Pretreatment liquid, pretreatment device, and pretreatment method

Abstract

The present application relates to a pretreatment liquid, a pretreatment device, and a pretreatment method, which can improve the wash fastness of an image formed on a cloth. The pretreatment liquid of the present disclosure is a pretreatment liquid applied to a cloth in a region including an ejection region of an ink containing a pigment before the ink is ejected, the pretreatment liquid containing a resin, a dry substance of an upper layer component after centrifugal separation of the pretreatment liquid having a storage modulus (G') at 25°C of 95 kPa or less and a storage modulus (G') at 160°C of 47 kPa or less.

Description

Technical Field

[0001] This disclosure relates to pretreatment solutions, pretreatment devices, and pretreatment methods. Background Technology

[0002] Patent document 1 discloses a resin-containing pretreatment liquid applied before the process of applying an ink containing pigment.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2020-63540 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] As disclosed in Patent Document 1, the image formed by applying ink to a pretreated fabric sometimes peels off during washing, raising the issue of wash fastness.

[0008] Therefore, the purpose of this disclosure is to provide a pretreatment liquid, a pretreatment apparatus, and a pretreatment method that can improve the wash fastness of images formed on fabrics.

[0009] Methods for solving problems

[0010] To achieve the above objectives, the pretreatment solution of this disclosure is applied to the fabric in the area containing the ink ejection region before the ink containing pigment is ejected, characterized in that...

[0011] The pretreatment solution contains resin, and the dried upper layer of the pretreatment solution after centrifugation is...

[0012] The energy storage modulus (G') at 25℃ is below 95 kPa.

[0013] The energy storage modulus (G') at 160℃ is below 47 kPa.

[0014] The pretreatment apparatus of this disclosure is used to apply a pretreatment liquid to a fabric in the area containing the ink ejection region before the ink containing pigment is ejected, characterized in that...

[0015] The pretreatment apparatus includes a pretreatment application unit that applies the pretreatment liquid to the fabric, and a dried upper layer of the pretreatment liquid after centrifugal separation.

[0016] The energy storage modulus (G') at 25℃ is below 95 kPa.

[0017] The energy storage modulus (G') at 160℃ is below 47 kPa.

[0018] The pretreatment method of this disclosure applies a pretreatment liquid to the fabric in the area containing the ink ejection region before the ink containing pigment is ejected, characterized in that...

[0019] This includes a pretreatment application step of applying the pretreatment liquid to the fabric.

[0020] The dried upper layer of the pretreatment liquid after centrifugation

[0021] The energy storage modulus (G') at 25℃ is below 95 kPa.

[0022] The energy storage modulus (G') at 160℃ is below 47 kPa.

[0023] Invention Effects

[0024] According to this disclosure, it is possible to improve the wash fastness of images formed on fabrics. Attached Figure Description

[0025] [ Figure 1 ] Figure 1 This is a schematic diagram illustrating an example of the configuration of the preprocessing apparatus of this disclosure.

[0026] [ Figure 2 ] Figure 2 This is a flowchart illustrating an example of a step in the preprocessing method of this disclosure.

[0027] [ Figure 3A ] Figure 3A This is a diagram illustrating an example of the application of a pretreatment liquid in the pretreatment method of this disclosure.

[0028] [ Figure 3B ] Figure 3B This is a diagram illustrating another example of the application of the pretreatment liquid in the pretreatment method of this disclosure.

[0029] [ Figure 4 ] Figure 4 This is a graph showing the storage modulus (G') of the dried upper layer obtained by centrifuging the pretreatment liquids of the examples and comparative examples. Detailed Implementation

[0030] The embodiments of this disclosure will be described. It should be noted that this disclosure is not limited to the embodiments described below. It should also be noted that in the following figures, the same symbols are used to label the same parts. Furthermore, the descriptions of each embodiment can be referenced from each other unless specifically mentioned otherwise. Moreover, the configurations of each embodiment can be combined unless specifically mentioned otherwise.

[0031] <Pretreatment solution>

[0032] First, the pretreatment liquid of this disclosure will be described. The pretreatment liquid of this disclosure is a pretreatment liquid applied to fabric in the area containing the ink ejection region before the ink containing pigment is ejected. The pretreatment liquid contains resin, and the storage modulus (G') of the dried upper component after centrifugation of the pretreatment liquid is 95 kPa or less at 25°C and 47 kPa or less at 160°C. It should be noted that the area containing the ink ejection region can be, for example, the entire area of ​​the ink ejection region or a portion of the ink ejection region.

