A set of processing solution and ink, a printing method, and a printing apparatus.

Abstract

To provide a printing method that can apply excellent concealment even to a cloth colored in a dark color.SOLUTION: Provided is a printing method that comprises a treatment liquid application step of applying a treatment liquid containing a flocculant, a nonionic resin particle, a film-forming aid for the nonionic resin particle, and water onto a cloth.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a set of processing solution and ink, a printing method, and a printing apparatus. [Background technology]

[0002] One method of printing on fabric involves applying a treatment solution to the fabric, and then applying an ink that is reactive with the treatment solution to the area where the treatment solution was applied, thereby fixing the ink to the fabric.

[0003] In printing methods using such processing solutions and inks, when printing on dark-colored fabrics, the opacity of the white ink layer is insufficient. As a result, the color of the white ink layer, and the color ink layer printed on top of it, are affected by the color of the underlying fabric, causing the color development to deviate from the intended result. In other words, the hue of the white ink layer varies depending on the color of the underlying fabric, and if the fabric is dark, the brightness decreases and the saturation becomes dull.

[0004] To solve the above problems, for example, an ink set has been proposed in which an ink contains particles, a surfactant, an organic solvent, a pigment, and water, and a processing solution containing a flocculant, a 1,2-alkanediol, a glycol ether solvent and / or a glycol ether acetate solvent, and water (see, for example, Patent Document 1). [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] The present invention aims to provide a printing method that can impart excellent opacity even to fabrics that are dyed in dark colors. [Means for solving the problem]

[0006] The present invention, as a means for solving the aforementioned problems, includes a processing liquid application step of applying a processing liquid containing a flocculant, nonionic resin particles, a film-forming aid for the nonionic resin particles, and water to a fabric, wherein 3-methoxy-3-methylbutanol is used as the film-forming aid. 0.5 parts by mass to 10 parts by mass per 100 parts by mass of nonionic resin particles Contains, and the nonionic resin particles Ethylene-vinyl acetate copolymer resin particles That is the case. [Effects of the Invention]

[0007] According to the present invention, a printing method is available that can impart excellent opacity even to fabrics that are dyed in dark colors. [Brief explanation of the drawing]

[0008] [Figure 1] Figure 1 is a graph showing the relationship between immersion time and degree of swelling. [Figure 2] Figure 2 is a graph showing the relationship between the content of the film-forming agent and the opacity. [Figure 3] Figure 3 is a schematic diagram showing an example of the printing apparatus of the present invention. [Figure 4] Figure 4 is a perspective view illustrating an example of a main tank. [Figure 5] Figure 5 is a graph showing the relationship between solvent concentration and opacity. [Modes for carrying out the invention]

[0009] (Printing method and printing apparatus) The printing method of the present invention includes a processing solution application step of applying a processing solution containing a flocculant, nonionic resin particles, a film-forming aid for the nonionic resin particles, and water to a fabric surface, preferably including an ink application step, and further including other steps as necessary.

[0010] The printing device of the present invention has a fabric, and a treatment liquid applying means for applying a treatment liquid containing a flocculant, nonionic resin particles, a film-forming aid for the nonionic resin particles, and water onto the fabric. It preferably has an ink applying means, and further has other means as required.

[0011] The printing method of the present invention can be preferably implemented by the printing device of the present invention. The treatment liquid applying step can be performed by the treatment liquid applying means, the ink applying step can be performed by the ink applying means, and the other steps can be performed by the other means.

[0012] In the present invention, as the fabric, there are those made of materials such as cotton, hemp, rayon, acrylic, polyester, etc. Specifically, examples include shirts, T-shirts, trainers, handkerchiefs, dishcloths, towels, noren, tote bags, etc. As the image to be formed on the fabric, any image such as characters, pictures, photographs, combinations of characters and pictures, combinations of characters and photographs, etc. may be used.

[0013] In the prior art, the glycol ether-based solvent and / or glycol ether acetate-based solvent contained in the treatment liquid act as a film-forming aid on the particles in the ink to activate film formation. However, it is necessary to continuously apply the ink while the treatment liquid is in an undried state, and there is a problem that the ink penetrates into the fabric and the concealability decreases.

[0014] As a result of intensive studies by the present inventors, by containing a film-forming aid for the nonionic resin particles in a treatment liquid containing a flocculant, nonionic resin particles, and water, it has been found that high concealability can be obtained even for fabrics colored in dark colors compared to the case where no film-forming aid is contained. A fabric colored in a dark color means a fabric colored with a non-white color (for example, black, red, blue, etc.).

[0015] When applying the treatment liquid used in the printing method of the present invention to the fabric and drying it to form a treatment liquid layer, the film-forming aid contained in the treatment liquid helps the film formation of the nonionic resin particles contained in the treatment liquid, and the film formation of the nonionic resin particles occurs earlier in drying compared to a treatment liquid not containing a conventional film-forming aid. And, due to the early film formation, the nonionic resin particles that have formed a film on the fabric mesh can block near the fabric surface layer, preventing the penetrant from penetrating into the fabric, and the penetrant also stays near the fabric surface layer in the same manner. When applying ink onto the treatment liquid layer formed by such a treatment liquid, (1) since a large amount of the aggregating agent exists near the fabric surface layer, a large amount of the coloring material contained in the ink aggregates near the fabric surface layer. (2) Since the mesh of the fabric surface layer is blocked by the nonionic resin film, the aggregated coloring material is difficult to penetrate into the fabric and stays near the fabric surface layer, forming an ink layer. In addition, if the ink contains resin particles, (3) if there is a film-forming aid remaining in the treatment liquid layer, it also promotes the film formation of the resin particles in the ink, making the ink even more difficult to penetrate, and the ink layer is formed near the fabric surface layer. Therefore, due to the effects (1), (2), and (3) above, a relatively thick ink layer is formed on the fabric surface layer even with a small ink application amount. Since the thick ink layer is difficult to transmit light, the color of the fabric can be concealed.

[0016] In the present invention, the action of the film-forming aid on the nonionic resin particles in the treatment liquid is greatly related to the concealability of the ink layer. As a guideline, when the swelling degree when the resin pieces composed of nonionic resin particles in the treatment liquid obtained as follows are immersed in the film-forming aid is 150% or more, sufficient concealability can be obtained.

[0017] The resin sample for measuring the swelling degree can be produced, for example, by the methods shown in (1) to (3) below. (1) Apply the treatment liquid containing nonionic resin particles onto a glass plate pasted with ETFE (Ethylene tetrafluoroethylene) tape by the casting method to produce a resin film. At this time, form a film by gradually cooling and drying in a normal temperature (23 °C) environment to produce a resin film. (2) Place the processing solution containing nonionic resin particles onto a fluororesin petri dish with high resin release properties, and dry it in an oven or the like on a flat surface to form a film of nonionic resin particles. Repeat this process several times to produce a film of the desired thickness. (3) The resin particles are removed from the processing solution containing the nonionic resin particles by centrifugation. The resin particles are then coated onto a glass plate with ETFE tape attached, which has been heated to a temperature above the glass transition temperature (Tg) of the resin particles, by casting. After coating, the resin is slowly cooled at room temperature (23°C) to form a film and produce a resin film. (4) Separate the resin particles from the processing solution containing nonionic resin particles by centrifugation. Remove the aggregated resin mass in the separation tube, slice it thinly, and polish it to an appropriate thickness to produce a resin film. It is preferable to dry the film prepared by the methods (1) to (4) described above using a vacuum dryer at 30°C for about 24 hours.

[0018] [Measurement of swelling degree] The resin film prepared using the above method, cooled to room temperature (23°C), is cut to create resin pieces approximately 1.0 mm thick x 10 mm long x 20 mm wide. The weight Wa of the resin pieces is measured using a chemical balance. Approximately 100 mL of solvent, liquid resin, or a mixture thereof was placed in a 250 mL test tube with a stopper, and a resin piece was immersed in it. A hook was attached to the underside of the stopper to prevent the resin piece from touching the tube wall, and the test tube was suspended by a single thread for measurement. Next, the container is kept at a constant temperature (30°C) in a constant temperature bath and left to stand in a dark room. After immersing the resin pieces in a solvent, liquid resin, or a mixture thereof and reaching swelling equilibrium within 1 to 20 days, the resin pieces are removed from the solvent, liquid resin, or mixture thereof, wiped with filter paper, and quickly placed in a pre-weighed weighing bottle. The weight Wb of the swollen resin pieces is then measured, and the degree of swelling Q can be calculated using the following formula. Swelling degree Q (%) = 100(Wb-Wa)ρ1 / Wa×ρ2 However, ρ1 represents the density of the resin piece, and ρ2 represents the density of the solvent, liquid resin, or mixture thereof. A graph is created, as shown in Figure 1, plotting the degree of swelling against immersion time. The linear segment of the swelling-time curve is extended, and the intercept at which the immersion time becomes zero is defined as the swelling equilibrium value.

