid for fabrics that suppresses the decrease in color development over time and yellowing while obtaining high color development in an image formed by ink.

Means for Solving the Problems

[0006] The treatment liquid for fabrics of the present invention as a means for solving the above problems is a treatment liquid for fabrics applied to fabrics, containing an amino group-containing resin and a polyvalent metal salt, where the amine value of the amino group-containing resin is, 400mgKOH / g or more and 1100mgKOH / g or less and the content of the amino group-containing resin is 0.01% by mass or more and 10% by mass or less with respect to the total amount of the treatment liquid for fabrics.

Effects of the Invention

[0007] According to the present invention, it is possible to provide a treatment liquid for fabrics that suppresses the decrease in color development over time and yellowing while obtaining high color development in an image formed by ink.

Brief Description of the Drawings

[0008] [Figure 1] Figure 1 is a schematic diagram showing an example of an image forming apparatus. [Figure 2] Figure 2 is a schematic diagram showing an example of a processing liquid containing means.

Mode for Carrying Out the Invention

[0009] Hereinafter, an embodiment of the present invention will be described.

[0010] (Processing Liquid for Fabric) The processing liquid for fabric of the present disclosure contains an amino group-containing resin and a polyvalent metal salt, and preferably contains other components such as water, an organic solvent, a resin other than the amino group-containing resin (hereinafter also referred to as "other resin"), and a surfactant as necessary. The processing liquid for fabric of the present disclosure is applied to a fabric containing colored fibers.

[0011] In the present disclosure, "fabric" refers to a form in which fibers are made into a woven fabric, knitted fabric, non-woven fabric, or the like. The fibers are preferably organic fibers such as synthetic fibers, semi-synthetic fibers, regenerated fibers, and natural fibers, and more preferably synthetic fibers. Examples of synthetic fibers include fibers such as polyester, polyamide, acrylic, polyolefin, polyvinyl alcohol, polyvinyl chloride, polyurethane, and polyimide. Examples of semi-synthetic fibers include fibers such as acetate, diacetate, and triacetate. Examples of regenerated fibers include fibers such as polynosic, rayon, lyocell, and cupra. Examples of natural fibers include fibers such as cotton, hemp, silk, and wool. Among these fibers, fibers colored with disperse dyes described later are preferable, polyester fibers and acetate fibers are more preferable, and polyester fibers are even more preferable.

[0012] Furthermore, fibers containing a biodegradable polyester composition may be used as the fiber. The biodegradable polyester composition may contain, for example, a biodegradable aliphatic-aromatic polyester or polylactic acid, and may optionally contain organic fillers or inorganic fillers. Examples of biodegradable aliphatic-aromatic polyesters include polybutylene adipate terephthalate (PBAT), polybutylene succinate terephthalate (PBST), and polybutylene sebacate terephthalate (PBSeT). Examples of organic fillers include natural starch, plasticized starch, modified starch, natural fibers, and wood flour. Examples of inorganic fillers include talc powder, montmorillonite, kaolin, chalk, calcium carbonate, graphite, gypsum, conductive carbon black, calcium chloride, iron oxide, dolomite, silica, wollastonite, titanium dioxide, silicates, mica, glass fibers, and mineral fibers.

[0013] The fibers used in the fabric are colored by retaining colorants such as pigments and dyes inside or on the surface. In this disclosure, "colored fiber" refers to the lightness (L) of the fiber. * When measured using a spectrophotometer (for example, device name: X-rite eXact, manufactured by X-Rite), 60 > L * The fiber meets the range of 50 > L * It is preferable that the fiber meets the range of 40 > L * It is more preferable that the fiber meets the range of 30 > L * It is even more preferable that the fibers satisfy the range of 20 > L * It is particularly preferable that the fibers satisfy the specified range. Note that the measurement of fiber brightness may also be performed on a fabric, which is an aggregate of fibers. Generally, if the brightness of the fabric is within the above range, the brightness of the fibers contained within the fabric will also be within the above range. The coloring agent is not particularly limited, and the same colorants as those contained in the ink described later can be used, but it is preferable that it be a dye, and more preferably a disperse dye. Dyeing of synthetic fibers such as polyester fibers is usually done by using a disperse dye as a coloring agent and applying high temperature and high pressure treatment to relax the internal structure of the fiber and push the disperse dye into the fiber matrix. Unlike reactive dyes that have binding force due to a reaction, when this disperse dye comes into contact with the components contained in the above-mentioned fabric treatment solution or ink, the disperse dye is more likely to transfer to the image, and the problems of this disclosure become more apparent (in other words, the effects obtained by the fabric treatment solution of this disclosure become more pronounced).

[0014] In this disclosure, "fabric treatment liquid" refers to a liquid composition applied to the area of ​​the fabric to be inked before the ink is applied to the fabric. It is preferable that the fabric treatment liquid does not contain colorants for practical purposes. Furthermore, since the processing solution is applied to the fabric before the ink is applied, the processing solution is sometimes referred to as the "pre-treatment solution."

[0015] <Amino group-containing resin> The processing solution for textiles contains an amino group-containing resin. In this disclosure, "amino group-containing resin" refers to a polymer having primary, secondary, or tertiary amino groups in its molecule. There are no particular restrictions on the polymer, and it can be appropriately selected depending on the purpose. For example, it may be a homopolymer having a repeating structure of one structural unit, or a copolymer having a repeating structure of two or more different structural units. There are no particular restrictions on the copolymer, and it can be appropriately selected depending on the purpose. For example, it may have a structure in which two or more different structural units are arranged regularly, or a structure in which two or more different structural units are arranged randomly, and so on. When an amino group-containing resin is a copolymer, it has structural units having amino groups (units derived from polymerizable compounds), but it may also have additional structural units that do not have amino groups. Furthermore, the amine value of the amino group-containing resin is preferably between 200 mg KOH / g and 1200 mg KOH / g, and between 400 mg KOH / g and 1100 mg KOH / g. In a fabric treatment solution, by including an amino group-containing resin with an amine value of 200 mg KOH / g or more and 1200 mg KOH / g or less, it is possible to suppress the gradual decrease in color development and yellowing of the image formed by ink applied later to the area of ​​the fabric treated with the fabric treatment solution.

[0016] Here, we will explain why the deterioration of color reproduction and yellowing over time in images formed by ink can be suppressed. Generally, when applying ink to fabrics containing colored fibers, a fabric treatment solution is used to enhance the opacity of the ink against the fabric's color. However, when a fabric treatment solution is applied to a fabric containing colored fibers, and then ink is applied to the treated area of ​​the fabric, while high color vibrancy can be obtained in the image formed by the ink, there is a problem that the color vibrancy decreases over time. Furthermore, there is a challenge in achieving this decrease in color vibrancy over time without the image yellowing. Specifically, when a coloring agent used to color a fiber comes into contact with a fabric treatment solution or ink, the coloring agent may transfer to the image formed by the ink, which can lead to a decrease in the image's color reproduction over time. This is because the fabric treatment liquid or ink contains components (such as organic solvents, resins, or oily additives) that are soluble in or have affinity for the colorant. Furthermore, this problem becomes even more pronounced when using white ink, because even a small amount of the coloring agent that colors the fibers migrating to the white image formed by the white ink can have a significant impact. Furthermore, this issue becomes particularly pronounced when using fabrics containing synthetic fibers such as polyester fibers. Dyeing synthetic fibers such as polyester fibers is usually done by using disperse dyes as colorants and applying high temperature and high pressure treatment to relax the internal structure of the fibers, thereby pushing the disperse dyes into the fiber matrix. Unlike reactive dyes, which have binding force due to reactions, when these disperse dyes come into contact with components contained in the above-mentioned fabric treatment solution or ink, the disperse dyes tend to transfer to the image. Furthermore, in this case, when a fabric is heated to dry a fabric treatment solution or ink, the internal structure of the fibers relaxes due to the heating, which promotes the transfer of colorants such as disperse dyes that color the fibers to the image, making the transfer more pronounced. Furthermore, this issue becomes more pronounced when the fabric is colored with a dark color such as black, as even a small amount of the coloring agent used to color the fibers can have a significant impact on the image. One method to suppress the migration of colorants from fabrics containing colored fibers to an image is to pre-treat the fabric with a treatment solution containing polyethyleneimine (see Japanese Patent Publication No. 10-88487). However, this method has the drawback that the image may turn yellow when the fabric is heated. Furthermore, this issue becomes more pronounced when the ink added later is white ink, because even a small amount of yellowing has a significant impact on the white image formed by the white ink.