[0033] The centrifugation method may be, for example, the method described in the embodiments described later. The upper component may also be referred to as the supernatant component, or as the separator containing the resin described later. The centrifugation method is not particularly limited, and may, for example, be a rotation speed of 1000 to 15000 rpm and a centrifugation time of 1 minute to 24 hours.

[0034] The drying method for the upper layer component can be, for example, the method described in the embodiments below. The drying method is not particularly limited, and can be, for example, a temperature range of 50°C to 100°C and a heating time range of 10 minutes to 6 hours, for example, heating can be carried out in a dryer, a constant temperature bath or other similar device.

[0035] The storage modulus (G') at 25°C can be, for example, 0.5 kPa or more, 1 kPa or more, 1.5 kPa or more, or 1.7 kPa or more, and can be 85 kPa or less, 75 kPa or less, 50 kPa or less, 30 kPa or less, or 26 kPa or less. It should be noted that the inventors have discovered that when the storage modulus (G') at 25°C is 95 kPa or less, the resin described later exhibits high flexibility, and therefore the image formed on the fabric is less prone to cracking due to external force. This insight is not disclosed in the prior art, including the aforementioned patent documents and non-patent documents, and is an insight independently discovered by the inventors.

[0036] The storage modulus (G') at 160°C can be, for example, 3 kPa or more, 3.5 kPa or more, or 3.9 kPa or more, and can be 45 kPa or less, 30 kPa or less, 15 kPa or less, or 12 kPa or less. It should be noted that the inventors of this disclosure have discovered that when the storage modulus (G') at 160°C is 47 kPa or less, the resin described later softens more easily during heat drying of the pretreatment liquid of this disclosure, thus tending to adhere sufficiently to the fabric, making the image formed on the fabric less prone to peeling. This means that wash fastness can be improved. Furthermore, the inventors of this disclosure have discovered that the lower the storage modulus (G') at 160°C, the easier it is for the resin described later to form a uniform film relative to the fabric during heat drying, thus improving the color development of the image formed on the fabric. This insight is not disclosed in the prior art, including the aforementioned patent documents and non-patent documents, and is an insight independently discovered by the inventors.

[0037] The storage modulus (G') can be measured, for example, using a rheometer. It should be noted that, unless otherwise specified, the term "storage modulus" in this disclosure refers to the storage modulus (G') in shear mode. The method for measuring the storage modulus (G') can be, for example, the method described in the embodiments described later.

[0038] The resin may be, for example, a resin contained as a component of a resin emulsion. The resin emulsion is, for example, composed of the resin and a dispersion medium (e.g., water). The resin is, for example, dispersed with respect to the dispersion medium not in a dissolved state, but at a specific particle size.

[0039] Examples of resins include acrylic resins, maleate resins, vinyl acetate resins, carbonate resins, polycarbonate resins, styrene resins, ethylene resins, polyethylene resins, propylene resins, polypropylene resins, urethane resins, polyurethane resins, and copolymers thereof. Styrene resins, acrylic resins, and copolymers thereof are preferred. One type of resin or two or more types of resins may be used.

[0040] Commercially available products can be used as the resin emulsion. Examples of such commercially available products include "Mowinyl 6770", "Mowinyl 966A", "Mowinyl 7320", "Mowinyl 6963" and "Mowinyl 6960" manufactured by JapanCoating Resin Co., Ltd., "VINYBLAN GV-6181" and "VINYBLAN GV-1002" manufactured by Nissin Chemical Industry Co., Ltd., and "VONCOAT SFC-55" and "VONCOAT SFC-571" manufactured by DIC Co., Ltd.

[0041] If the total amount of all components contained in the pretreatment liquid is set to 100% by weight, then the content of the resin is, for example, 0.1% to 30% by weight, 0.5% to 20% by weight, or 1% to 10% by weight.

[0042] The pretreatment solution may further include, for example, at least one component selected from polyvalent metal salts, organic acids, organic solvents, amino acids, surfactants, and water.

[0043] Examples of the multivalent metal salts include calcium salts, magnesium salts, and aluminum salts. Examples of calcium salts include calcium chloride, calcium bromide, calcium iodide, calcium nitrite, calcium nitrate, calcium dihydrogen phosphate, calcium thiocyanate, calcium lactate, calcium fumarate, calcium citrate, and their hydrates. Examples of magnesium salts include magnesium chloride, magnesium bromide, magnesium iodide, magnesium sulfate, magnesium nitrate, and their hydrates. Examples of aluminum salts include aluminum chloride, aluminum bromide, aluminum sulfate, aluminum nitrate, aluminum acetate, and their hydrates. One or more multivalent metal salts may be used. It should be noted that, from the viewpoint of suppressing discoloration of the fabric caused by pretreatment, it is preferable to include at least one of calcium and magnesium salts. Furthermore, from the viewpoints of color development of the formed image and cost, it is preferable to include a calcium salt.