[0019] A film-forming aid is defined as a solvent, liquid resin, or mixture thereof, in which, when a resin piece prepared by any of the methods (1) to (4) above reaches swelling equilibrium, the weight of the resin piece becomes Wb > Wa due to swelling. In other words, when the rate of weight change reaches swelling equilibrium, and the swelling equilibrium value is 105% or higher, the solvent or liquid resin is considered to have function as a film-forming aid for nonionic resin particles. Furthermore, it is possible to quantitatively estimate the ease of film formation of a film-forming aid on nonionic resin particles based on the HSP solubility parameter (HSP value) obtained from molecular structure or statistical data, even without measuring the degree of swelling. This is useful for formulating a large number of candidate film-forming aids with high swelling degrees. However, there are many exceptions, and it is not always reliable, so it is essential to confirm and evaluate the degree of swelling when selecting a film-forming aid.

[0020] The HSP values ​​of a resin chain consisting of one unit structure among the resin chain group constituting the nonionic resin particles are (δd1, δp1, δh1), Let R0 be the interaction sphere radius of the polymer composed of the aforementioned resin chains. The HSP values ​​of the film-forming aid for the nonionic resin particles are (δd2, δp2, δh2). The distance Ra between the HSP value of the resin chain and the HSP value of the film-forming aid is given by the following formula: 2 =4(δd1-δd2) 2 +(δp1-δp2) 2 +(δh1-δh2) 2 Therefore, film-forming aids that satisfy the following equation, Ra ≤ R0, often exhibit high film-forming properties for nonionic resin particles. Sufficient opacity can be obtained by using a processing solution containing such a film-forming aid.

[0021] The interaction sphere radius R0 can be determined as follows. First, examine the solubility in solvents (slightly less than 20 types) for which the HSP value has been determined. Then, find a sphere that encloses all the points in three dimensions of the solvent in which the polymer is dissolved inside the sphere, and the points of the solvents in which it does not dissolve are outside the sphere. (The search for this value can be performed using the HSPiP software, "Sphere".). In the present invention, solvents that swell and those that do not swell are classified using a swelling degree of 150% as a threshold value. Define the center coordinates (δd1, δp1, δh1) of the sphere as the HSP value of the polymer. Define the radius of the sphere as the interaction sphere radius R0. If the coordinates (δd2, δp2, δh2) of the HSP value of the film-forming aid are inside the sphere, then Ra < R0 holds. In HSP, three Hansen parameters are given to a molecule, and usually the unit is MPa 0.5 is. δD is the energy derived from the dispersion force between molecules, δP is the energy derived from the polar force between molecules, and δH is the energy derived from the hydrogen bonding force between molecules

[0022] Regarding the HSP value (δd1, δp1, δh1) of the resin chain, δd1 represents the energy derived from the dispersion force between the molecules of the resin chain, δp1 represents the energy derived from the polar force between the molecules of the resin chain, and δh1 represents the energy derived from the hydrogen bonding force between the molecules of the resin chain. Regarding the HSP value (δd2, δp2, δh2) of the film-forming aid for nonionic resin particles, δd2 represents the energy derived from the dispersion force between the molecules of the film-forming aid, δp2 represents the energy derived from the polar force between the molecules of the film-forming aid, and δh2 represents the energy derived from the polar force between the molecules of the film-forming aid.

[0023] The above interaction sphere radius R0 is a range indicated by a sphere on the (δd, δp, δh) coordinate axis, which is calculated to assume that when a resin piece composed only of a resin chain is immersed in the corresponding film-forming aid when R0 ≤ Ra, the swelling degree of the resin piece becomes 150% or more. For such nonionic resin particles composed only of a resin chain, the film-forming aid corresponds to a good solvent.

[0024] The HSP values ​​(δD, δP, δH) of typical solvents are shown below. [Table A] *MMB: 3-Methoxy-3-methylbutanol *M100:3-Methoxy-N,N-dimethylpropanamide *DPG: Dipropylene glycol *2-E-1,3-HD: 2-ethyl-1,3-hexanediol *DEGMBE: Diethylene glycol monobutyl ether *PGnPE: Propylene glycol-n-propyl ether *DEGMEE: Diethylene glycol monomethyl ether *Y-PE: Manufactured by Yokkaichi Synthetic Co., Ltd., 2-phenoxyethanol

[0025] If the nonionic resin particles contain segments that exhibit a swelling degree of 150% or more in the resin chain alone, and if the film-forming aid is also included, the nonionic resin particles in the treatment solution can achieve faster film formation than the treatment solution without the film-forming aid. When the treatment solution is applied to a fabric, the nonionic resin particles in the treatment solution form a film on the shallower surface layer of the fabric before penetrating deeply, efficiently filling the weave of the fabric. As a result, the ink applied on top of the treatment solution layer can achieve high opacity.

[0026] The film-forming aid in the treatment solution before drying is mixed with other solvents such as water, so it does not swell the nonionic resin particles. Film-forming properties are exhibited when the fast-evaporating solvents such as water evaporate during drying, leaving a concentrated layer of the film-forming aid. When preparing the processing solution, it is necessary to mix the film-forming aid after the main solvent such as water to prevent swelling of the nonionic resin particles, and then mix in the nonionic resin particle dispersion. Mixing the film-forming aid and nonionic resin particles in the reverse order may impair storage and quality stability.

[0027] The ideal amount of film-forming aid in the processing solution depends on whether the film-forming aid dries sufficiently during film formation or whether a large amount remains in the resin being formed as non-volatile components. The drying of the treatment solution is carried out at a drying temperature ranging from room temperature to around 200°C, taking into consideration workability, the heat resistance of the fabric fibers, and the heat resistance and transition properties of the dyed pigments, although this also depends on the type of fabric used as the base material. High-boiling point solvents and liquid resins tend to leave residue. When the film-forming aid dries and evaporates sufficiently during film formation, the ideal content is 1% by mass or more and 30% by mass or less in the processing solution. If a graph like the one shown in Figure 2 is created with the content of the film-forming aid x on the X axis and the opacity I(x) on the Y axis, the resulting opacity I(x) will have a peak somewhere. The opacity value at the maximum peak will be higher than the opacity I0 when there is no film-forming aid (x=0% by mass) (see Figure 2).

[0028] The inventors believe that the above phenomenon can be explained as follows. This is thought to be because the surface tension of the treatment solution decreases as the amount of film-forming aid increases, increasing the permeability of the treatment solution and thus reducing the opacity of the white ink. This is a result of the combined effect of negative effect A and positive effect B, where the permeability of the treatment solution decreases due to the high concentration of film-forming aid. Negative effect A is a monotonically decreasing effect of the film-forming aid content, while positive effect B tends to increase with the amount of film-forming aid in relation to the amount of nonionic resin particles, but saturates beyond a certain amount. Thus, the interplay between negative effect A and positive effect B can result in a curve similar to that shown in Figure 2. Depending on the amount of film-forming aid, negative effect A may be stronger than positive effect B, resulting in weaker opacity compared to no film-forming aid at all. However, when an appropriate amount of film-forming aid is included, positive effect B becomes stronger than negative effect A. Therefore, it is preferable to optimize the film-forming aid content by appropriately evaluating it, as it varies depending on factors such as the HSP value, the content of nonionic resin particles, and the ease with which the film-forming aid dries.

[0029] On the other hand, if the film-forming aid has poor drying properties and tends to remain in the resin as a non-volatile component in large quantities, the content of the film-forming aid is preferably 0.5 parts by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 7 parts by mass or less, per 100 parts by mass of nonionic resin particles contained in the treatment solution. If the content of the film-forming aid is less than 0.5 parts by mass, sufficient opacity cannot be obtained due to the low amount of film-forming aid and the decrease in the surface tension of the treatment solution. On the other hand, if the content of the film-forming aid exceeds 10 parts by mass, too much film-forming aid remains in the resin, which actually inhibits film formation and prevents the acquisition of a strong film. In addition, drawbacks such as stickiness on the film surface may occur.

[0030] <Processing liquid application process and processing liquid application means> The treatment solution application step involves applying a treatment solution containing a flocculant, nonionic resin particles, a film-forming aid for the nonionic resin particles, and water to the fabric surface, and is carried out by a treatment solution application means. The treatment solution may also be referred to as "pretreatment solution" or "pre-coating solution."

[0031] There are no particular restrictions on the method of applying the processing solution, and it can be appropriately selected according to the purpose. Examples include the inkjet method, blade coating method, gravure coating method, gravure offset coating method, bar coating method, roll coating method, spray coating method, knife coating method, air knife coating method, comma coating method, U-comma coating method, AKKU coating method, smoothing coating method, microgravure coating method, reverse roll coating method, 4-roll coating method, 5-roll coating method, dip coating method, curtain coating method, slide coating method, and die coating method. Among these, the roll coating method and spray coating method are preferred.

[0032] For fabrics to which the treatment solution has been applied, it is preferable to perform a heating step to dry the treatment solution by heating the fabric as needed. The heating step is a process of heating the fabric using known heating means such as a roll heater, drum heater, or hot air to dry the treatment solution applied to the fabric.

[0033] The processing solution contains a flocculant, nonionic resin particles, a film-forming aid for the nonionic resin particles, and water, and further contains other components as needed.

[0034] <<Agglutinant>> The coagulant is included for the purpose of imparting to the treatment solution layer the function of coagulating pigments, resin particles, etc., contained in the ink that are applied on top of the treatment solution layer. The ink set is envisioned in which the pigments and resin particles contained in the ink are ion-dispersed, having anionic or cationic charges, and the coagulant has the function of canceling out these charges. Examples of flocculants include cationic resin particles, polyvalent metal salts, and polyvalent organic salts. Among these, polyvalent metal salts have high solubility in water and readily dissolve and penetrate ink applied in layers to the treatment solution. Therefore, they can be suitably used as flocculants that have a high flocculation effect on colorants and resin particles ionically dispersed in the ink.