[0017] To address these challenges, the present inventors have found that when a fabric treatment solution containing an amino group-containing resin with an amine value of 200 mgKOH / g or more is used, the coloring agent that colors the fibers is trapped (captured) by the fibers, preventing the coloring agent from transferring to the image formed by the ink, and thus suppressing the deterioration of color development over time. Furthermore, the inventors have found that when a fabric treatment solution containing an amino group-containing resin with an amine value of 1200 mgKOH / g or less is used, the occurrence of yellowing in images formed by the ink can be suppressed.

[0018] As long as the amine value is between 200 mg KOH / g and 1200 mg KOH / g, it can be appropriately selected according to the purpose. Examples include polyamines such as polyethyleneimine and polyetheramine polyol; copolymers having polyamines such as polyamine-epihalohydrin copolymers and amine-epihalohydrin copolymers; polyamides such as polyacrylamide; and copolymers having polyamides such as polyamide-epihalohydrin copolymers and polyamide-polyamine-epihalohydrin copolymers. Among these, polyethyleneimine is preferred because it more effectively suppresses the deterioration of color development over time. These can be used individually or in combination of two or more types.

[0019] The content of the amino group-containing resin is preferably 0.01% by mass or more and 10.0% by mass or less, and more preferably 0.1% by mass or more and 5.0% by mass or less, relative to the total amount of the fabric treatment solution. A content of 0.01% by mass or more of the amino group-containing resin can suppress the gradual decline in color development in the image. Furthermore, a content of 10.0% by mass or less of the amino group-containing resin can suppress the occurrence of yellowing in the image formed by the ink.

[0020] <Polyvalent metal salts> The treatment solution for textiles contains polyvalent metal salts. By including a polyvalent metal salt in the fabric treatment solution, high color development can be imparted to the image formed by ink applied later to the area of ​​the fabric treated with the fabric treatment solution. This is because, when the polyvalent metal salts contained in the fabric treatment solution applied to the fabric first come into contact with the colorants contained in the ink applied later, the electrostatic effect causes aggregates of the colorants to form, separating the colorants from the liquid phase and promoting their fixation to the fabric surface. By incorporating polyvalent metal salts into the fabric treatment solution, even when using a medium with large voids like fabric, the pigment can be retained on the surface of the fabric by forming a layer of aggregated pigment, thereby creating a highly pigmented image. Furthermore, even when using fabrics with low ink absorption, beading can be suppressed, and high-quality images can be formed. Furthermore, unlike flocculants such as cationic polymers, polyvalent metal salts can suppress the transfer of the fabric treatment solution to contact members, even when contact members such as transport members come into contact with the area treated with the fabric treatment solution between the time the fabric treatment solution is applied and the time the ink is applied.

[0021] There are no particular restrictions on the polyvalent metal salts, and they can be appropriately selected according to the purpose. Examples include salts of titanium compounds, chromium compounds, copper compounds, cobalt compounds, strontium compounds, barium compounds, iron compounds, aluminum compounds, calcium compounds, magnesium compounds, zinc compounds, and nickel compounds. These may be used individually or in combination of two or more. Furthermore, hydrates can also be used as polyvalent metal salts.

[0022] There are no particular restrictions on the magnesium compound used; it can be appropriately selected depending on the purpose. Examples include magnesium chloride, magnesium acetate, magnesium sulfate, magnesium nitrate, and magnesium silicate. There are no particular restrictions on the calcium compound used, and it can be appropriately selected depending on the purpose. Examples include calcium carbonate, calcium nitrate, calcium chloride, calcium acetate, calcium sulfate, and calcium silicate. There are no particular restrictions on the barium compound used; it can be appropriately selected depending on the purpose, for example, barium sulfate. There are no particular restrictions on the zinc compound used; it can be appropriately selected depending on the purpose. Examples include zinc sulfide and zinc carbonate. There are no particular restrictions on the aluminum compound used; it can be appropriately selected for the purpose, and examples include aluminum silicate and aluminum hydroxide. Among these, calcium compounds, magnesium compounds, and nickel compounds are preferred because they can effectively aggregate the colorants in the ink, and calcium compounds and magnesium compounds that are alkaline earth metal salts are more preferred. Furthermore, calcium nitrate is particularly preferred because of its high deliquescence, which improves the storage stability of the fabric treatment solution.

[0023] The polyvalent metal salt content is preferably 5.0% by mass or more, more preferably 5.0% by mass or more and 30.0% by mass or less, and even more preferably 10.0% by mass or more and 25.0% by mass or less, based on the total amount of the fabric treatment solution. When the polyvalent metal salt content is 5.0% by mass or more, the aggregation of colorants in the ink is promoted, and a highly colored image can be obtained by retaining the colorants on the fabric with large voids. Furthermore, when the polyvalent metal salt content is 30.0% by mass or less, the precipitation and crystallization of polyvalent metal salts in the fabric treatment solution can be suppressed.

[0024] <Water> The fabric treatment solution may contain water. There are no particular restrictions on the water content, and it can be appropriately selected depending on the purpose. However, from the viewpoint of the drying properties of the fabric treatment solution, it is preferable that the water content be between 10.0% by mass and 90.0% by mass, and more preferably between 20.0% by mass and 60.0% by mass, relative to the total amount of the fabric treatment solution.

[0025] <Organic solvents> The fabric treatment solution may contain an organic solvent. The type of organic solvent is not particularly limited and includes, for example, polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds. Specific examples of organic solvents include, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 1, Polyhydric alcohols such as 2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl-1,3-pentanediol, petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether Examples include polyhydric alcohol alkyl ethers such as ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether; nitrogen-containing heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, and γ-butyrolactone; amides such as formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropionamide, and 3-butoxy-N,N-dimethylpropionamide; amines such as monoethanolamine, diethanolamine, triethanolamine, and triethylamine; sulfur-containing compounds such as dimethyl sulfoxide, sulfolane, and thiodiethanol; propylene carbonate, and ethylene carbonate.

[0026] There are no particular restrictions on the content of the organic solvent, and it can be appropriately selected depending on the purpose, but it is preferable that it be 10.0% by mass or more and 90.0% by mass or less of the total amount of the fabric treatment solution.

[0027] <Other resins> The fabric treatment solution may contain other resins besides amino group-containing resins. The type of other resin is not particularly limited and examples include urethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, styrene-butadiene resin, vinyl chloride resin, acrylic styrene resin, and acrylic silicone resin. Resin particles made from these resins may also be used. A fabric treatment solution can be obtained by mixing the resin particles, dispersed in water as a dispersion medium in a resin emulsion, with materials such as organic solvents. The resin particles may be synthesized as appropriate, or commercially available products may be used. Furthermore, these may be used individually or in combination of two or more types of resin particles.

[0028] There are no particular restrictions on the volume-average particle size of the resin particles, and they can be appropriately selected depending on the purpose. The volume-average particle size can be measured, for example, using a particle size analyzer (NanoTrac Wave-UT151, manufactured by MicroTrac-Bell Co., Ltd.).

[0029] There are no particular restrictions on the content of other resins, and they can be appropriately selected depending on the purpose, but it is preferable that they be between 1.0% by mass and 30.0% by mass relative to the total amount of the fabric treatment solution.

[0030] <Other ingredients> The fabric treatment solution may also contain other ingredients such as surfactants, defoamers, preservatives and fungicides, rust inhibitors, and pH adjusters.