[0044] If the total amount of all components contained in the pretreatment solution is set to 100% by weight, then the content of the polyvalent metal salt is, for example, 1% to 50% by weight, 5% to 30% by weight, or 10% to 25% by weight.

[0045] Examples of organic acids include, but are not limited to, saturated fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, and valeric acid; hydroxy acids such as lactic acid, malic acid, and citric acid; aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, and gallic acid; dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, and fumaric acid; uronic acids such as glucuronic acid, galacturonic acid, and iduronic acid; and ascorbic acid. The organic acid may, for example, be a salt whose cation is not a metal ion (e.g., an ammonium salt or an amine salt).

[0046] The molecular weights of the organic solvent and the amino acid can be, for example, 90 or more, 100 or more, or 105 or more, or 170 or more, 180 or more, 190 or more, or 200 or more. The molecular weights of the organic solvent and the amino acid can be, for example, 120 or less, or 500 or less, or 400 or less. It should be noted that when the organic solvent is a high molecular weight organic solvent, the molecular weight can be understood as the number average molecular weight. When the molecular weights of the organic solvent and the amino acid are 100 or more, there is a tendency for the boiling point to become higher; therefore, when drying the pretreatment solution, the generation of fumes (vapors) caused by the evaporation of the organic solvent and the amino acid can be reduced. By reducing the generation of fumes, for example, the visibility of the operating environment is improved, thus improving the operability of the pretreatment application operation. It should be noted that in this disclosure, the organic solvent and the amino acid function, for example, as wetting agents.

[0047] Examples of organic solvents include glycol-based solvents and glycerol-based solvents. Examples of glycol-based solvents include ethylene glycol, diethylene glycol, polyalkylene glycols, 1,3-propanediol, and their derivatives. The polyalkylene glycols may be, for example, polyalkylene glycols with a molecular weight (number average molecular weight) of 200, 300, or 400. Examples of glycerol-based solvents include glycerol, diglycerol, and their derivatives. One organic solvent or two or more organic solvents may be used.

[0048] Examples of the polyalkylene glycols include polyethylene glycol, polypropylene glycol, polybutane glycol, and polyoxyethylene polyoxypropylene glycol. Examples of derivatives of the polyalkylene glycols include polyglycerol, polyoxyethylene glycerol, polyethylene glycol monolauryl ether, polyethylene glycol monododecyl ether, and polyethylene glycol monomethyl ether.

[0049] Examples of the amino acids mentioned include betaine. Examples of betaine include trimethylglycine, carnitine, γ-butyl betaine, taurine betaine, lysine betaine, and alanine betaine. Examples of amino acids other than betaine include glycine, alanine, aspartic acid, glutamic acid, lysine, arginine, and histidine.

[0050] If the total percentage of all components contained in the pretreatment solution is set to 100% by weight, then the content of the organic solvent and the amino acid can be, for example, 15% by weight or more, and can be 25% by weight or less, or 20% by weight or less. From the viewpoint of wash fastness after image formation, the content of the organic solvent and the amino acid is preferably, for example, 15% by weight or more. Furthermore, from the viewpoint of drying efficiency, the content of the organic solvent and the amino acid is preferably, for example, 20% by weight or less.

[0051] It should be noted that, in the case where the pretreatment solution contains at least one of an organic solvent and an amino acid, wherein the organic solvent is at least one of an organic solvent with a molecular weight of 120 or less and an organic solvent with a molecular weight of 170 or more, and the amino acid is at least one of an amino acid with a molecular weight of 120 or less and an amino acid with a molecular weight of 170 or more, if the total percentage of all components contained in the pretreatment solution is set to 100% by weight, then the content of at least one of the organic solvent and the amino acid can, for example, be 15% by weight or more. By setting the content to 15% by weight or more, for example, the scratch resistance of the pretreatment application area can be improved.

[0052] It should be noted that the improved scratch resistance may be due to the following reasons. When the pretreatment solution of this disclosure is dried, the resin component in the resin emulsion contained in the pretreatment solution melts and forms a film due to heat. At this time, the film is formed simultaneously with the organic solvents and amino acids contained in the pretreatment solution. The film strength is reduced when the organic solvents and amino acids are encapsulated, thus making it prone to damage from scratches. This may be a major cause of scratch marks. On the other hand, the phenomenon of encapsulation of the organic solvents and amino acids refers to the organic solvents and amino acids entering the molecular structure of the resin. Therefore, components with lower molecular weights in the organic solvents and amino acids tend to enter the molecular structure more easily. Furthermore, the organic solvents and amino acids move to the upper surface of the fabric through water evaporation accompanying the drying of the pretreatment solution, without entering the molecular structure. This movement tends to occur more easily with lower molecular weights; therefore, when the molecular weight of the organic solvents and amino acids is 120 or less, scratch marks are less likely to occur. Furthermore, when the molecular weight is 170 or higher, the organic solvent and the amino acid have large molecular sizes, making it difficult for them to penetrate the molecular structure and thus less likely to cause scratches. However, the above principle is merely an assumption, and this disclosure is not limited to the above principle.