[0035] -Polyvalent metal salts- Polyvalent metal salts rapidly cause pigments in the ink to aggregate after being dropped, suppressing color bleeding and improving color development. Examples of the polyvalent metal salts include magnesium chloride, magnesium sulfate, magnesium nitrate, magnesium acetate, magnesium bromide, calcium nitrate, calcium acetate, aluminum chloride, aluminum nitrate, or their anhydrous or hydrated forms. These may be used individually or in combination of two or more. Among these, at least one selected from calcium salts, magnesium salts, nickel salts, and aluminum salts is preferred because it can effectively aggregate the pigment, and salts of alkaline earth metals such as calcium and magnesium are more preferred.

[0036] The coagulant content is preferably 0.1% to 20.0% by mass, more preferably 0.5% to 10.0% by mass, and even more preferably 1.0% to 3.0% by mass, relative to the total volume of the treatment solution. When the coagulant content is 0.1% by mass or more, a beading suppression effect is exhibited due to the aggregation of ink components during image formation with ink. On the other hand, when the coagulant content is 20.0% by mass or less, the strength and transparency of the dried coating film are improved.

[0037] <<Nonionic resin particles>> Nonionic resin particles are included in the treated solution layer to some extent when applied to the fabric, with the purpose of physically blocking the penetration of ink printed on top of the treated solution layer into the fabric by partially blocking the weave of the fabric. The more pigment in the ink remains on the surface of the fabric, the better the ink layer can conceal the color of the underlying fabric, resulting in an image with good color development. To ensure dispersion stability, the resin particles contained in the treatment solution must have high dispersion stability that makes them less susceptible to salting out with respect to the coagulant, especially the salt, that is, the resin particles are preferably self-dispersing, nonionic dispersed resin particles that do not have anionic charge.

[0038] Nonionic resin particles are resin particles that can be dispersed without the use of electric charge. In the present invention, nonionic resin particles refer to resin particles in which monomers containing acidic functional groups such as carboxyl groups and sulfo groups, or basic functional groups such as amino groups, are not detected by thermal decomposition GC-MS (for example, GC-17A manufactured by Shimadzu Corporation) after the solid components have been isolated from the liquid composition by centrifugation. Regarding the chemical structure of the resin particles, there are no particular restrictions as long as they are nonionic resin particles that can be nonionically dispersed, and they can be appropriately selected according to the purpose. Examples of the nonionic resin particles include acrylic resins, urethane resins, polyolefin resins; vinyl resins such as ethylene-vinyl acetate resin, polyvinyl acetate resin, and polyvinyl chloride resin; polyamide resins, polyester resins, silicone resins, fluororesins, epoxy resins, vinyl chloride resins, and polystyrene resins. Among these, polyolefin resins, polyvinyl acetate resins, polyvinyl chloride resins, urethane resins, styrene-butadiene resins, or copolymers thereof are particularly noteworthy. These may be used individually or in combination of two or more. Among these, vinyl resins obtained by emulsion polymerization of vinyl monomers such as polyvinyl acetate resin and ethylene-vinyl acetate resin, as well as acrylic resins, urethane resins, polyamide resins, and polyester resins obtained by emulsion polymerization, exhibit excellent film-forming properties at low temperatures (below 180°C), and high opacity can be obtained when white ink is printed over them. Furthermore, because of their excellent adhesion and viscoelasticity, they do not impair the elasticity of fabrics when applied as a base layer, and when printed on clothing, they are less likely to cause image cracking, resulting in printed materials with excellent wash fastness.

[0039] Examples of vinyl monomers used in emulsion polymerization include acrylic monomers such as acrylic acid esters, methacrylic acid esters, acrylic acid, methacrylic acid, and acrylonitrile; styrene monomers such as styrene and α-methylstyrene; and vinyl acetate, acrylamide, maleic acid, fumaric acid, and itaconic acid. These may be used individually or in combination of two or more. Resin aqueous particles are produced by emulsion polymerization of these monomers using conventional methods. Furthermore, the aqueous resin particles may also contain inorganic pigments such as clay, calcium carbonate, titanium dioxide, and talc, as well as coloring pigments, thickeners, plasticizers, defoamers, preservatives, and release agents, which are added when used as a coating composition.

[0040] As nonionic resin particles, the following commercially available products can be used. Examples of polyester resin particles include ES509 (manufactured by Sumitomo Seika Co., Ltd.). Examples of polyamide resin particles include NE205N (manufactured by Sumitomo Seika Co., Ltd.). Examples of vinyl resin particles include VA406, VA407 (manufactured by Sumitomo Chemical Co., Ltd.); S-465HQ, S-401HQ, S-408HQE, S-500HQ, S-801HQ, S-808HQ, S-830, S-850HQ, S-900HL, S-951HQ, S-1010 (manufactured by Sumitomo Chemical Industries, Ltd.); Vinibran 1002, Vinibran 1017-AD, Vinibran GV-6181, Vinibran 4003 (manufactured by Nisshin Chemical Industry Co., Ltd.). Examples of acrylic resin particles include Vinibran 1225, Vinibran 1245L, Vinibran 2680, and Vinibran 2682 (manufactured by Nisshin Chemical Industry Co., Ltd.). Examples of urethane resin particles include Superflex 500M and Superflex E-2000 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.); PUE-1000 and PUE-1370 (manufactured by Murayama Chemical Co., Ltd.); and Hydran WLI-611 (manufactured by DIC Corporation).

[0041] The glass transition temperature (Tg) of the nonionic resin particles is preferably between -30°C and 30°C, and more preferably between -25°C and 25°C. If the glass transition temperature Tg is -30°C or higher, the resin film becomes sufficiently tough, and the treatment solution layer becomes more robust. If it is 30°C or lower, the film-forming properties of the resin improve, and sufficient flexibility is also ensured, resulting in strong adhesion to the substrate, which is preferable. The glass transition temperature can be measured, for example, using a differential scanning calorimetry (DSC) device (device name: DSC120U, manufactured by Seiko Instruments Inc.) at a measurement temperature of 30°C to 300°C and a heating rate of 2.5°C per minute.

[0042] The content of nonionic resin particles is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 0.5% by mass or more and 20% by mass or less, relative to the total amount of the processing solution. If the content is 0.5% by mass or more, the resin can sufficiently cover the fabric, improving adhesion to the fabric. If the content is 30% by mass or less, the film thickness does not become too thick, so there is no risk of reduced adhesion to the substrate.

[0043] There are no particular restrictions on the volume-average particle size of the nonionic resin particles, and they can be appropriately selected depending on the purpose. However, from the viewpoint of obtaining good fixation and high image hardness, a size of 10 nm to 1,000 nm is preferred, 10 nm to 200 nm is more preferred, and 10 nm to 100 nm is particularly preferred. The volume-average particle size can be measured, for example, using a particle size analyzer (NanoTrac Wave-UT151, manufactured by MicroTrac-Bell Co., Ltd.).

[0044] The minimum film-forming temperature (MFT) for nonionic resin particles is preferably 20°C or lower, and more preferably 5°C or lower. When a resin with a low minimum film-forming temperature (MFT) is included, film formation is rapid, and when applied to fabric, the penetration of the treatment solution is suppressed, forming an undercoat layer near the surface of the fabric. As a result, the flocculant remains near the surface along with the resin, and the nonionic resin does not diffuse but fills the weave of the fabric well, thus increasing the effect of blocking ink penetration.

[0045] <<Membrane-forming aid>> A film-forming aid refers to a solvent, liquid resin, or mixture thereof that dissolves and swells the surface layer of nonionic resin particles, thereby assisting and accelerating film formation of nonionic resin particles. A film-forming aid is defined as a relative solvent, liquid resin, or mixture thereof contained in a processing solution, depending on the nonionic resin contained in the processing solution, which is determined to be applicable or not applicable based on its swelling characteristics, evaluated and judged by the method described above for nonionic resin particles contained in the processing solution.

[0046] Organic solvents (e.g., alcohols, glycols, glycol ethers, aldehydes, ketones, etc.), liquid resins, or mixtures thereof with HSP values ​​close to those of nonionic resin particles blended into the treatment solution can swell the target nonionic resin particles well and, when blended into the treatment solution, can act as film-forming aids for the nonionic resin particles. The SP value has traditionally been used as an indicator of whether or not a resin is likely to swell in response to a certain solvent. While the accuracy of determining whether or not swelling actually occurs is lower than that of using the HSP value as an indicator, it does show a general trend. In particular, polyvinyl acetate resin has an SP value of 9.4 to 9.6, and many alcohols, glycols, glycol ethers, aldehydes, and phthalates act as effective film-forming aids when combined with vinyl acetate resins. Furthermore, the SP value of acrylic resin is approximately 9.5, which is close to that of polyvinyl acetate, and similar alcohols, glycols, glycol ethers, aldehydes, and phthalates often act as effective film-forming aids. The SP value of urethane resin is approximately 10, which is somewhat different from the SP values ​​of vinyl acetate resin and acrylic resin. Some alcohols, glycols, glycol ethers, aldehydes, and ketones act as effective film-forming aids, but these do not necessarily correspond to film-forming aids that are effective for polyvinyl acetate resin and acrylic resin.