[0031] - Surfactants - Any of the following surfactants can be used: silicone-based surfactants, fluorine-based surfactants, amphoteric surfactants, nonionic surfactants, and anionic surfactants. There are no particular restrictions on silicone-based surfactants, and they can be selected appropriately depending on the purpose. Among these, those that do not decompose even at high pH are preferred. Examples of silicone-based surfactants include side-chain modified polydimethylsiloxane, both-end modified polydimethylsiloxane, one-end modified polydimethylsiloxane, and both-end modified polydimethylsiloxane. Those having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group are particularly preferred because they exhibit good properties as aqueous surfactants. In addition, polyether-modified silicone-based surfactants can also be used as silicone-based surfactants, for example, compounds in which a polyalkylene oxide structure is introduced into the Si side chain of dimethylsiloxane. Examples of fluorinated surfactants include perfluoroalkyl sulfonic acid compounds, perfluoroalkyl carboxylic acid compounds, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in their side chains, as they exhibit low foaming properties. Examples of perfluoroalkyl sulfonic acid compounds include perfluoroalkyl sulfonic acid and perfluoroalkyl sulfonate salts. Examples of perfluoroalkyl carboxylic acid compounds include perfluoroalkyl carboxylic acid and perfluoroalkyl carboxylic acid salts. Examples of polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in their side chains include sulfate ester salts of polyoxyalkylene ether polymers having perfluoroalkyl ether groups in their side chains, and salts of polyoxyalkylene ether polymers having perfluoroalkyl ether groups in their side chains. Examples of counterions for the salts of these fluorinated surfactants include Li, Na, K, NH4, NH3CH2CH2OH, NH2(CH2CH2OH)2, and NH(CH2CH2OH)3. Examples of amphoteric surfactants include laurylaminopropionate, lauryldimethylbetaine, stearyldimethylbetaine, and lauryldihydroxyethylbetaine. Examples of nonionic surfactants include polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene propylene block polymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and ethylene oxide adducts of acetylene alcohol. Examples of anionic surfactants include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl salt, and salts of polyoxyethylene alkyl ether sulfate. These can be used individually or in combination of two or more types.

[0032] There are no particular restrictions on the silicone-based surfactant, and it can be appropriately selected depending on the purpose. Examples include side-chain modified polydimethylsiloxane, both-end modified polydimethylsiloxane, one-end modified polydimethylsiloxane, and both-end modified polydimethylsiloxane. Polyether-modified silicone-based surfactants having a polyoxyethylene group or a polyoxyethylene-polyoxypropylene group as a modifying group are particularly preferred as they exhibit good properties as aqueous surfactants. Such surfactants may be synthesized as appropriate, or commercially available products may be used. Commercially available products include, for example, those from BIC Chemie Inc., Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., Nippon Emulsion Co., Ltd., and Kyoeisha Chemical Co., Ltd. There are no particular limitations on the polyether-modified silicone surfactants mentioned above, and they can be appropriately selected depending on the purpose. For example, one example is a polyalkylene oxide structure represented by the general formula (S-1), in which a polyalkylene oxide structure is introduced into the Si side chain of dimethylpolysiloxane. [ka] (However, in general formula (S-1), m, n, a, and b each independently represent integers, R represents an alkylene group, and R' represents an alkyl group.) As the above polyether-modified silicone surfactant, commercially available products can be used. For example, KF-618, KF-642, KF-643 (Shin-Etsu Chemical Co., Ltd.), EMALEX-SS-5602, SS-1906EX (Nippon Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (Toray Dow Corning Silicone Co., Ltd.), BYK-33, BYK-387 (BYK Chemie GmbH), TSF4440, TSF4452, TSF4453 (Toshiba Silicone Co., Ltd.), etc. can be mentioned.

[0033] As the fluorosurfactant, compounds having 2 to 16 carbon atoms substituted with fluorine are preferred, and compounds having 4 to 16 carbon atoms substituted with fluorine are more preferred. As the fluorosurfactant, perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having a perfluoroalkyl ether group in the side chain can be mentioned. Among these, polyoxyalkylene ether polymer compounds having a perfluoroalkyl ether group in the side chain are preferred because of their low foaming properties, and particularly fluorosurfactants represented by general formula (F-1) and general formula (F-2) are preferred.

Chemical formula

[0034] There are no particular restrictions on the surfactant content, and it can be appropriately selected depending on the purpose, but it is preferable that it be 0.001% by mass or more and 5% by mass or less relative to the mass of the fabric treatment solution.

[0035] -Antifoaming agent- There are no particular restrictions on the defoaming agent; examples include silicone-based defoaming agents, polyether-based defoaming agents, and fatty acid ester-based defoaming agents. These may be used individually or in combination of two or more. Among these, silicone-based defoaming agents are preferred due to their superior foam-breaking effect.

[0036] -Preservative and fungicidal agent- There are no particular restrictions on the preservatives and fungicides used; for example, 1,2-benzisothiazolin-3-one can be used.

[0037] -Rust Inhibitor- There are no particular restrictions on the rust inhibitors used; examples include acidic sulfites and sodium thiosulfate.

[0038] - pH adjuster - As a pH adjusting agent, it can be used without any particular restrictions, as long as it can adjust the pH to 7 or higher.

[0039] <Physical properties of the treatment solution for textiles> There are no particular restrictions on the physical properties of the fabric treatment solution, and it can be appropriately selected according to the purpose. For example, it is preferable that the viscosity, surface tension, etc., are within the following ranges. The viscosity of the fabric treatment solution at 25°C is preferably 0.5 mPa·s to 30 mPa·s, and more preferably 0.5 mPa·s to 10 mPa·s, in order to obtain good application properties. Here, viscosity can be measured using, for example, a rotational viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.). Measurement conditions are 25°C, standard cone rotor (1°34' × R24), sample volume 1.2 mL, rotation speed 50 rpm, and measurement can be performed in 3 minutes. The surface tension of the fabric treatment solution is preferably 35 mN / m or less, and more preferably 32 mN / m or less, at 25°C, in order to ensure that the fabric treatment solution is adequately leveled on the fabric and shorten the drying time of the fabric treatment solution.

[0040] (Processing solution and ink set) A set of processing fluid and ink according to the present disclosure comprises the processing fluid, ink, and, if necessary, other components. The aforementioned processing solution is the same as the processing solution in this disclosure.

[0041] <ink> As described above, the ink is a liquid composition applied to the area of ​​the fabric to which the fabric treatment solution has been applied. Depending on the purpose, ink may contain organic solvents, water, colorants, resins, and other components such as surfactants. Regarding other components such as organic solvents, water, resins, and surfactants, the same components as those used for fabric treatment solutions can be used, so their explanation will be omitted.

[0042] The ink is preferably white ink. When the ink is white ink, even a small amount of the coloring agent that colors the fibers can transfer to the white image formed by the white ink, significantly affecting the color development and yellowing of the image formed by the ink, and thus the effect obtained by the fabric treatment solution of this disclosure becomes more pronounced. In this disclosure, "white ink" refers to ink that can form an image of a color commonly referred to as "white," and includes inks that are slightly colored. This also includes inks sold under names such as "white ink" or "white ink." Furthermore, the "white ink" has an ink adhesion amount of 30 mg / cm² to white polyester fabric. 2 A solid image is formed, and the brightness (L) of the solid image is measured using a spectrophotometer (e.g., X-rite eXact, manufactured by X-Rite). * ) and chromaticity (a * , b * When measuring 60≦L * ≤100, -4.5 ≤a * ≤2, -6 ≤b * Contains inks that satisfy the range ≤ 2.5. Note that the brightness (L) of the aforementioned solid image * ) and chromaticity (a * , b * ) is a method of color representation established by the International Commission on Illumination (CIE). Furthermore, it is preferable that the white ink be used as a white base ink to form a white image on the fabric, thereby creating a base that enhances the color development of the non-white image formed by the non-white ink further applied to the white image. Furthermore, this non-white ink also contains other components such as organic solvents, water, non-white colorants, resins, and surfactants, depending on the purpose, as described above. In this disclosure, "non-white ink" refers to inks that are not included in the white ink described above.