[0053] The pretreatment solution of this disclosure may, for example, contain other organic solvents. Examples of such other organic solvents include other polyols, other polyol derivatives, sugar alcohols, alcohols, amides, ketones, ketols, ethers, nitrogen-containing solvents other than amides, sulfur-containing solvents, propylene carbonate, ethylene carbonate, and 1,3-dimethyl-2-imidazolinone.

[0054] Other polyols mentioned include, for example, propylene glycol, butanediol, hexanediol, triethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, trimethylolpropane, 1,5-pentanediol, and 1,2,6-hexanetriol. Other examples of the aforementioned polyol derivatives include ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, diethylene glycol n-hexyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol n-propyl ether, triethylene glycol n-butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, tripropylene glycol n-propyl ether, and tripropylene glycol n-butyl ether. Examples of sugar alcohols include sorbitol, mannitol, idutol, tarottol, galactitol, allitol, xylitol, ribitol, arabinitol, erythritol, threitol, isomaltitol, lactitol, avocadoitol, borsitol, and pentaerythritol. Examples of alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, and benzyl alcohol. Examples of amides include dimethylformamide, dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, and cyclohexylpyrrolidone. Examples of ketones include acetone. Examples of ketols include diacetone alcohol. Examples of ethers include tetrahydrofuran and dioxane. Examples of nitrogen-containing solvents other than amides include triethanolamine, triethylamine, and pyridine. Examples of sulfur-containing solvents include thiodiethanol, thiodiethylene glycol, thiodiglycerol, sulfolane, and dimethyl sulfoxide.

[0055] Examples of surfactants include nonionic surfactants. Examples of nonionic surfactants include acetylenic diol surfactants. Commercially available nonionic surfactants can be used. Examples of commercially available products include, for instance, those manufactured by Nissin Chemical Industries, Ltd., such as "OLFINE (registered trademark) E1004", "OLFINE (registered trademark) E1006", "OLFINE (registered trademark) E1010", "OLFINE (registered trademark) E1020", "OLFINE (registered trademark) EXP4001", "OLFINE (registered trademark) EXP4200", "OLFINE (registered trademark) EXP4123", "OLFINE (registered trademark) EXP4300", "OLFINE (registered trademark) PD-001", "OLFINE (registered trademark) PD-002W", "OLFINE (registered trademark) PD-005", "SURFYNOL (registered trademark) 420", "SURFYNOL (registered trademark) 440", "SURFYNOL (registered trademark) 465", and "SURFYNOL (registered trademark) 485".

[0056] The surfactant may also contain surfactants other than nonionic surfactants (e.g., anionic surfactants, cationic surfactants, amphoteric surfactants, etc.).

[0057] If the total amount of all components contained in the pretreatment liquid is set to 100% by weight, then the content of the surfactant can be, for example, more than 0.01% by weight, more than 0.02% by weight, more than 0.03% by weight, or more than 0.04% by weight, and can be less than 2% by weight, less than 1.5% by weight, less than 1% by weight, less than 0.8% by weight, less than 0.5% by weight, less than 0.3% by weight, or less than 0.1% by weight.

[0058] Examples of water include, for example, ion-exchanged water and pure water.

[0059] If the total amount of all components contained in the pretreatment solution is set to 100% by weight, then the water content is, for example, 10% to 90% by weight, or 20% to 80% by weight. The water content can be set as the balance of other components.

[0060] The pretreatment solution disclosed herein may be further included with additives such as crosslinking agents, pH adjusters, viscosity adjusters, preservatives, and fungicides as needed.