[0047] Similarly, for polyamides (e.g., nylon 66: SP value = 13.6) and polyethylene resins (SP value = 7.9), the effective film-forming aids differ depending on the SP value of the resin. The film-forming aid may be a solvent or liquid resin alone, or a mixture thereof. In particular, by mixing the components in an appropriate ratio as a mixture, it is possible to create a liquid with an SP value closer to that of the resin, resulting in a film-forming aid with higher effectiveness (the ability to effectively lower the MFT value of the resin with a small concentration). When determining the ratio, it is necessary to consider factors such as vapor pressure difference, and it is desirable that these factors are equivalent.

[0048] Examples of alcohols include 3-methoxy-3-methyl-1-butanol (SP value = 9.6), 3-methyl-1-butanol, and 1-dodecanol (SP value = 9.8). Examples of glycols include dipropylene glycol (SP value = 9.5), 2-ethyl-1,3-hexanediol (SP value = 9.9), and ethylene glycol diacetate (SP value = 10.0). Examples of aliphatic ester alcohols include propylene glycol mono-2-ethylhexanoate (manufactured by Yokkaichi Synthetic Co., Ltd.: product name: Wydenol EHP01). Examples of glycol ethers include ethylene glycol monoethyl ether (SP value = 9.9), ethylene glycol monopropyl ether (SP value = 10.2), ethylene glycol monobutyl ether (SP value = 9.5), diethylene glycol monomethyl ether (SP value = 9.7), diethylene glycol monoethyl ether (SP value = 10.2), diethylene glycol monobutyl ether (SP value = 9.5), triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether (SP value = 9.7), dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether (SP value = 9.4), propylene glycol-n-propyl ether (SP value = 9.8), and triethylene glycol monoethyl ether (SP value = 10.1).

[0049] Other commercially available film-forming aids include polypropylene glycol monomethyl ether (manufactured by Kao Corporation, product name: Smac MP-40), which is a type of polyether. Examples include polyphenyl glycols, primarily composed of polyoxyethylene monophenyl ether (manufactured by Yokkaichi Gosei Co., Ltd.: product name Y-PE), which is also a type of aromatic glycol ether, and products containing a small amount of a component with a high number of ethylene oxide addition moles (manufactured by Yokkaichi Gosei Co., Ltd.: product name YG-15). The above-mentioned Y-PE and TG-15 are also a mixture mainly composed of 2-phenoxyethanol and 2-(2-phenoxyethoxy)ethanol, with the mixing ratio appropriately adjusted as a film-forming aid for water-based vinyl acetate resins.

[0050] Examples of aldehydes include acetaldehyde (SP value = 10.3), isobutyraldehydes such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (manufactured by JNC, trade name: CS-12), and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (manufactured by JNC, trade name: CS-16).

[0051] Examples of ketones include acetone (SP value = 10.0) and ε-caprolactone (SP value = 10.1). Examples of phthalate esters include DEHP: bis(2-ethylhexyl) phthalate, DBP: bis-butyl phthalate, BBP: butyl benzyl phthalate, DIBP: bis-isobutyl phthalate, DINP: bis-isonoryl phthalate, and DIDP: bis-isodecyl phthalate. Examples include DNOP (bis-n-octyl phthalate), DPENP (bispentyl phthalate), DHEXP (bishexyl phthalate), and DCHP (biscyclohexyl phthalate).

[0052] Examples of amines include N-methyl-2-pyrrolidone (SP value = 10.1) and 1,3-dimethyl-2-imidazolidinone (SP value = 10.1).

[0053] These solvents, liquid resins, or mixtures thereof may be used individually or in combination of two or more.

[0054] <<Water>> There are no particular restrictions on the type of water used; it can be selected appropriately depending on the purpose. Examples include pure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water, as well as ultrapure water. These may be used individually or in combination of two or more types. There are no particular restrictions on the water content in the processing solution; it is sufficient to contain a sufficient amount so that polyvalent metal salts do not precipitate when stored at room temperature.

[0055] <<Other ingredients>> The aforementioned treatment solution may contain, as needed, colorants (pigments or dyes), surfactants, defoamers, preservatives and antifungal agents, rust inhibitors, pH adjusters, and the like.

[0056] -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.

[0057] -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.

[0058] -Rust Inhibitor- There are no particular restrictions on the rust inhibitors used; examples include acidic sulfites and sodium thiosulfate.

[0059] - pH adjuster - As a pH adjusting agent, there are no particular restrictions as long as it can adjust the pH to 7 or higher, and examples include amines such as diethanolamine and triethanolamine.

[0060] The aforementioned treatment liquid can be prepared by mixing a flocculant, nonionic resin particles, a film-forming aid for the nonionic resin particles, and water, and optionally other components, and stirring the mixture as needed. Stirring and mixing can be carried out using a conventional agitator with a stirring blade, a magnetic stirrer, a high-speed disperser, etc.

[0061] <Ink application process and ink application means> The ink application process involves applying ink containing resin particles and colorants to the area to which the processing solution has been applied, and is carried out by an ink application means. In this invention, the ink is applied after the processing solution is applied to the fabric. The ink may be applied before or after the processing solution dries, but it is preferable to apply it after drying.

[0062] There are no particular restrictions on the method of applying the ink, and examples include the inkjet method, blade coating method, gravure coating method, gravure offset coating method, bar coating method, roll coating method, knife coating method, air knife coating method, comma coating method, U-comma coating method, AKKU coating method, smoothing coating method, microgravure coating method, reverse roll coating method, 4-roll coating method, 5-roll coating method, dip coating method, curtain coating method, slide coating method, and die coating method. Among these, the inkjet method is preferred due to its ease of maintenance and high work efficiency.

[0063] It is preferable to have a heating step after the ink application step. The heating process is preferably carried out at a temperature between 80°C and 200°C, as this allows for sufficient drying without damaging the fabric. The heating time is preferably between 10 seconds and 10 minutes, as this ensures sufficient drying without damaging the fabric.

[0064] The ink applied to the processing liquid layer used in the printing method of the present invention preferably contains resin particles and a colorant, and contains water, an organic solvent, and a surfactant, and may further contain other components as needed.

[0065] <<Resin particles>> Examples of resins in the aforementioned resin particles 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.

[0066] The aforementioned resin particles may be synthesized as appropriate, or commercially available products may be used. Examples of the commercially available resin particles include Microgel E-1002, E-5002 (styrene-acrylic resin particles, manufactured by Nippon Paint Co., Ltd.), Boncoat 4001 (acrylic resin particles, manufactured by DIC Corporation), Boncoat 5454 (styrene-acrylic resin particles, manufactured by DIC Corporation), SAE-1014 (styrene-acrylic resin particles, manufactured by Nippon Zeon Co., Ltd.), Saibinol SK-200 (acrylic resin particles, manufactured by Saiden Chemical Co., Ltd.), Primal AC-22, AC-61 (acrylic resin particles, manufactured by Rohm & Haas), Nanocryl SBCX-2821, 3689 (acrylic silicone resin particles, manufactured by Toyo Ink Co., Ltd.), and #3070 (methyl methacrylate polymer resin particles, manufactured by Mikuni Pigment Co., Ltd.). Among these, acrylic resin, urethane resin, and polyester resin are more preferred.

[0067] Because the resin particles form a film and create an ink layer, the penetration of pigments in the ink can be suppressed. It is desirable that the resin particles are reactive with the flocculant in the treatment solution, i.e., anionic. Furthermore, resin particles of a resin species whose film-forming properties are promoted by the film-forming aid remaining in the treatment solution layer are preferred. 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. However, from the standpoint of obtaining good adhesion and high image hardness, a size of 10 nm to 1,000 nm is preferred, 10 nm to 200 nm is more preferred, and 10 nm to 100 nm is particularly preferred. The volume-average particle size can be measured, for example, using a particle size analyzer (NanoTrac Wave-UT151, manufactured by MicroTrac-Bell Co., Ltd.).

[0068] There are no particular restrictions on the resin particle content, and it can be appropriately selected depending on the purpose. However, from the viewpoint of fixation and storage stability of the ink, it is preferable that the content be 1% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 20% by mass or less, relative to the total amount of ink.

[0069] <<Colorants>> By applying ink to a processing solution layer treated with the processing solution used in the printing method of the present invention, the fabric color can be better concealed with white ink, and high image density can be obtained with colored inks or black ink, compared to formulations in which the processing solution does not contain a film-forming aid.

[0070] The colorants are not particularly limited; pigments and dyes can be used. In addition, resin hollow particles and inorganic hollow particles can also be used.

[0071] Inorganic or organic pigments can be used as the pigment. These may be used individually or in combination of two or more. Mixed crystals may also be used. 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. As inorganic pigments, for example, titanium dioxide, iron oxide, 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. Examples of organic pigments include azo pigments, polycyclic pigments (e.g., phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinoflarone pigments, etc.), dye chelates (e.g., basic dye type chelates, acid dye type chelates, etc.), nitro pigments, nitroso pigments, and aniline black. Of these pigments, those with good affinity for the solvent are preferably used.

[0072] 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). 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 (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 Examples include 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; and CI Pigment Green 1, 4, 7, 8, 10, 17, 18, 36. These can be used individually or in combination of two or more.