[0043] <<Colorants>> Pigments and dyes can be used as colorants. Inorganic or organic pigments can be used. These may be used individually or in combination of two or more. Mixed crystals may also be used.

[0044] Examples of pigments that can be used include black pigment, yellow pigment, magenta pigment, cyan pigment, white pigment, green pigment, orange pigment, and glossy or metallic pigments such as gold and silver. Among these, as mentioned above, it is preferable to use white pigment from the viewpoint that it is possible to create white ink.

[0045] As inorganic pigments, titanium dioxide, iron oxide, tin oxide, zirconium oxide, iron titanate (a composite oxide of iron and titanium), calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chromium yellow can be used, as well as carbon black produced by known methods such as the contact method, furnace method, and thermal method. Among these inorganic pigments, titanium dioxide, iron oxide, tin oxide, zirconium oxide, and iron titanate (a composite oxide of iron and titanium) are preferred because they can be used as white pigments, and titanium dioxide is more preferred because it has a high refractive index and can produce high whiteness.

[0046] In addition, organic pigments such as azo pigments, polycyclic pigments (e.g., phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.), dye chelates (e.g., basic dye type chelates, acid dye type chelates, etc.), nitro pigments, nitroso pigments, and aniline black can be used. Of these pigments, those with good affinity to the solvent are preferably used. Other uses such as resin hollow particles and inorganic hollow particles are also possible.

[0047] Specific examples of pigments include carbon blacks (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, or metals such as copper, iron (CI Pigment Black 11), and titanium dioxide, as well as organic pigments such as aniline black (CI Pigment Black 1).

[0048] Furthermore, for color applications, we have CI Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 138, 150, 153, 155, 180, 185, 213, and CI Pigment Ole. Orange 5, 13, 16, 17, 36, 43, 51, CI Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48:2, 48:2 (Permanent Red 2B(Ca)), 48:3, 48:4, 49:1, 52:2, 53:1, 57:1 (Brilliant Carmine 6B), 60:1, 63:1, 63:2, 64:1, 81, 83, 88, 101 (Bengara), 104, 105, 106, 108 (Cadmium Red), 112, 114, 122 (Quinacridone Magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 184, 185, 190, 193, 202, 207, 208, 209, 213, 219, 224, 254, 264, CI Pigment Violet 1 (Rhodamine Lake), 3, 5:1, 16, 19, 23, 38; CI Pigment Blue 1, 2, 15 (Phthalocyanine Blue), 15:1, 15:2, 15:3, 15:4 (Phthalocyanine Blue), 16, 17:1, 56, 60, 63; CI Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, etc. are available.

[0049] The dyes used are not particularly limited and include acid dyes, direct dyes, reactive dyes, and basic dyes. They may be used individually or in combination of two or more types. As dyes, for example, CI Acid Yellow 17, 23, 42, 44, 79, 142, CI Acid Red 52, 80, 82, 249, 254, 289, CI Acid Blue 9, 45, 249, CI Acid Black 1, 2, 24, 94, CI Food Black 1, 2, CI Direct Yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 142, 144, Examples include 173, CI Direct Red 1, 4, 9, 80, 81, 225, 227, CI Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202, CI Direct Black 19, 38, 51, 71, 154, 168, 171, 195, CI Reactive Red 14, 32, 55, 79, 249, and CI Reactive Black 3, 4, 35.

[0050] The amount of colorant in the ink is preferably 0.1% to 15.0% by mass, and more preferably 1.0% to 10.0% by mass, relative to the total amount of ink, from the viewpoint of improving image density, good fixation, and ejection stability.

[0051] The amount of white pigment in the ink is preferably 1% to 20.0% by mass, and more preferably 6% to 15.0% by mass, relative to the total amount of ink, from the viewpoint of improving image density and ejection stability.

[0052] Methods for obtaining ink by dispersing pigments include introducing hydrophilic functional groups into the pigment to create a self-dispersible pigment, coating the surface of the pigment with a resin and dispersing it, and using a dispersant to disperse it. One method for creating self-dispersible pigments by introducing hydrophilic functional groups into pigments is to add functional groups such as sulfone groups or carboxyl groups to a pigment (e.g., carbon) to make it dispersible in water. One method for coating and dispersing pigments with resin is to encapsulate the pigments in microcapsules, making them dispersible in water. This can be rephrased as resin-coated pigments. In this case, it is not necessary for all pigments incorporated into the ink to be coated with resin; uncoated pigments or partially coated pigments may be dispersed in the ink. Methods of dispersion using dispersants include the use of known low-molecular-weight dispersants, such as surfactants, and high-molecular-weight dispersants. Depending on the pigment, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc., can be used as dispersants. Takemoto Oil & Fat Co., Ltd.'s RT-100 (nonionic surfactant) and sodium naphthalene sulfonate formalin condensate can also be suitably used as dispersants. Dispersants may be used individually or in combination of two or more.

[0053] <<Other ingredients>> Other components that can be used, in addition to those described for the fabric treatment solution, include, for example, auxiliary agents. Examples of auxiliary agents include silicon dioxide. By including auxiliary agents, light scattering can be made easier, and the whiteness of the ink can be improved when using white ink.

[0054] [Ink properties] There are no particular restrictions on the physical properties of the ink, and they can be appropriately selected according to the purpose. For example, it is preferable that the viscosity, surface tension, pH, etc., are within the following ranges. The viscosity of the ink at 25°C is preferably between 5 mPa·s and 30 mPa·s, and more preferably between 5 mPa·s and 25 mPa·s, as this improves print density and character quality and ensures good ejection. Here, viscosity can be measured using, for example, a rotational viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.). Measurement conditions are 25°C, standard cone rotor (1°34' × R24), sample volume of 1.2 mL, rotation speed of 50 rpm, and measurement can be performed in 3 minutes. The surface tension of the ink is preferably 35 mN / m or less, and more preferably 32 mN / m or less, at 25°C, in order to allow the ink to level nicely on the fabric and shorten the ink drying time. From the viewpoint of preventing corrosion of metal components in contact with the ink, the pH of the ink is preferably 7 to 12, and more preferably 8 to 11.

[0055] The above-mentioned fabric treatment liquid and ink may be used in combination as a set. Furthermore, as mentioned above, the ink is preferably white. Furthermore, an ink set is not limited to cases where the fabric treatment solution and ink exist separately, for example, when the treatment solution container and the ink container are manufactured and sold as a single unit. For example, even if the processing solution container and the ink container are manufactured and sold independently, they are included in the ink set if it is assumed that the processing solution and ink for fabrics will be used together, or if the use of the processing solution and ink for fabrics is substantially encouraged.

[0056] (Processing liquid dispensing device and processing liquid dispensing method) The processing liquid application device comprises a processing liquid storage means for storing the processing liquid for fabrics of the present disclosure, and a processing liquid application means for applying the processing liquid for fabrics to the fabric, and may include other means as needed. The form of the processing liquid dispensing device is not particularly limited as long as it has a processing liquid storage means and a processing liquid dispensing means, and may be a standalone, independent device, or it may be a device that is incorporated into and integrated with an image forming apparatus by being combined with other means (for example, an ink dispensing means). The method for applying the treatment solution includes a step of applying a treatment solution for fabrics to the fabric, and may include other steps as necessary.

[0057] The method for dispensing the processing liquid disclosed herein is preferably carried out by the processing liquid dispensing apparatus disclosed herein. The method for dispensing the processing liquid disclosed herein will be described below, along with a description of the processing liquid dispensing apparatus disclosed herein.

[0058] <Means for containing processing liquid> There are no particular restrictions on the means for containing the processing liquid; known inkjet cartridges and the like can be used.

[0059] <Means for applying processing solution and process for applying processing solution> The processing liquid application means is a means for applying a processing liquid for fabrics to a fabric. The processing solution application step is the step of applying a processing solution for fabrics to the fabric. The aforementioned fabric treatment solution is the same as the fabric treatment solution described herein. The aforementioned fabric is the same as that described in the fabric treatment solution of this disclosure.