[0061] The pigments contained in the ink can include, for example, carbon black, inorganic pigments, and organic pigments. Examples of carbon black include furnace black, lamp black, acetylene black, and channel black. Examples of inorganic pigments include titanium oxide, iron oxide-based inorganic pigments, and carbon black-based inorganic pigments. Examples of organic pigments include azo pigments such as azo lake pigments, insoluble azo pigments, condensed azo pigments, and chelated azo pigments; polycyclic pigments such as phthalocyanine pigments, perylene and pyrene pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindolinone pigments, isoindolineone pigments, and quinophthalone pigments; dye lake pigments such as basic dye-type lake pigments and acid dye-type lake pigments; nitro pigments; nitroso pigments; aniline black daylight fluorescent pigments; and so on. Furthermore, any other pigment that can be dispersed in an aqueous phase can be used. Specific examples of these pigments include CI pigments white 1, 4, 5, 6, 7, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, and 28; CI pigments black 1, 6, and 7; CI pigments yellow 1, 2, 3, 12, 13, 14, 15, 16, 17, 55, 74, 78, 150, 151, 154, 180, 185, and 194; CI pigments orange 31 and 43; and CI pigments red 2, 3, 5, 6, 7, 12, 15, 16, 48, and 48:1. 53:1, 57, 57:1, 112, 122, 123, 139, 144, 146, 149, 150, 166, 168, 175, 176, 177, 178, 184, 185, 190, 202, 209, 221, 222, 224 and 238; CI pigments Violet 19 and 196; CI pigments Blue 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:4, 16, 22 and 60; CI pigments Green 7 and 36; and solid solutions of these pigments, etc.

[0062] The pigment can be dispersed in a solvent using a resin dispersant (also known as a resin-dispersed pigment). As the resin dispersant, for example, a general polymeric dispersant (also known as a pigment dispersion resin or resin dispersant, etc.) can be used, or it can be prepared in-house. Furthermore, in the ink of this disclosure, the pigment can be a pigment encapsulated with a polymer. As the resin dispersant, for example, a resin dispersant containing at least one of methacrylic acid and acrylic acid as monomers can be used, such as commercially available products. The resin dispersant can be, for example, a block copolymer, graft copolymer, or random copolymer, or a salt thereof, composed of two or more monomers selected from the group consisting of hydrophobic monomers such as styrene, styrene derivatives, vinylnaphthalene, vinylnaphthalene derivatives, and α,β-ene unsaturated carboxylic acids, or acrylic acid, acrylic acid derivatives, maleic acid, maleic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, and fumaric acid derivatives. Examples of commercially available products include: "JONCRYL (registered trademark) 611", "JONCRYL (registered trademark) 60", "JONCRYL (registered trademark) 586", "JONCRYL (registered trademark) 687", "JONCRYL (registered trademark) 63" and "JONCRYL (registered trademark) HPD296" manufactured by Johnson Polymer Co., Ltd.; "Disperbyk190" and "Disperbyk191" manufactured by BYK-Chemie Co., Ltd.; "Solsperse20000" and "Solsperse27000" manufactured by Zeneca Co., Ltd.; etc.

[0063] As a method for dispersing the pigment using the pigment dispersion resin, a method of dispersing the pigment using a dispersion device can be cited as an example. The dispersion device used for dispersing the pigment is not particularly limited as long as it is a general disperser, such as a ball mill, roller mill, sand mill (e.g., high-speed type), etc.

[0064] The pigment may be a self-dispersible pigment. Such a self-dispersible pigment, for example, is one in which at least one of hydrophilic functional groups, such as carbonyl, hydroxyl, carboxylic acid, sulfonic acid, and phosphate groups, and their salts are introduced directly into the pigment particles or via other groups through chemical bonds, and can be dispersed in water even without the use of a dispersant. For example, the self-dispersible pigment can be a self-dispersible pigment treated by the methods described in Japanese Patent Application Publication No. 8-3498, Japanese Patent Application Publication No. 2000-513396, Japanese Patent Application Publication No. 2008-524400, Japanese Patent Application Publication No. 2009-515007, and Japanese Patent Application Publication No. 2011-515535. Both inorganic and organic pigments can be used as raw materials for such self-dispersible pigments. Furthermore, examples of pigments suitable for such treatment include carbon black such as "MA8" and "MA100" manufactured by Mitsubishi Chemical Corporation. Commercially available self-dispersible pigments can be used, for example. Examples of commercially available products include: Cabot Corporation's "CAB-O-JET 200", "CAB-O-JET 250C", "CAB-O-JET 260M", "CAB-O-JET 270Y", "CAB-O-JET 300", "CAB-O-JET 400", "CAB-O-JET 450C", "CAB-O-JET 465M", and "CAB-O-JET 470Y"; Orient Chemical Industries, Ltd.'s "BONJET BLACK CW-2" and "BONJET BLACK CW-3"; and Toyo Ink Manufacturing Co., Ltd.'s "LIOJET WD BLACK". "002C", etc.

[0065] The pigment can be one type of pigment or two or more types of pigment.