[0073] 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 the aforementioned 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. These can be used individually or in combination of two or more.

[0074] The colorant content is preferably 0.1% to 15% by mass, and more preferably 1% to 10% by mass, relative to the total amount of ink, from the viewpoint of improving image density and good fixation and ejection stability.

[0075] Methods for dispersing pigments in ink include introducing hydrophilic functional groups into the pigment to create a self-dispersible pigment, coating the surface of the pigment with a resin to disperse it, and using a dispersant to disperse it. One method for creating self-dispersible pigments by introducing hydrophilic functional groups into pigments is to use self-dispersible pigments that can be dispersed in water by adding functional groups such as sulfone groups or carboxyl groups to a pigment (e.g., carbon). As a method for coating and dispersing the surface of a pigment with a resin, the pigment can be encapsulated in microcapsules that are dispersible in water. This can be rephrased as resin-coated pigment. In this case, it is not necessary for all pigments incorporated into the ink to be coated with resin; as long as the effects of the present invention are not impaired, uncoated pigments or partially coated pigments may be dispersed in the ink. Methods of dispersion using dispersants include the use of well-known low-molecular-weight dispersants, such as surfactants, and high-molecular-weight dispersants. Depending on the pigment, dispersants such as anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants can be used. RT-100 (nonionic surfactant) manufactured by Takemoto Oil & Fat Co., Ltd., and sodium naphthalene sulfonate formalin condensate can also be suitably used as dispersants. Dispersing agents may be used individually or in combination of two or more.

[0076] -Pigment dispersion- It is possible to obtain ink by mixing colorants with materials such as water and organic solvents. Alternatively, ink can be manufactured by mixing pigments with other materials such as water and dispersants to create a pigment dispersion, and then mixing this dispersion with water and organic solvents. The aforementioned pigment dispersion is obtained by dispersing water, pigment, pigment dispersant, and other components as needed, and adjusting the particle size. Dispersion is preferably carried out using a disperser. While there are no particular restrictions on the particle size of the pigment in the pigment dispersion, a volume-average particle size of 30 to 110 nm is preferable because it improves the dispersion stability of the pigment and enhances image quality, including ejection stability and image density. The particle size of the pigment can be measured using a particle size analyzer (NanoTrac Wave-UT151, manufactured by MicroTrac-Bell Co., Ltd.). The pigment content in the pigment dispersion is not particularly limited and can be appropriately selected depending on the purpose, but from the standpoint of obtaining good discharge stability and increasing image density, it is preferably 0.1% by mass or more and 50% by mass or less, and more preferably 0.1% by mass or more and 30% by mass or less. The pigment dispersion is preferably filtered to remove coarse particles and degassed using a filter, centrifuge, or other means, as needed.

[0077] <<Organic Solvents>> There are no particular restrictions on the organic solvent; water-soluble organic solvents can be used. Examples of the aforementioned water-soluble organic solvents include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers and other ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds. Examples of the water-soluble organic solvents include polyhydric alcohols such as ethylene glycol, diethylene glycol, 1,4-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, 1,6-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, etc.; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether Examples include polyhydric alcohol alkyl ethers such as diethylene 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, and triethylamine; sulfur-containing compounds such as dimethyl sulfoxide, sulfolane, and thiodiethanol; and propylene carbonate. It is preferable to use an organic solvent with a boiling point of 250°C or lower, as it not only functions as a wetting agent but also provides good drying properties.

[0078] There are no particular restrictions on the content of the organic solvent, and it can be appropriately selected depending on the purpose. However, from the viewpoint of ink drying properties and ejection reliability, it is preferable that the content be 10% to 60% by mass of the total ink amount, and more preferably 20% to 60% by mass.

[0079] <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 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. Those having a polyoxyethylene group or a polyoxyethylene polyoxypropylene group as a modifying group are particularly preferred as they exhibit good properties as aqueous surfactants. Furthermore, a polyether-modified silicone surfactant can also be used as the silicone surfactant. Examples include compounds in which a polyalkylene oxide structure is introduced into the Si side chain of dimethylsiloxane.

[0080] As fluorine-based surfactants, 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 are particularly preferred because they have low foaming properties. Examples of the perfluoroalkyl sulfonic acid compounds include perfluoroalkyl sulfonic acid and perfluoroalkyl sulfonate salts. Examples of alkylcarboxylic acid compounds include perfluoroalkylcarboxylic acids and perfluoroalkylcarboxylic acid salts. Examples of polyoxyalkylene ether polymer compounds having a perfluoroalkyl ether group in the side chain include sulfate ester salts of polyoxyalkylene ether polymers having a perfluoroalkyl ether group in the side chain, and salts of polyoxyalkylene ether polymers having a perfluoroalkyl ether group in the side chain. These may be used individually or in combination of two or more. Examples of counterions for the salts of these fluorine-based surfactants include Li, Na, K, NH4, NH3CH2CH2OH, NH2(CH2CH2OH)2, and NH(CH2CH2OH)3.

[0081] Examples of amphoteric surfactants include laurylaminopropionate, lauryldimethylbetaine, stearyldimethylbetaine, and lauryldihydroxyethylbetaine. These may be used individually or in combination of two or more.

[0082] 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. These may be used individually or in combination of two or more.

[0083] Examples of anionic surfactants include polyoxyethylene alkyl ether acetate, dodecylbenzene sulfonate, lauryl salt, and polyoxyethylene alkyl ether sulfate salts. These may be used individually or in combination of two or more.

[0084] <<Water>> There are no particular restrictions on the type of water used; it can be selected appropriately depending on the purpose. Examples include pure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water, as well as ultrapure water. These may be used individually or in combination of two or more types. There are no particular restrictions on the water content in the ink; it is sufficient to contain enough water to prevent the precipitation of polyvalent metal salts when stored at room temperature.

[0085] <<Other ingredients>> Other ingredients are not particularly limited and can be selected as appropriate depending on the purpose. Examples include defoaming agents, antiseptics and antifungal agents, rust inhibitors, and pH adjusters.

[0086] -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.

[0087] -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.

[0088] -Rust Inhibitor- There are no particular restrictions on the rust inhibitors used; examples include acidic sulfites and sodium thiosulfate.

[0089] - pH adjuster - As for pH adjusting agents, there are no particular restrictions as long as they can adjust the pH to 7 or higher, and examples include amines such as diethanolamine and triethanolamine.

[0090] 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 5 mPa·s to 30 mPa·s, and more preferably 5 mPa·s to 25 mPa·s, as this improves print density and character quality and provides good ejection performance. 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 ensure that the ink levels well on the recording medium 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.

[0091] (Processing solution and ink set) The present invention provides a set of processing solution and ink, comprising a processing solution containing a coagulant, nonionic resin particles, a film-forming aid for the nonionic resin particles, and water. It comprises an ink containing resin particles and a colorant.

[0092] <Printing device and printing method> The ink used in this invention can be suitably used in various recording devices using the inkjet recording method, such as printers, facsimile machines, copying machines, printer / fax / copier combination machines, and 3D modeling devices. In the present invention, a printing apparatus and a printing method refer to an apparatus capable of ejecting ink, various processing liquids, etc., onto a recording medium, and a method of recording using the apparatus. A recording medium refers to a material to which ink or various processing liquids can be temporarily attached. This recording device may include not only the ink ejection head, but also means for feeding, transporting, and ejecting the recording medium, as well as other devices referred to as pre-processing devices and post-processing devices. The printing apparatus and printing method may include heating means for the heating process and drying means for the drying process. The heating means and drying means include, for example, means for heating and drying the printing surface and the back surface of the recording medium. The heating means and drying means are not particularly limited, but for example, a hot air heater and an infrared heater can be used. Heating and drying can be performed before printing, during printing, or after printing. Furthermore, printing devices and methods are not limited to those that visualize meaningful images such as characters and figures using ink. For example, they also include those that form patterns such as geometric designs, and those that create three-dimensional images. Furthermore, unless otherwise specified, printing equipment includes both serial type equipment, which moves the ejection head, and line type equipment, which does not move the ejection head. Furthermore, printing devices include not only desktop models, but also wide-format recording devices capable of printing on A0-sized recording media, and continuous-feed printers that can use, for example, continuous paper wound in a roll as a recording medium.

[0093] An example of a printing apparatus will be described with reference to Figures 3 and 4. Figure 3 is a perspective view of the printing apparatus. Figure 4 is a perspective view of the main tank. The image forming apparatus 400, as an example of a printing apparatus, is a serial type image forming apparatus. A mechanism 420 is provided inside the exterior 401 of the image forming apparatus 400. The ink storage sections 411 of the main tanks 410 (410k, 410c, 410m, 410y) for each color, black (K), cyan (C), magenta (M), and yellow (Y), are formed from packaging materials such as aluminum laminate film. The ink storage sections 411 are housed in, for example, plastic storage container cases 414. Thus, the main tanks 410 are used as ink cartridges for each color. 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. The main tank 410 is detachably mounted on the cartridge holder 404. As a result, the ink outlets 413 of the main tank 410 and the ejection heads 434 for each color are connected via supply tubes 436 for each color, enabling ink to be ejected from the ejection heads 434 to the recording medium.