[0060] The processing liquid application process can include methods such as dispensing and coating. There are no particular restrictions on the discharge method, and it can be appropriately selected according to the purpose. Examples include methods using piezoelectric element actuators, methods applying thermal energy, methods using actuators that utilize electrostatic force, and methods using a continuous-jet type charged control head. Examples of coating methods include blade coating, gravure coating, gravure offset coating, wire bar coating, bar coating, roll coating, knife coating, air knife coating, comma coating, U-comma coating, AKKU coating, smoothing coating, microgravure coating, reverse roll coating, 4- or 5-roll coating, dip coating, curtain coating, slide coating, and die coating.

[0061] In the processing solution application step, the amount of processing solution applied to the fabric is 10 mg / cm³. 2 More than 50mg / cm 2 The following is preferred: 20 mg / cm³ 2 More than 40mg / cm 2 The following is more preferable: The amount administered is 10 mg / cm³. 2 If the above is achieved, image quality can be improved, and 50 mg / cm² 2The following conditions can suppress the occurrence of color unevenness caused by the precipitation of solid components in the processing solution.

[0062] <Other means and other processes> Other means are not particularly limited and can be selected as appropriate depending on the purpose, such as heating methods. Other processes are not particularly limited and can be selected as appropriate depending on the purpose, such as heating processes.

[0063] <<Heating means and heating process>> The heating means is a means of heating the fabric to which the fabric treatment liquid has been applied. The heating process involves heating the fabric that has been treated with the fabric processing solution.

[0064] The method for applying the processing solution and the method for forming an image preferably include a heating step (also referred to as the first heating step) in which the fabric to which the processing solution for fabrics has been applied is heated after the processing solution application step. The fabric treatment solution applied to the fabric is dried by performing a heating process. The heating temperature in the heating process is preferably 60°C or higher, more preferably 80°C or higher, and even more preferably 100°C or higher. In the image forming method described later, the heating step is performed before the ink application step, which will be described later.

[0065] There are no particular restrictions on the heating method, and any known heating method can be appropriately selected, such as a roll heater, drum heater, hot air generator, or heat press.

[0066] (Image forming apparatus and image forming method) The image forming apparatus includes a processing liquid storage means for containing a processing liquid for fabrics, a processing liquid application means for applying the processing liquid for fabrics to a fabric, and an ink application means for applying ink to the area of ​​the fabric to which the processing liquid for fabrics has been applied, and may include other means as needed. The image forming method includes a processing liquid application step of applying a processing liquid for fabrics to a fabric, and an ink application step of applying ink to the area of ​​the fabric to which the processing liquid for fabrics has been applied, and may include other steps as needed.

[0067] The image forming method disclosed herein is preferably carried out using the image forming apparatus disclosed herein. The image forming method disclosed herein will be described below in conjunction with a description of the image forming apparatus disclosed herein.

[0068] <Means for containing processing liquid> The processing liquid storage means is the same as the processing liquid storage means in the processing liquid dispensing device of the present disclosure.

[0069] <Means for applying processing solution and process for applying processing solution> The processing liquid dispensing means is the same as the processing liquid dispensing means in the processing liquid dispensing apparatus of the present disclosure. The processing liquid application step is the same as the processing liquid application step in the processing liquid application method of the present disclosure.

[0070] <Ink application means and ink application process> The ink application means is a means for applying ink to the area of ​​the fabric to which the fabric treatment liquid has been applied. The ink application process is a process of applying ink to the area of ​​the fabric to which the fabric treatment liquid has been applied.

[0071] There are no particular restrictions on the ink, and it can be appropriately selected depending on the purpose. The ink in the set of processing solution and ink of this disclosure is preferred as the ink.

[0072] There are no particular restrictions on the ink application method, and it can be appropriately selected depending on the purpose. Examples include ejection methods and coating methods. Among these, ejection methods are preferred, and inkjet ejection methods are more preferred.

[0073] <Other means and other processes> Other means are not particularly limited and can be selected as appropriate depending on the purpose, and examples include a first heating means, a second heating means, etc. Other processes are not particularly limited and can be selected as appropriate depending on the purpose, for example, a first heating process and a second heating process.

[0074] <<First heating means and first heating process>> The first heating method is a method for heating a fabric that has been treated with a fabric treatment solution. The first heating step is the step of heating the fabric to which the fabric treatment solution has been applied. The first heating means and the first heating step are the same as the heating means and heating step in the processing liquid application apparatus and processing liquid application method described above.

[0075] <<Second heating means and second heating step>> The second heating means is a heating means that heats the fabric to which the fabric treatment liquid and ink have been applied after the ink application process. The second heating step is a heating step that takes place after the ink application step, in which the fabric to which the fabric treatment solution and ink have been applied is heated. The second heating step dries the fabric treatment solution and ink applied to the fabric. The heating temperature in the second heating step is preferably 60°C or higher, more preferably 80°C or higher, and even more preferably 100°C or higher.

[0076] The second heating means is not particularly limited and can be appropriately selected from known heating means, such as roll heaters, drum heaters, hot air generators, and heat presses.

[0077] Next, the processing liquid dispensing apparatus and the image forming apparatus will be described with reference to Figures 1 and 2. Figure 1 is a schematic diagram showing an example of an image forming apparatus. Figure 2 is a schematic diagram showing an example of a processing liquid containment means.

[0078] The image forming apparatus 400 shown in Figure 1 is an image forming apparatus having a serial-type inkjet head. A mechanism unit 420 is provided inside the outer casing 401 of the image forming apparatus 400. The storage sections 411 of the processing liquid storage means 410p for fabric processing liquid, the white ink storage means 410w for white ink, the black ink storage means 410k for black ink, and the cyan ink storage means 410c for cyan ink are formed from a packaging material such as aluminum laminate film. The storage sections 411 are housed in a storage container case 414 made of plastic, for example. Thus, each storage means 410 is used as a cartridge.

[0079] Meanwhile, a cartridge holder 404 is provided at the back of the opening when the cover 401c of the main body of the device is opened. Each storage means 410 is detachably attached to the cartridge holder 404. As a result, the discharge port 413 of each storage means 410 and the inkjet ejection head 434 are connected via each supply tube 436, and the fabric processing liquid and each ink can be ejected from the inkjet ejection head 434 to the fabric. In the image forming apparatus 400 shown in Figure 1, the fabric processing solution is applied to the fabric using an inkjet ejection method, but the method of applying the fabric processing solution is not limited to this. For example, it may be applied using a blade coating method, a roll coating method, a spray coating method, etc.

[0080] The image forming apparatus 400 may also have a heating means for drying the fabric treatment liquid or white ink or other liquid applied to the fabric. Examples of known heating means include roll heaters, drum heaters, hot air generators, and heat presses. [Examples]

[0081] The following describes embodiments of the present invention, but the present invention is not limited in any way to these embodiments.

[0082] (Examples 1-19 and Comparative Examples 1-5) <Example of fabric treatment solution preparation> The fabric treatment solutions for Examples 1-19 and Comparative Examples 1-5 were obtained by mixing and stirring the materials of the formulations shown in Tables 1-5 below. The units of the numerical values ​​for each formulation shown in Tables 1-5 below are "mass%". Furthermore, the content of amino group-containing resins and resin emulsions shown in Tables 1-5 below are expressed as solid content. Furthermore, the content of polyvalent metal salts shown in Tables 1-5 below are expressed as the amount of polyvalent metal salts including hydration water.

[0083] Furthermore, the details of each material shown in Tables 1 to 5 below (product name, manufacturer name, etc.) are as follows:

[0084] -Organic Solvents- • Propylene glycol (manufactured by Kanto Chemical Co., Ltd.) Glycerin (manufactured by Kanto Chemical Co., Ltd.)

[0085] - Amino group-containing resin - • SP-003 (Product name: Epomin (registered trademark), polyethyleneimine, amine value: 1178 mg / KOH / g, manufactured by Nippon Shokubai Co., Ltd.) • SP-012 (Product name: Epomin (registered trademark), polyethyleneimine, amine value: 1066 mg / KOH / g, manufactured by Nippon Shokubai Co., Ltd.) • HM-2000 (Product name: Epomin (registered trademark), polyethyleneimine, amine value: 1010 mg / KOH / g, manufactured by Nippon Shokubai Co., Ltd.)