[0066] Examples of the fabrics mentioned include woven and woven fabrics. The fabric can be made of natural or synthetic fibers. Examples of natural fibers include cotton and silk. Examples of synthetic fibers include polyester, acrylic fibers, rayon, urethane, and nylon. The fabric can also be a blend made by mixing and weaving multiple of the aforementioned fibers, such as cotton / polyester ratios of 50% / 50%.

[0067] <Pretreatment device>

[0068] Next, the preprocessing apparatus for the content of this disclosure will be described. Figure 1 An example of the configuration of the preprocessing apparatus described in this disclosure is shown. For example... Figure 1 As shown, the pretreatment apparatus 10 of this disclosure applies a pretreatment liquid to the fabric in the area containing the ink ejection region before the ink containing the pigment is ejected. The pretreatment apparatus 10 is characterized in that it includes a pretreatment application unit 11 for applying the pretreatment liquid to the fabric.

[0069] Examples of pretreatment application units 11 include liquid spraying units such as liquid nozzles, sprayers, molds, brushes, rollers, etc.

[0070] The pretreatment liquid in the pretreatment apparatus 10 of this disclosure is the same as the pretreatment liquid of this disclosure described above, and can be described by reference thereto.

[0071] It should be noted that the pretreatment apparatus of this disclosure may also include a heat treatment unit, for example. The heat treatment unit may be, for example, a commercially available hot press and oven.

[0072] <Preprocessing Methods>

[0073] Next, the preprocessing method for the content of this disclosure will be explained. Figure 2 This is a flowchart illustrating an example of a step in the pretreatment method of this disclosure. The pretreatment method of this disclosure is a pretreatment method for applying a pretreatment liquid to the fabric in the area containing the ink ejection region before the ink containing the pigment is ejected, including a pretreatment application step.

[0074] The pretreatment application step (S11) applies the pretreatment liquid to the fabric. This pretreatment application step can be performed, for example, by the pretreatment application unit 11 of the pretreatment apparatus 10 of this disclosure. In this pretreatment application step, the application of the pretreatment liquid can be performed, for example, by inkjet printing, spraying, die coating, brushing, roller coating, padding, or other methods.

[0075] In the pretreatment application step, the pretreatment liquid can be applied to the entire surface of the image-forming surface of the fabric, or only a portion thereof. When applying to a portion, for example, an area approximately the same as the ink ejection area of ​​the image-forming surface of the fabric can be designated as the pretreatment liquid application area. When applying to a portion, the size of the pretreatment liquid application area is preferably larger than the printing area. Figure 3A This is a diagram illustrating an example of the application of a pretreatment liquid in the pretreatment method of this disclosure. For example, as... Figure 3A As shown, when printing text (X) on fabric (in this example, a T-shirt) 100, it is preferable to apply the pretreatment liquid in such a way that the pretreatment liquid application part 110 is formed with a line width greater than the line width of the text. Figure 3B This is a diagram illustrating another example of the application of the pretreatment liquid in the pretreatment method of this disclosure. (See diagram for example.) Figure 3B As shown, when printing a pattern on a fabric (T-shirt) 100, it is preferable to apply the pretreatment liquid in such a way that a pretreatment liquid application portion 120 larger than the pattern is formed.

[0076] It should be noted that the pretreatment method of this disclosure can also be performed after the pretreatment liquid application step, for example, by performing a heat treatment step. The heat treatment step can be performed, for example, by at least one of a hot press and an oven. The hot press and the oven can be, for example, commercially available products. The heat treatment temperature in the heat treatment step can differ, for example, between the case where heat treatment is performed by the hot press and the case where heat treatment is performed by the oven. The heat treatment temperature when using the hot press is, for example, 140°C to 200°C. The heat treatment temperature when using the oven is, for example, 140°C to 180°C. It should be noted that the pretreatment method of this disclosure can be implemented, for example, by the pretreatment apparatus 10 described above.

[0077] [Example]

[0078] Next, embodiments and comparative examples of the present disclosure will be described together. It should be noted that the present disclosure is not limited to or restricted by the embodiments and comparative examples described below.

[0079] [Examples 1-8, Comparative Examples 1-3]

[0080] By mixing the components in the pretreatment solution composition (Table 2), the pretreatment solutions of Examples 1-8 and Comparative Examples 1-2 shown in Table 2 were obtained. Specifically, the polyvalent metal salts and water in Table 2 were pre-mixed. Then, a surfactant, an organic solvent or amino acid, a resin emulsion, and a preservative were added sequentially to obtain the pretreatment solution described in Table 2. In addition, the pretreatment solution of Comparative Example 3 was a commercially available pretreatment solution, which, in addition to the components described in Table 2, also contained an acrylic resin (content unknown) as a resin emulsion. It should be noted that the amounts of each component in Table 2 all represent the amount of the active ingredient.