[0094] This printing apparatus may include not only the ink ejection unit, but also devices referred to as pre-treatment devices and post-treatment devices. One embodiment of the pre-treatment device and post-treatment device is to add a liquid storage unit and a liquid ejection head containing pre-treatment liquid and post-treatment liquid, similar to the case of black (K), cyan (C), magenta (M), and yellow (Y) inks, and to eject the pre-treatment liquid and post-treatment liquid using an inkjet recording method. Other embodiments of the pre-processing and post-processing devices include those that utilize methods other than inkjet recording, such as blade coating, roll coating, or spray coating.

[0095] Furthermore, the method of using inks and processing solutions is not limited to inkjet recording methods and can be used in a wide range of applications. In addition to inkjet recording methods, other methods such as blade coating, gravure coating, bar coating, roll coating, dip coating, curtain coating, slide coating, die coating, and spray coating can also be used.

[0096] The inks and processing solutions used in this invention are not particularly limited in their applications and can be appropriately selected according to the purpose. For example, they can be applied to printed materials, paints, coatings, and undercoats. Furthermore, they can be used not only as inks to form two-dimensional characters and images, but also as materials for forming three-dimensional objects (three-dimensional sculptures). The three-dimensional molding apparatus used to create three-dimensional objects can be any known apparatus and is not particularly limited, but for example, one equipped with means for containing, supplying, and dispensing ink, as well as a drying means, can be used. Three-dimensional objects include those obtained by applying multiple coats of ink. Molded products also include those made by processing a structure onto which ink has been applied, such as a recording medium. The molded products are, for example, those obtained by applying molding processes such as heat stretching or punching to recording materials or structures formed in the form of sheets or films, and are suitably used in applications where the surface is decorated before molding, such as meters and control panels for automobiles, office automation equipment, electrical and electronic equipment, and cameras.

[0097] Furthermore, in the terminology of this invention, image formation, recording, printing, etc., are all synonymous. Recording media, media, and printed material are all considered synonyms. [Examples]

[0098] The following describes embodiments of the present invention, but the present invention is not limited in any way to these embodiments.

[0099] (Example 1 of resin sample production) -Preparation of resin sample 1- Four g of undiluted ethylene-vinyl acetate copolymer resin particles (Sumikaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.) were placed in a fluororesin petri dish and dried at 80°C for more than 40 hours to obtain disc-shaped solids with less than 1% residual solvent. A disc-shaped solid of ethylene-vinyl acetate resin cooled to room temperature (23°C) was cut to prepare resin sample 1, which was a resin piece measuring approximately 0.9 mm thick x 30 mm long x 15 mm wide.

[0100] (Example 2 of resin sample manufacturing) -Preparation of resin sample 2- Resin sample 2, which is a resin piece made of acrylic resin, was prepared in the same manner as in resin sample preparation example 1, except that the ethylene-vinyl acetate copolymer resin particles (Sumikaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.) in resin sample preparation example 1 were replaced with nonionic acrylic resin particles (Vinibran 2682, manufactured by Nisshin Chemical Co., Ltd.).

[0101] (Example 3 of resin sample manufacturing) -Preparation of resin sample 3- Resin sample 3, which is a resin piece made of urethane resin, was prepared in the same manner as in resin sample preparation example 1, except that the ethylene-vinyl acetate copolymer resin particles (Sumikaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.) in resin sample preparation example 1 were replaced with nonionic urethane resin particles (isocyanate ester-based urethane resin particles, Superflex E-2000, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

[0102] <Measurement of swelling degree> The weight Wa of each of the obtained resin samples 1-3 was measured using a chemical balance. Approximately 100 mL of solvent, liquid resin, or a mixture thereof was placed in a 250 mL stoppered test tube, and each resin sample was immersed in it. The resin samples were suspended by a single thread with a hook attached to the underside of the stopper to prevent them from touching the tube wall, and then measured. Next, the container was kept at a constant temperature (30°C) in a constant temperature bath and left to stand in a dark room. Each resin sample was immersed in a solvent, liquid resin, or a mixture thereof for 1 to 20 days until swelling equilibrium was reached. After that, each resin sample was removed from the solvent, liquid resin, or mixture thereof, wiped with filter paper, and quickly placed in a pre-weighed weighing bottle. The weight Wb of each swollen resin sample was then measured. The degree of swelling Q was calculated as follows. Swelling degree Q (%) = 100(Wb-Wa)ρ1 / Wa×ρ2 However, ρ1 represents the density of the resin piece, and ρ2 represents the density of the solvent, liquid resin, or mixture thereof. A graph was created, as shown in Figure 1, plotting the degree of swelling against immersion time. The linear segment of the swelling-time curve was extended, and the intercept at which the immersion time became zero was defined as the swelling equilibrium value.

[0103] For the resin samples 1-3 described above, the samples were immersed in different solvents, liquid resins, or mixtures thereof, as shown in Tables 2-4 below. The degree of swelling was measured, the swelling equilibrium value was determined, and the swelling equilibrium value rank was evaluated based on Table 1 below. The results are shown in Tables 2-4.

[0104] [Table 1]

[0105] [Table 2]

[0106] [Table 3]

[0107] [Table 4]

[0108] When the swelling equilibrium value rank is B or higher (swelling equilibrium value of 105% or higher), the solvent, liquid resin, or a mixture thereof is considered to have the function of a film-forming aid for nonionic resin particles.

[0109] (Comparative manufacturing example of the processed solution 1) -Preparation of treatment solution 1- • Flocculant: Calcium chloride...6% by mass Nonionic resin particles: Ethylene-vinyl acetate copolymer resin particles (Sumikaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.) ... 3% by mass • Pure water... Remaining amount (Total: 100% by mass)

[0110] (Comparative manufacturing example of the processed solution 2) -Preparation of treatment solution 2- • Flocculant: Calcium chloride...6% by mass Nonionic resin particles: Ethylene-vinyl acetate copolymer resin particles (Sumikaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.) ... 3% by mass 1,2-Propanediol ···2.5% by mass • Pure water... Remaining amount (Total: 100% by mass)

[0111] (Comparative manufacturing example of the processed solution 3) -Preparation of treatment solution 3- • Flocculant: Calcium chloride...6% by mass Nonionic resin particles: Ethylene-vinyl acetate copolymer resin particles (Sumikaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.) ... 3% by mass 1,2-Propanediol ···5% by mass • Pure water... Remaining amount (Total: 100% by mass)

[0112] (Comparative manufacturing example of the processed liquid 4) -Preparation of treatment solution 4- • Flocculant: Calcium chloride...6% by mass Nonionic resin particles: Ethylene-vinyl acetate copolymer resin particles (Sumikaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.) ... 3% by mass 1,2-Propanediol ···10% by mass • Pure water... Remaining amount (Total: 100% by mass)

[0113] (Comparative manufacturing example of the processed solution 5) -Preparation of treatment solution 5- • Flocculant: Calcium chloride...6% by mass Nonionic resin particles: Ethylene-vinyl acetate copolymer resin particles (Sumikaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.) ... 3% by mass 1,2-Propanediol ···15% by mass • Pure water... Remaining amount (Total: 100% by mass)

[0114] (Comparative manufacturing example of the processed liquid 6) -Preparation of treatment solution 6- • Flocculant: Calcium chloride...6% by mass Nonionic resin particles: Ethylene-vinyl acetate copolymer resin particles (Sumikaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.) ... 3% by mass 1,2-Propanediol ···20% by mass • Pure water... Remaining amount (Total: 100% by mass)

[0115] (Example of processing solution production 1) -Preparation of treatment solution 7- • Flocculant: Calcium chloride...6% by mass Nonionic resin particles: Ethylene-vinyl acetate copolymer resin particles (Sumikaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.) ... 3% by mass ·3-Methoxy-3-methylbutanol···2.5% by mass • Pure water... Remaining amount (Total: 100% by mass)

[0116] (Example of processing solution production 2) -Preparation of treatment solution 8- • Flocculant: Calcium chloride...6% by mass Nonionic resin particles: Ethylene-vinyl acetate copolymer resin particles (Sumikaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.) ... 3% by mass ·3-Methoxy-3-methylbutanol···5% by mass • Pure water... Remaining amount (Total: 100% by mass)

[0117] (Example of processing solution production 3) -Preparation of treatment solution 9- • Flocculant: Calcium chloride...6% by mass Nonionic resin particles: Ethylene-vinyl acetate copolymer resin particles (Sumikaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.) ... 3% by mass ·3-Methoxy-3-methylbutanol···10% by mass • Pure water... Remaining amount (Total: 100% by mass)

[0118] (Example of processing solution production 4) -Preparation of processing solution 10- • Flocculant: Calcium chloride...6% by mass Nonionic resin particles: Ethylene-vinyl acetate copolymer resin particles (Sumikaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.) ... 3% by mass ·3-Methoxy-3-methylbutanol···15% by mass • Pure water... Remaining amount (Total: 100% by mass)

[0119] (Example of processing solution production 5) -Preparation of processing solution 11- • Flocculant: Calcium chloride...6% by mass Nonionic resin particles: Ethylene-vinyl acetate copolymer resin particles (Sumikaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.) ... 3% by mass ·3-Methoxy-3-methylbutanol···20% by mass • Pure water... Remaining amount (Total: 100% by mass)

[0120] [Table 5]

[0121] (Comparative Example 1, Comparative Example 2, and Example 1) <Method for applying the treatment solution to the fabric> (1) Apply 22.5g of each of the above treatment solutions 1 to 11 evenly to a piece of cotton cloth (a 100% cotton T-shirt, product name: 085-CVT, manufactured by Toms Co., Ltd., size: XL, color: black) cut to A4 size) using a spray bottle. (2) The cotton cloth coated with the above processing liquids 1 to 11 was placed in a heat press machine (manufactured by Europort Co., Ltd., product number: CHP-2938), a release paper (manufactured by UACJ Foil Co., Ltd., product name: Cooking Sheet) was placed on top of the cotton cloth, and drying was performed for 90 seconds at a setting of 165°C while pressing.