[0086] -Resin emulsion (other resins)- • Sumikaflex 850HQ (ethylene-vinyl acetate-vinyl chloride copolymer resin emulsion, manufactured by Sumika Chemtex Co., Ltd., solids content: 45.5% by mass)

[0087] -Polyvalent metal salts- • Calcium nitrate tetrahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Magnesium nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Magnesium sulfate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0088] The synthesis methods and amine value measurement methods for the amino group-containing resins A to C shown in Tables 1 to 5 below are as follows.

[0089] -Synthesis example of amino group-containing resin A- In a 500 mL four-necked flask equipped with a stirrer, thermometer, and reflux condenser, 134.7 g (0.5 mol) of a 60% by mass aqueous solution of diallyldimethylammonium chloride and 176 g of distilled water were charged, and the pH was adjusted to 3-4 with hydrochloric acid. Next, 18.3 g (0.25 mol) of acrylamide and 3.9 g of sodium hypophosphite were added and dissolved by stirring at 50°C. Then, the internal temperature was raised to 60°C, and 1.7 g of a 28.5% by mass aqueous solution of ammonium persulfate was added. While maintaining the internal temperature at 60°C-65°C, after 4 hours, another 3.5 g of a 28.5% by mass aqueous solution of ammonium persulfate was added. After that, the reaction was carried out at 60°C for 20 hours to obtain a diallyldimethylammonium chloride-acrylamide copolymer (amino group-containing resin A) with a solid content of 30% by mass. Furthermore, the amine value of amino group-containing resin A, determined by the following method, was 420 mg KOH / g.

[0090] --Method for measuring amine value-- The total amine value, which represents the sum of primary, secondary, and tertiary amines, was used as the amine value. It was defined as the number of mg of hydrochloric acid and equivalent potassium hydroxide required to neutralize 1 g of the sample, and the amine value was determined by the neutralization titration method described below. First, the amino group-containing resin A obtained in the synthesis example of amino group-containing resin A was washed with pure water and dried. 0.5 g to 2.0 g of the dried sample (amino group-containing resin A) was accurately weighed and placed in an Erlenmeyer flask, where it was thoroughly dissolved in 30 mL of ethanol. Next, a 0.2 mol / L ethanolic hydrochloric acid solution (titer f2) was added dropwise from a burette. The titration volume (mL) was read when the solution changed from green to yellow, and the amine value was calculated using the following formula. Amine value (mgKOH / g) = {titration volume (mL) × 56.11 (mg / mL) × 0.2 × f²} / sample (g)

[0091] -Synthesis example of amino group-containing resin B- In a 300 mL four-necked flask equipped with a stirrer, thermometer, and reflux condenser, 100 mL of 1 mol / L diallyldimethylamine hydrochloride / dimethyl sulfoxide solution and 100 mL of 1 mol / L sulfur dioxide / dimethyl sulfoxide solution were mixed. 0.82 g of azobisisobutyronitrile was added as a polymerization initiator, and polymerization was carried out at 40°C for 24 hours. The reaction solution was added dropwise to methanol to precipitate the copolymer, filtered through a glass filter, and dried under reduced pressure to obtain 18 g of copolymer (amino group-containing resin B). Distilled water was added to this solution to prepare an aqueous solution with a solid content of 50% by mass. The amine value of amino group-containing resin B, determined by the same method as for amino group-containing resin A, was 250 mg KOH / g.

[0092] -Synthesis example of amino group-containing resin C- 495 g (4.8 mol) of diethylenetriamine was charged into a 3-liter four-necked round-bottom flask equipped with a thermometer, condenser, stirrer, and nitrogen inlet tube. 877 g (6.0 mol) of adipic acid was added while stirring, and the temperature was increased while removing the generated water from the system. The reaction was carried out at 150°C for 5 hours, after which 1,000 g of water was gradually added to obtain a polyamide-polyamine-containing solution. This polyamide-polyamine-containing solution had a solid content of 52.1% by mass, and its viscosity at 25°C when the solid content was 50% by mass was 380 mPa·s. 100 g of the obtained polyamide polyamine-containing solution (0.214 moles as amino groups), 3.8 g of acetic acid (30 equivalents%), and 4.3 g of 30% by mass sodium hydroxide aqueous solution (15 equivalents%) were charged together, and 6.7 g of water was added to bring the solid content to 50% by mass. Next, 19.8 g (100 equivalents) of epichlorohydrin was added dropwise over 1 hour at 30°C, and the mixture was held at the same temperature for 1 hour. Then, 0.8 g (2 equivalents) of sodium metabisulfite was added, and the mixture was held at the same temperature for 5 hours from the start of the epichlorohydrin addition. Next, 1.1 g (10 equivalents) of 98% sulfuric acid and 127.0 g of water were added to bring the solid content to 30% by mass, and then the mixture was heated to 75°C. Furthermore, the reaction solution was maintained at this temperature until its viscosity at 25°C reached 300 mPa·s. Then, 40.5 g of water was added to bring the solid content to 26% by mass. After cooling to below 25°C, the pH was adjusted to 3.5 with 30% by mass sulfuric acid. Next, the pH was adjusted to 3.0 with 88% by mass formic acid to obtain amino group-containing resin C with a solid content concentration of 25.0% by mass and a viscosity of 51.6 mPa·s at 15% by mass. The amine value of amino group-containing resin C, determined by the same method as amino group-containing resin A, was 185 mgKOH / g.

[0093] <Example of white ink preparation> -Preparation of urethane resin emulsion- In a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet, 75 g of polycarbonate polyol (Duranol T5651, manufactured by Asahi Kasei Chemicals) with a number-average molecular weight (Mn) of 1000, 90 g of dicyclohexylmethane diisocyanate (H12MDI), and 200 g of acetone were added and reacted at 75°C for 4 hours to obtain an acetone solution of urethane prepolymer. This solution was cooled to 40°C, and 450g of water was gradually added, followed by emulsification and dispersion using a homogenizer. Subsequently, an aqueous solution of 15 g of 2-methyl-1,5-pentanediamine dissolved in 100 g of water was added, and stirring was continued for 1 hour. This was then desolvated under reduced pressure at 50°C to obtain a urethane resin emulsion with a non-volatile content of approximately 45% by mass.

[0094] -Preparation of white pigment dispersion A (titanium dioxide pigment dispersion)- In a beaker, 37.5 parts of acrylic copolymer (DISPERBYK-2008: manufactured by BYK, solid content concentration: 60% by mass) were dissolved in 100.0 parts of high-purity water. 30.0 parts of titanium dioxide (JR-600A: manufactured by Teika (primary particle size 250 nm, surface treatment: Al)) were added, and the mixture was stirred at 5000 rpm for 30 minutes using an Excel autohomogenizer manufactured by Nippon Seiki Seisakusho until it was dispersed without clumps. The rotation speed was then gradually increased to 10000 rpm for 30 minutes. The obtained titanium dioxide pigment dispersion was treated with water cooling using a US-300T ultrasonic homogenizer (tip φ26) manufactured by Nippon Seiki Seisakusho at 200 μA for 1 hour, and then filtered through a 5 μm membrane filter (cellulose acetate membrane) to obtain a white pigment dispersion A with a titanium dioxide pigment solid content concentration of 17.9% by mass.