[0081] Using the pretreatment solutions of Examples 1-8 and Comparative Examples 1-3, an image was formed on a black T-shirt (manufactured by GILDAN Corporation, trade name: GILDAN (registered trademark) Ultra cotton, material: 100% cotton) through the following process.

[0082] (Pretreatment application process)

[0083] As shown in Table 2, water was added to the prepared pretreatment solution to dilute it to three times its original volume. Using an automated pretreatment coating apparatus (PRINTSYSTEM, trade name: THE CUBE), the diluted pretreatment solution was applied to the image forming surface of the T-shirt (24 mg / cm²). 2).

[0084] (Heat treatment process (1))

[0085] The pretreatment liquid application area of ​​the T-shirt after the pretreatment process was pretreated and fixed using a hot press (manufactured by STAHLS' Hotronix, trade name: AIR FUSION IQ (registered trademark)). The heat treatment was performed for 35 seconds at a set temperature of 185°C and a set pressure of 31 psi.

[0086] (Image printing process)

[0087] An inkjet printer (manufactured by Brother Industries, Ltd., trade name: GTX (registered trademark) pro) is used to spray white ink (“W ink” in Table 2) onto a T-shirt that has been pretreated with a liquid ink to print an image. White ink (manufactured by Brother Industries, Ltd., trade name: GCX-4W) is used as the ink. It should be noted that the amount of white ink is as described in Table 2.

[0088] (Heat treatment process (2))

[0089] After the image printing process, the ink is heat-fixed on the printed portion of the T-shirt using a dryer (manufactured by ADELCO, trade name: Drawer Drying Cabinet, model: DDC-3A) set to 160°C. The heating time for heat fixing is 3.5 minutes.

[0090] It should be noted that in this embodiment, evaluation samples were prepared through various processes, but this is merely an illustration and not a limitation of the above-described preparation method. For example, the order of each process can be appropriately changed. The evaluation results described later will not change due to changes in the preparation method of the evaluation samples.

[0091] For the pretreatment solutions of Examples 1-8 and Comparative Examples 1-3, the following methods were used to evaluate (a) storage modulus (G'), (b) color development, (c) wash fastness, (d) smoke generation, and (e) scratch resistance.

[0092] (a) Evaluation of energy storage modulus (G')

[0093] The pretreated solution prepared as described above was transferred to centrifuge tubes and centrifuged using a centrifuge (Kubota Corporation, trade name: KUBOTA3200) at 12,000 rpm. Centrifugation was continued until the volume ratio of the upper component (supernatant) to the lower component (precipitate) reached approximately 1:1. After centrifugation, the upper component was transferred to any container and dried at 80°C for 3 hours using a small environmental testing machine (ESPEC Corporation, model: SH-241) to obtain the dried product. It should be noted that the upper component after centrifugation contains components lighter than the lower component. The obtained dried product was punched using an 8mm leather punching machine as an evaluation sample. The storage modulus (G') of the obtained dried product at 25°C and 160°C was determined using a rheometer (TA Instruments, trade name: Discovery HR 20). It should be noted that the measurement conditions for the storage modulus (G') are as follows.

[0094] • Geometry: φ8mm parallel plate

[0095] • Geometric gap: 100~1000μm

[0096] • Gap adjustment during measurement: None

[0097] • Measurement frequency: 1Hz

[0098] • Strain measurement: 1%

[0099] • Axial force adjustment: None

[0100] Here, the storage modulus (G') measured after holding the obtained dried material at 25°C for 5 minutes is defined as "storage modulus (G') at 25°C". Alternatively, the storage modulus (G') measured after holding the obtained dried material at 25°C for 5 minutes, increasing the temperature to 160°C at a rate of 5°C / min, and then holding it at 160°C for 5 minutes is defined as "storage modulus (G') at 160°C". It should be noted that in this embodiment, centrifugation is performed until the volume ratio of the upper component (supernatant) to the lower component (precipitate) is approximately 1:1, but this is not a limitation. For example, the upper component separated in any volume ratio can be used as the evaluation sample for the storage modulus (G').