[0122] <How to print on fabric> A solid image was printed on cotton cloth coated with the above processing solutions 1 to 11 using an inkjet printer (Ricoh Co., Ltd., Ri1000) with white ink (Ricoh Co., Ltd., P3590). The amount of white ink applied was 21.5 g / m². 2After printing with white ink, the sheet was placed in a heat press machine (manufactured by Europort Co., Ltd., product number: CHP-2938), and a release paper (manufactured by UACJ Foil Co., Ltd., product name: Cooking Sheet) was placed on top of a cotton cloth. The sheet was then dried for 90 seconds at a temperature of 165°C while being pressed.

[0123] <Image Evaluation Method> Using a spectrophotometer (X-rite, eXact Standard), the black density of the fabric (product name: 085-CVT, manufactured by Toms Co., Ltd., size: XL, color: black) was measured as K0, and the black density of the solid white images in each print sample was measured as K i The opacity I was calculated using the following formula by measuring the opacity. Hiding I = (K0 - Ki) / K0 However, K0 refers to the black density of the fabric (085-CVT, manufactured by TOM'S Co., Ltd., size: XL, color: black), K i This represents the black density of each solid white image.

[0124] A graph was created with solvent concentration on the X-axis and opacity I on the Y-axis, and is shown in Figure 5. Based on the opacity rank 1 described in Table 6 below, the opacity rank 1 of Comparative Example 1, Comparative Example 2, and Example 1 were evaluated. The results are shown in Table 7. Note that opacity rank 1 is based on the opacity of Comparative Example 1 (treatment solution 1) as the standard, and indicates the difference in opacity of the target sample compared to that standard.

[0125] [Table 6]

[0126] [Table 7]

[0127] From the results in Table 7 and Figure 5, the treatment solution of Example 1, which contains 3-methoxy-3-methylbutanol (MMB) with a swelling equilibrium value rank of A, showed higher opacity compared to treatment solution 1 of Comparative Example 1, which does not contain an organic solvent, in treatment solutions (treatment solutions 8, 9, 10, and 11) containing 3-methoxy-3-methylbutanol at a certain concentration (5% to 20% by mass). In treatment solution 10 (MMB: 15% by mass), the opacity I peaked. On the other hand, the treatment solution of Comparative Example 2, which contained 1,2-propanediol with a swelling equilibrium value rank of C, showed lower opacity compared to treatment solution 1 of Comparative Example 1, which did not contain an organic solvent. The higher the concentration of 1,2-propanediol, the lower the opacity I. When the contained organic solvent is a highly volatile solvent (approximately 0.5 mmHg or higher vapor pressure at 25°C) and does not easily remain in the resin layer formed by the treatment solution, it is preferable to omit the organic solvent if the degree of swelling of the organic solvent in the resin is low (rank C). On the other hand, if the organic solvent has a high degree of swelling in the resin (rank A), including a certain amount of it can improve opacity compared to not including the organic solvent (rank A). The appropriate amount of solvent is thought to depend on the strength of the degree of swelling Q and the ease of evaporation (vapor pressure). In the combination of 3-methoxy-3-methylbutanol and ethylene vinyl acetate, the appropriate amount was 3% / 15% in terms of resin solids / film-forming aid ratio.

[0128] (Comparative manufacturing example of the processed solution 7) -Preparation of processing solution 12- • Flocculant: Calcium chloride...6% by mass Nonionic resin particles: Ethylene-vinyl acetate copolymer resin particles (Sumikaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.) ... 3% by mass • Dipropylene glycol... 0.12% by mass • Pure water... Remaining amount (Total: 100% by mass)

[0129] (Example of processing solution production 6) -Preparation of processing solution 13- • Flocculant: Calcium chloride...6% by mass · Nonionic resin particles: Ethylene-vinyl acetate copolymer resin particles (Sumicaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.)... 3% by mass · 2-Ethyl-1,3-hexanediol... 0.12% by mass · Pure water... balance (total: 100% by mass)

[0130] (Production Example 7 of treatment liquid) - Preparation of treatment liquid 14 · Coagulant: Calcium chloride... 6% by mass · Nonionic resin particles: Ethylene-vinyl acetate copolymer resin particles (Sumicaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.)... 3% by mass · Wijinol (R) EHP01 (propylene glycol mono-2-ethylhexanoate, manufactured by Yokkaichi Gosei Co., Ltd.)... 0.12% by mass · Pure water... balance (total: 100% by mass)

[0131] (Production Example 8 of treatment liquid) - Preparation of treatment liquid 15 · Coagulant: Calcium chloride... 6% by mass · Nonionic resin particles: Ethylene-vinyl acetate copolymer resin particles (Sumicaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.)... 3% by mass · Diethylene glycol monobutyl ether... 0.12% by mass Le)... 0.12% by mass · Pure water... balance (total: 100% by mass)

[0132] (Production Example 9 of treatment liquid) - Preparation of treatment liquid 16 · Coagulant: Calcium chloride... 6% by mass · Nonionic resin particles: Ethylene-vinyl acetate copolymer resin particles (Sumicaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.)... 3% by mass · Diethylene glycol monoethyl ether... 0.12% by mass · Pure water... balance (total: 100% by mass)

[0133] (Example of processing solution production 10) -Preparation of processing solution 17- • Flocculant: Calcium chloride...6% by mass Nonionic resin particles: Ethylene-vinyl acetate copolymer resin particles (Sumikaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.) ... 3% by mass • Smac MP-40 (manufactured by Kao Corporation, polypropylene glycol monomethyl ether) ... 0.12% by mass • Pure water... Remaining amount (Total: 100% by mass)

[0134] (Example of processing solution production 11) -Preparation of processing solution 18- • Flocculant: Calcium chloride...6% by mass Nonionic resin particles: Ethylene-vinyl acetate copolymer resin particles (Sumikaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.) ... 3% by mass • Y-PE (manufactured by Yokkaichi Synthetic Co., Ltd.) (2-phenoxyethanol: 85 parts by mass, 2-(2-phenoxyethoxy)ethanol: 15 parts by mass) ... 0.12% by mass • Pure water... Remaining amount (Total: 100% by mass)

[0135] (Example of processing solution production 12) -Preparation of treatment solution 19- • Flocculant: Calcium chloride...6% by mass Nonionic resin particles: Ethylene-vinyl acetate copolymer resin particles (Sumikaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.) ... 3% by mass • YG-15 (manufactured by Yokkaichi Synthetic Co., Ltd.) (2-phenoxyethanol, 2-(2-phenoxyethoxy)ethanol, polyethylene glycol monophenoxy ether) ... 0.12% by mass • Pure water... Remaining amount (Total: 100% by mass)

[0136] (Example of processing solution production 13) -Preparation of treatment solution 20- • Flocculant: Calcium chloride...6% by mass Nonionic resin particles: Ethylene-vinyl acetate copolymer resin particles (Sumikaflex 465HQ, manufactured by Sumitomo Chemical Co., Ltd.) ... 3% by mass • CS-12 [manufactured by JNC Corporation] (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate) ... 0.12% by mass • Pure water... Remaining amount (Total: 100% by mass)

[0137] [Table 8]

[0138] (Comparative Example 1, Comparative Example 3, and Examples 2-9) <Method for applying the treatment solution to the fabric> In the same manner as in Comparative Example 1 (treatment solution 1) described above, treatment solutions 12 to 20 were spray-applied to a cotton cloth (100% cotton T-shirt: 085-CVT, manufactured by Toms Co., Ltd., size: XL, cut to A4 size), and then pressed dry (165°C for 90 seconds).

[0139] <How to print on fabric> Each processing solution (processing solution 12-20) was applied to cotton cloth, and a solid image of white ink (Ricoh Co., Ltd., P3590) was printed on it using an inkjet printer (Ricoh Co., Ltd., Ri1000) to create each printed sample. The amount of white ink applied was 21.5 g / m². 2 That was the case.

[0140] <Image Evaluation Method> Using a spectrophotometer (X-rite, eXact Standard), the black density of the fabric (product name: 085-CVT, manufactured by Toms Co., Ltd., size: XL, color: black) was measured at K0, and the black density of the solid white images in each print sample was measured at K. i The opacity I was calculated using the following formula after measuring the opacity. I = (K0 - Ki) / K0 However, K0 refers to the black density of the fabric (085-CVT, manufactured by TOM'S Co., Ltd., size: XL, color: black), K i This represents the black density of each solid white image.

[0141] Next, the opacity of Comparative Examples 1 and 3 and Examples 2 to 9 was evaluated based on the opacity rank 1 described in Table 6 above. The results are shown in Table 9. Note that opacity rank 1 is based on the opacity of Comparative Example 1 (treatment solution 1) as the standard, and indicates the difference in opacity of the target sample compared to that standard.