[0095] -Preparation of white pigment dispersion B (silica fine particle dispersion)- In a beaker, 5.0 parts of DISPERBYK102 (Big Chemie Co., Ltd., solid content concentration: 60% by mass) were dissolved in 35.0 parts of high-purity water. 30.0 parts of hydrophobic silica microparticles AEROSI R106 (primary particle size: 7 nm; manufactured by Nippon Aerosil Co., Ltd.) were added, and the mixture was stirred at 5000 rpm for 30 minutes using an Excel autohomogenizer manufactured by Nippon Seiki Seisakusho until it was dispersed without clumps. The rotation speed was then gradually increased to 10000 rpm for 30 minutes. The obtained dispersion was treated with water cooling using a US-300T ultrasonic homogenizer (tip φ26) manufactured by Nippon Seiki Seisakusho at 200 μA for 1 hour, and then filtered through a 5 μm membrane filter (cellulose acetate membrane) to obtain a white pigment dispersion B with a solid content concentration of silica fine particles of 42.9% by mass.

[0096] -Preparation of white inks A and B- A vehicle was prepared by dissolving the materials of the following formulations, excluding white pigment dispersion A or B and urethane resin emulsion, in deionized water (adjusted so that the total ink volume is 100%). This vehicle was then mixed with urethane resin emulsion, and further mixed with white pigment dispersion A or B. The mixture was then filtered through a filter with an average pore size of 0.8 μm to obtain white inks A and B. [White ink A] • White pigment dispersion A: 45.0% by mass (Titanium dioxide pigment: 8.06% by mass relative to the total ink amount) • Urethane resin emulsion: 20.0% by mass • 1,3-Butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.): 15.0% by mass Glycerin (manufactured by Kanto Chemical Co., Ltd.): 15.0% by mass • Surfinol 104 (manufactured by Nisshin Chemical, acetylene glycol-based surfactant): 0.9% by mass • 2-amino-2-ethyl-1,3-propanediol (manufactured by Kanto Chemical Co., Ltd.): 0.5% by mass • Proxel XLII (manufactured by Arch Chemicals Japan): 0.3% by mass • Deionized water: Remaining amount [White ink B] • White pigment dispersion B: 45.0% by mass (titanium dioxide pigment 8.06% by mass) • Urethane resin emulsion: 20.0% by mass Glycerin (manufactured by Kanto Chemical Co., Ltd.): 6.9% by mass • Silica particle dispersion: 4.5% by mass (Silica particles: 1.93% by mass relative to the total ink amount) Triethylene glycol monobutyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.): 2.9% by mass • BYK-387 (manufactured by Big Chemie Co., Ltd.): 0.9% by mass Triethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.): 0.4% by mass • Deionized water: Remaining amount [White ink C] • White pigment dispersion A: 33.6% by mass (Titanium dioxide pigment: 6.01% by mass relative to the total ink amount) • Urethane resin emulsion: 20.0% by mass • 1,3-Butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.): 15.0% by mass Glycerin (manufactured by Kanto Chemical Co., Ltd.): 15.0% by mass • Surfinol 104 (manufactured by Nisshin Chemical, acetylene glycol-based surfactant): 0.9% by mass • 2-amino-2-ethyl-1,3-propanediol (manufactured by Kanto Chemical Co., Ltd.): 0.5% by mass • Proxel XLII (manufactured by Arch Chemicals Japan): 0.3% by mass • Deionized water: Remaining amount [White ink D] • White pigment dispersion A: 80.0% by mass (Titanium dioxide pigment: 14.32% by mass relative to the total ink amount) • Urethane resin emulsion: 3.0% by mass • 1,3-Butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.): 5.0% by mass Glycerin (manufactured by Kanto Chemical Co., Ltd.): 10.0% by mass • Surfinol 104 (manufactured by Nisshin Chemical, acetylene glycol-based surfactant): 0.9% by mass • 2-amino-2-ethyl-1,3-propanediol (manufactured by Kanto Chemical Co., Ltd.): 0.5% by mass • Proxel XLII (manufactured by Arch Chemicals Japan): 0.3% by mass • Deionized water: Remaining amount [White ink E] • White pigment dispersion A: 28.0% by mass (Titanium dioxide pigment: 5.01% by mass relative to the total ink amount) • Urethane resin emulsion: 20.0% by mass • 1,3-Butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.): 15.0% by mass Glycerin (manufactured by Kanto Chemical Co., Ltd.): 15.0% by mass • Surfinol 104 (manufactured by Nisshin Chemical, acetylene glycol-based surfactant): 0.9% by mass • 2-amino-2-ethyl-1,3-propanediol (manufactured by Kanto Chemical Co., Ltd.): 0.5% by mass • Proxel XLII (manufactured by Arch Chemicals Japan): 0.3% by mass • Deionized water: Remaining amount [White ink F] • White pigment dispersion A: 62.0% by mass (Titanium dioxide pigment: 11.1% by mass relative to the total ink amount) • Urethane resin emulsion: 13.0% by mass • Ethylene glycol (Tokyo Chemical Industries, Ltd.): 18.0% by mass • BYK-387 (BIG Chemie Co., Ltd.): 0.9% by mass Triethanolamine (Tokyo Chemical Industries, Ltd.): 0.1% by mass • 1,2-Benzothiazolin-3-one (Tokyo Chemical Industries, Ltd.): 0.3% by mass • Deionized water: Remaining amount

[0097] The obtained fabric treatment solution and white ink were used to evaluate "color development (whiteness)," "change in color development (whiteness) over time," and "yellowing" as follows. The results are shown in Tables 1 to 5 below.

[0098] [Color development (whiteness)] First, the fabric treatment solution and white ink manufactured as described above were filled into an image forming apparatus (Ricoh, Ri6000), and the amount of fabric treatment solution applied was 30 mg / cm². 2 The amount of white ink adhering to the surface is 30 mg / cm². 2 It was adjusted to be as follows. Then, black polyester fabric (a woven fabric containing polyester fibers colored with black disperse dye, 60>L * A solid 2cm x 8cm image at 600dpi x 600dpi was printed onto a fabric treatment solution (manufactured by Toms Co., Ltd.), and then dried at 130°C for 90 seconds. Furthermore, a solid 2cm x 8cm image at 600dpi x 600dpi was printed onto the area of ​​the black polyester fabric treated with the fabric treatment solution, and then dried at 110°C for 10 minutes to obtain an image sample. Next, the brightness (L) of the solid image portion of the obtained image sample was measured using a spectrophotometer (device name: X-rite eXact, manufactured by X-Rite Corporation). * The color rendering properties (whiteness) were measured and evaluated based on the following evaluation criteria. (Evaluation Criteria) A:L * 70 or more B:L * 60 or more but less than 70 C:L * less than 60

[0099] [Changes in color development (whiteness) over time] First, an image sample was obtained in the same manner as the evaluation of [color development (whiteness)] described above. Next, within 10 minutes of preparing the image sample, the brightness (L) was measured in the solid image area using a spectrophotometer (device name: X-rite eXact, manufactured by X-Rite). *The color of the color was measured, and then the resulting image sample was left to stand for 30 days in an environment of 25°C and 40RH, and the brightness (L) was measured again in the same manner. * The brightness (L) before and after being placed in a constant temperature bath was measured. * ) rate of change (|L before standing * -L after settling * | / L before settling * The value ) × 100 was calculated, and the change in color development (whiteness) over time was evaluated based on the following evaluation criteria. (Evaluation Criteria) A:L * The rate of change is less than 5% B:L * The rate of change is between 5% and less than 10% C:L * The rate of change is 10% or more.

[0100] [Yellowing] First, an image sample was obtained in the same manner as the evaluation of [color rendering (whiteness)] described above. Next, 24 hours after the image sample was prepared, the chromaticity (b) was measured in the solid image portion of the image sample using a spectrophotometer (device name: X-rite eXact, manufactured by X-Rite). * The color of the sample was measured, and the yellowing was evaluated based on the following evaluation criteria. (Evaluation Criteria) A:b * is less than -1 B:b * -1 or greater, less than 1 C:b * is 1 or more

[0101] [Table 1]

[0102] [Table 2]

[0103] [Table 3]

[0104] [Table 4]

[0105] [Table 5]

[0106] Examples of embodiments of the present invention include the following: <1> A fabric treatment solution applied to a fabric, It contains an amino group-containing resin and a polyvalent metal salt, The amine value of the aforementioned amino group-containing resin is 200 mg KOH / g or more and 1200 mg KOH / g or less. The fabric treatment solution is characterized in that the content of the amino group-containing resin is 0.01% by mass or more and 10% by mass or less, relative to the total amount of the fabric treatment solution. <2> The amine value of the amino group-containing resin is 400 mg KOH / g or more and 1100 mg KOH / g or less. <1> This is the fabric treatment solution described in [reference]. <3> The content of the polyvalent metal salt is 5.0% by mass or more relative to the total amount of the fabric treatment solution. <1> or <2> This is the fabric treatment solution described in [reference]. <4> The content of the amino group-containing resin is 0.1% by mass or more and 5.0% by mass or less, relative to the total amount of the fabric treatment solution. <1> from <3> It is a fabric treatment solution described in any one of the items. <5> The amino group-containing resin contains polyethyleneimine. <1> from <4> It is a fabric treatment solution described in any one of the items. <6> The fabric comprises at least one of polyester fibers and acetate fibers. <1> from <5> It is a fabric treatment solution described in any one of the items. <7> The fabric includes the fibers colored with a disperse dye. <1> from <6> It is a fabric treatment solution described in any one of the items. <8> The aforementioned <1> from <7> A fabric treatment solution as described in any one of the items, This is a set of a fabric treatment liquid and ink, characterized by having ink. <9> The aforementioned <1> from <7> A fabric treatment solution as described in any one of the items, This is a fabric treatment solution and ink set characterized by comprising a white ink containing water, titanium dioxide, glycerin, silicon dioxide, triethylene glycol monobutyl ether, and triethanolamine. <10> The aforementioned <1> from <7> A fabric treatment solution as described in any one of the items, This is a set of a fabric treatment liquid and ink, characterized by having an ink containing 6% to 15% by mass of a white pigment. <11> The aforementioned <1> from <7> A processing liquid containing a processing liquid for fabrics as described in any one of the items, The processing liquid application device is characterized by having a means for applying the aforementioned processing liquid for fabrics to a fabric. <12> The aforementioned <1> from <7> A processing liquid containing a processing liquid for fabrics as described in any one of the items, A means for applying the aforementioned fabric treatment solution to the fabric, The image forming apparatus is characterized by having an ink application means for applying ink to a region of the fabric to which the fabric processing liquid has been applied. <13> The aforementioned <1> from <7> A method for applying a processing liquid, characterized by including a processing liquid application step of applying the processing liquid for fabrics described in any one of the above items to the fabric. <14> The aforementioned <1> from <7> A process of applying a fabric treatment solution described in any one of the items to the fabric, The image forming method is characterized by including an ink application step of applying ink to a region of the fabric to which the fabric treatment liquid has been applied.

[0107] The aforementioned <1> from <7> The fabric treatment liquid described in any of the above, <8> from <10> A set of fabric treatment liquid and ink as described in any of the above, <11> The processing liquid dispensing device described above, <12> The image forming apparatus described above, <13> The method of applying the processing liquid described above, and the <14> According to the image forming method described above, the aforementioned problems in the conventional method can be solved, and the objective of the present invention can be achieved. [Explanation of Symbols]

[0108] 400 Image forming apparatus 401 Exterior of the image forming apparatus 401c Cover of the main unit of the device 404 Cartridge Holder 410p Pretreatment liquid containment means 410W White Ink Storage Method 410k Black Ink Storage 410c Cyan Ink Storage Means 411 Detention Unit 413 Outlet 414 Storage container case 420 Mechanism Department 434 Inkjet ejection head 436 Supply Tube [Prior art documents] [Patent Documents]

[0109] [Patent Document 1] Japanese Patent Publication No. 2019-131919

Claims

1. A fabric treatment solution applied to a fabric, It contains an amino group-containing resin and a polyvalent metal salt, The amine value of the aforementioned amino group-containing resin is 400 mg KOH / g or more and 1100 mg KOH / g or less. The fabric treatment solution is characterized in that the content of the amino group-containing resin is 0.01% by mass or more and 10% by mass or less, relative to the total amount of the fabric treatment solution.

2. The fabric treatment solution according to claim 1, wherein the content of the polyvalent metal salt is 5.0% by mass or more with respect to the total amount of the fabric treatment solution.

3. The fabric treatment solution according to claim 1 or 2, wherein the content of the amino group-containing resin is 0.1% by mass or more and 5.0% by mass or less with respect to the total amount of the fabric treatment solution.

4. The aforementioned amino group-containing resin contains polyethyleneimine, and the fabric treatment solution according to any one of claims 1 to 3.

5. The fabric treatment solution according to any one of claims 1 to 4, wherein the fabric comprises at least one of polyester fibers and acetate fibers.

6. The fabric treatment solution according to any one of claims 1 to 5, wherein the fabric comprises the fibers colored with a disperse dye.

7. A fabric treatment solution applied to a fabric, It contains an amino group-containing resin and a polyvalent metal salt, The amine value of the aforementioned amino group-containing resin is 200 mg KOH / g or more and 1200 mg KOH / g or less. The content of the amino group-containing resin is 0.01% by mass or more and 10% by mass or less, relative to the total amount of the fabric treatment solution. The fabric treatment solution is characterized in that the content of the polyvalent metal salt is 5.0% by mass or more relative to the total amount of the fabric treatment solution.

8. A fabric treatment solution applied to a fabric, It contains an amino group-containing resin and a polyvalent metal salt, The amine value of the aforementioned amino group-containing resin is 200 mg KOH / g or more and 1200 mg KOH / g or less. The content of the amino group-containing resin is 0.01% by mass or more and 10% by mass or less, relative to the total amount of the fabric treatment solution. The aforementioned amino group-containing resin is characterized by containing polyethyleneimine, and is a treatment solution for textiles.

9. A fabric treatment solution according to any one of claims 1 to 8, A set of a fabric treatment liquid and ink, characterized by having ink.

10. A fabric treatment solution according to any one of claims 1 to 8, A set of fabric treatment liquid and ink, characterized by comprising a white ink containing water, titanium dioxide, glycerin, silicon dioxide, triethylene glycol monobutyl ether, and triethanolamine.

11. A fabric treatment solution according to any one of claims 1 to 8, A set of fabric treatment liquid and ink, characterized by comprising an ink containing 6% to 15% by mass of a white pigment.

12. It contains an amino group-containing resin and a polyvalent metal salt, The amine value of the aforementioned amino group-containing resin is 200 mg KOH / g or more and 1200 mg KOH / g or less. The content of the amino group-containing resin is 0.01% by mass or more and 10% by mass or less relative to the total amount of the fabric treatment solution, and is applied to the fabric treatment solution. A white ink containing water, titanium dioxide, glycerin, silicon dioxide, triethylene glycol monobutyl ether, and triethanolamine, A set of fabric treatment liquid and ink characterized by having [a specific feature].

13. It contains an amino group-containing resin and a polyvalent metal salt, The amine value of the aforementioned amino group-containing resin is 200 mg KOH / g or more and 1200 mg KOH / g or less. The content of the amino group-containing resin is 0.01% by mass or more and 10% by mass or less relative to the total amount of the fabric treatment solution, and is applied to the fabric treatment solution. A set of fabric treatment liquid and ink, characterized by comprising an ink containing 6% to 15% by mass of a white pigment.

14. A processing liquid containing a processing liquid for fabrics according to any one of claims 1 to 8, A processing liquid application apparatus characterized by having means for applying the aforementioned processing liquid for fabrics to a fabric.

15. A processing liquid containing a processing liquid for fabrics according to any one of claims 1 to 8, A means for applying the aforementioned fabric treatment solution to the fabric, An image forming apparatus characterized by having an ink application means for applying ink to a region of the fabric to which the fabric processing liquid has been applied.

16. A method for applying a processing liquid, characterized by comprising a step of applying the processing liquid for fabrics described in any one of claims 1 to 8 to the fabric.

17. A process of applying a fabric treatment solution according to any one of claims 1 to 8 to the fabric, An image forming method characterized by comprising an ink application step of applying ink to a region of the fabric to which the fabric treatment liquid has been applied.

Images