[0142] [Table 9] From the results in Table 9, it was found that all of the treatment solutions 13 to 20 containing the above film-forming aid had superior opacity compared to treatment solution 1 and treatment solution 3 (Comparative Examples 1 and 3).

[0143] (Comparative production examples of the treatment solution 8-9 and production examples of the treatment solution 14-21) -Preparation of processing solutions 21-30- Next, treatment solutions 21 to 30 containing nonionic acrylic resin particles according to the formulations shown in Table 11 below were prepared.

[0144] [Table 11]

[0145] (Comparative Examples 4-5 and Examples 10-17) <Method for applying the treatment solution to the fabric> In the same manner as in Comparative Example 1 (treatment solution 1), the above treatment solutions 21 to 30 were spray-applied to a cotton cloth (100% cotton T-shirt: 085-CVT, manufactured by Toms Co., Ltd., size: XL, cut to A4 size), and then pressed dry (165°C for 90 seconds).

[0146] <How to print on fabric> Cotton cloth coated with each of the processing solutions (processing solutions 21-30) prepared using the method described above was printed with a solid image of white ink (Ricoh Co., Ltd., P3590) using an inkjet printer (Ricoh Co., Ltd., Ri1000) to create printed samples. The amount of white ink applied was 21.5 g / m². 2 That was the case.

[0147] <Image Evaluation Method> For the prepared print samples, a spectrophotometer (X-rite, eXact Standard) was used to determine the black density (K0) of the fabric (product name: 085-CVT, manufactured by Toms Co., Ltd., size: XL, color: black), and the black density (K) of the solid white image in each print sample. i The opacity I was calculated using the following formula after measuring the opacity. Hiding I = (K0 - Ki) / K0 However, K0 refers to the black density of the fabric (085-CVT, manufactured by TOM'S Co., Ltd., size: XL, color: black), K i This represents the black density of each solid white image.

[0148] Next, the opacity of Comparative Examples 4-5 and Examples 10-17 was evaluated based on the opacity rank 2 described in Table 12 below. The results are shown in Table 13. Note that opacity rank 2 is based on the opacity of Comparative Example 4 (treatment solution 21) as the standard, and indicates the difference in opacity of the target sample compared to that standard.

[0149] [Table 12]

[0150] [Table 13] From the results in Table 13, it was found that the film-forming aids in the above-mentioned treatment solutions 23 to 30, as used in Examples 10 to 17, all had superior opacity compared to treatment solutions 21 and 22 (Comparative Examples 4 and 5).

[0151] (Comparative manufacturing examples of the processed solution 10-13 and manufacturing examples of the processed solution 22-27) -Preparation of processing solutions 31-40- Next, treatment solutions 31 to 40 containing nonionic urethane resin particles according to the formulations shown in Table 14 below were prepared.

[0152] [Table 14]

[0153] (Comparative Examples 6-9 and Examples 18-23) <Method for applying the treatment solution to the fabric> In the same manner as in Comparative Example 1 (treatment solution 1), the above treatment solutions 31 to 40 were spray-applied to a cotton cloth (100% cotton T-shirt: 085-CVT, manufactured by Toms Co., Ltd., size: XL, cut to A4 size), and then pressed dry (165°C for 90 seconds).

[0154] <How to print on fabric> A solid image of white ink (Ricoh Co., Ltd., P3590) was printed onto cotton cloth coated with each processing solution (processing solution 31-40) using an inkjet printer (Ricoh Co., Ltd., Ri1000) to create samples for print evaluation. The amount of white ink applied was 21.5 g / m². 2 That was the case.

[0155] <Image Evaluation Method> Using a spectrophotometer (X-rite, eXact Standard), the black density of the fabric (product name: 085-CVT, manufactured by Toms Co., Ltd., size: XL, color: black) was measured at K0, and the black density of the solid white images in each print sample was measured at K. i The opacity I was calculated using the following formula after measuring the opacity. I = (K0 - Ki) / K0 However, K0 refers to the black density of the fabric (085-CVT, manufactured by TOM'S Co., Ltd., size: XL, color: black), K i This represents the black density of each solid white image.

[0156] Next, the opacity of Comparative Examples 6-9 and Examples 18-23 was evaluated based on opacity rank 3 as shown in Table 15 below. The results are shown in Table 16. Note that opacity rank 3 is based on the opacity of Comparative Example 6 (treatment solution 31) as the standard, and indicates the difference in opacity of the target sample compared to that standard.

[0157] [Table 15]

[0158] [Table 16]

[0159] From the results in Table 16, it was found that the film-forming aids in any of the treatment solutions 34-36 and 38-40 used in Examples 18-23 had equivalent or superior opacity to any of the treatment solutions 31-33 and 37 (Comparative Examples 6-8 and 9).

[0160] Examples of the present invention are as follows: <1> The printing method is characterized by including a step of applying a processing solution containing a flocculant, nonionic resin particles, a film-forming aid for the nonionic resin particles, and water to a fabric surface. <2> The degree of swelling of the resin piece made of the nonionic resin particles when immersed in the film-forming aid is 150% or more, <1> This is the printing method described. <3> The nonionic resin particles are either vinyl resin particles or acrylic resin particles. The film-forming aid is at least one organic solvent selected from alcohols, glycols, and glycol ethers. <1> from <2> This is the printing method described in one of the following. <4> The nonionic resin particles are either vinyl resin particles or acrylic resin particles. The film-forming aid is at least one organic solvent selected from isobutyraldehyde and polyphenyl glycols. <1> from <3> This is the printing method described in one of the following. <5> The nonionic resin particles are urethane resin particles, The film-forming aid is at least one organic solvent selected from alcohols, glycols, glycol ethers, and amides. <1> from <2> This is the printing method described in one of the following. <6> The alcohols are 3-methoxy-3-methylbutanol, <3> and <5> This is the printing method described in one of the following. <7> The printing method according to any one of <3> and <5>, wherein the glycol ethers are polyethers. <8> The printing method according to any one of <3> and <5>, wherein the glycol ethers are aliphatic ester alcohols. <9> The printing method according to any one of <1> to <8>, wherein the nonionic resin particles are polyvinyl acetate resin particles. <10> The printing method according to any one of <1> to <9>, including an ink application step of applying ink containing resin particles and a colorant to a site where the treatment liquid has been applied. <11> A printing apparatus comprising a fabric and a treatment liquid application means for applying a treatment liquid containing a flocculant, nonionic resin particles, a film-forming aid for the nonionic resin particles, and water onto the fabric. <12> The printing apparatus according to <11>, having an ink application means for applying ink containing resin particles and a colorant to a site where the treatment liquid has been applied. <13> A treatment liquid containing a flocculant, nonionic resin particles, a film-forming aid for the nonionic resin particles, and water, An ink containing resin particles and a colorant, and a set of the treatment liquid and the ink.

[0161] According to the printing method according to any one of <1> to <10>, the printing apparatus according to any one of <11> to <12>, and the set of the treatment liquid and the ink according to <13>, various problems in the prior art can be solved, and the object of the present invention can be achieved.

Explanation of Reference Numerals

[0162] 400 Image forming apparatus 401 Exterior of the image forming apparatus 401c Cover of the apparatus main body 404 Cartridge holder 410 Main tank 410k, 410c, 410m, 410y Main tanks for each color of black (K), cyan (C), magenta (M), and yellow (Y) 411 Ink reservoir 413 Ink outlet 414 Storage container case 420 Mechanism Department 434 Discharge head 436 Supply Tube [Prior art documents] [Patent Documents]

[0163] [Patent Document 1] International Publication No. 2017 / 154683

Claims

1. The process includes a step of applying a treatment solution containing a flocculant, nonionic resin particles, a film-forming aid for the nonionic resin particles, and water to a fabric surface. The aforementioned film-forming aid contains 0.5 to 10 parts by mass of 3-methoxy-3-methylbutanol per 100 parts by mass of nonionic resin particles. A printing method characterized in that the nonionic resin particles are ethylene-vinyl acetate copolymer resin particles.

2. The printing method according to claim 1, wherein the degree of swelling of a resin piece made of nonionic resin particles when immersed in 3-methoxy-3-methylbutanol is 150% or more.

3. The printing method according to claim 1 or 2, further comprising an ink application step of applying an ink containing resin particles and a colorant to the area to which the processing liquid has been applied.

4. The device comprises a fabric and a means for applying a treatment solution containing a flocculant, nonionic resin particles, a film-forming aid for the nonionic resin particles, and water to the fabric. The aforementioned film-forming aid contains 0.5 to 10 parts by mass of 3-methoxy-3-methylbutanol per 100 parts by mass of nonionic resin particles. A printing apparatus characterized in that the nonionic resin particles are ethylene-vinyl acetate copolymer resin particles.

5. The printing apparatus according to claim 4, further comprising an ink-applying means for applying ink containing resin particles and a colorant to the area to which the processing liquid has been applied.

6. A treatment solution containing a flocculant, nonionic resin particles, a film-forming aid for the nonionic resin particles, and water, The ink contains resin particles and a colorant, The aforementioned film-forming aid contains 0.5 to 10 parts by mass of 3-methoxy-3-methylbutanol per 100 parts by mass of nonionic resin particles. The nonionic resin particles are ethylene-vinyl acetate copolymer resin particles. A set of processing solution and ink.

Images