[0101] It should be noted that, as described later, the good wash fastness of Examples 1-8 compared to Comparative Examples 1-3 indicates that it is important that the storage modulus (G') of the dried upper layer after centrifugation of the pretreated liquid is within a specific range at room temperature and also within a specific range at high temperatures. Therefore, the storage modulus (G') at high temperatures is not limited to a specific temperature. Figure 4Table 1 shows the storage modulus (G') of the dried upper layer obtained by centrifuging the pretreatment liquids of Examples 1-8 and Comparative Examples 1-3, as the temperature was increased from 130°C to 160°C under the same heating conditions. Figure 4 The results in Table 1 confirm that the numerical range of the storage modulus (G') in this disclosure can be set based on the storage modulus (G') at various temperatures from 130°C to 160°C. Therefore, although "storage modulus (G') at 160°C" is exemplified in this disclosure, the storage modulus (G') at any temperature between 130°C and 160°C also satisfies the numerical range of the storage modulus (G') in this disclosure. Thus, even if a temperature below 160°C is applied to the pretreatment liquid during the heat treatment process, as long as the storage modulus (G') at 160°C is within the numerical range of this disclosure, it is understood to be included within the technical scope of this disclosure.

[0102] Table 1

[0103]

[0104] (b) Colorimetric evaluation

[0105] Using the pretreatment solutions of Examples 1-8 and Comparative Examples 1-3, evaluation samples were obtained in the order described above, from "Pretreatment Application Step" to "Heat Fixing Step (2)". CIE1976L was used. * a * b * The color space scaling colorimeter (X-Rite PANTONE, trade name: X-Rite eXact) measures the L-color of the printed portion of a T-shirt with an image of an evaluation sample. * The value was measured.

[0106] (c) Evaluation of wash fastness

[0107] The T-shirt with the image was washed with regular household detergent in a washer-dryer (MAYTAG, model: MWI74140JB2) on COTTON mode at 60°C. Then it was dried in a garment dryer (Panasonic, model: NH-D603) on standard mode with the heater on "strong" setting. CIE1976L was used. * a * b * A color space scaling colorimeter (X-Rite PANTONE, trade name: X-Rite eXact) measures the lightness (L1) of an ink coating (image) before and after washing. * L2 * ΔL is calculated from the measured brightness based on the following equation (1). *This is used as an indicator of wash fastness. It should be noted that the higher the wash fastness, the greater the ΔL. * The smaller the value, the better.

[0108] ΔL * =|L2 * -L1 * | (1)

[0109] L1 * Brightness of the ink coating before washing

[0110] L2 * Brightness of the ink coating after washing

[0111] (d) Evaluation of smoke generation

[0112] The pretreatment solution prepared as described above was sprayed onto the fabric (24 mg / cm²). 2 Then, the fabric with the pretreatment liquid applied was heated at 200°C using a hot plate (manufactured by Seieido Inouchi Co., Ltd., model: PMC-720). Between 2 and 2.5 minutes after heating, the presence or absence of fumes from the area coated with the pretreatment liquid was observed, and the results were evaluated based on the following evaluation criteria.

[0113] Smoke generation evaluation criteria

[0114] 〇: No smoke was produced.

[0115] ×: Smoke is produced. It should be noted that "smoke is produced" refers to the situation where smoke is produced multiple times during the heating period from 2 to 2.5 minutes after heating begins, with each smoke produced less than 3 seconds apart.

[0116] (e) Scratch resistance evaluation

[0117] For the T-shirt after the heat treatment process (1) described above, the part with the pretreatment liquid applied was scratched with a metal plate at an angle of 45 degrees ± 15 degrees relative to the surface of the T-shirt while a load of 0.5 kgf ± 0.1 kgf was applied. The scratch resistance was evaluated based on the following evaluation criteria. It should be noted that the width of the metal plate used was 15 mm and the thickness was 0.7 mm.

[0118] Scratch resistance evaluation criteria

[0119] 〇: No scratches were found.

[0120] ×: Scratches or marks have appeared.

[0121] The composition and evaluation results of the pretreatment solutions of Examples 1-8 and Comparative Examples 1-3 are shown in Table 2.

[0122] [Table 2]

[0123]

[0124] As shown in Table 2, Examples 1-8 exhibited good wash fastness under both high and low ink application conditions. Specifically, the pretreatment solutions with a storage modulus (G') of 95 kPa or less at 25°C and 47 kPa or less at 160°C after centrifugation showed good wash fastness in all examples. Furthermore, in Examples 1-6 and 8, by having the molecular weights of the organic solvent and the amino acid 100 or more, smoke generation was reduced compared to other examples. Moreover, in Examples 3-6 and 8, the molecular weights of the organic solvent and the amino acid were 120 or less or 170 or more, and the total amount of all components contained in the pretreatment solution was set to 100% by weight. By having at least one of the organic solvent and the amino acid at a content of 15% by weight or more, scratch resistance was good compared to other examples. Furthermore, in Examples 4 and 5, the storage modulus (G') of the dried upper component after centrifugation was 95 kPa or less at 25°C and 47 kPa or less at 160°C, resulting in better color development of the image formed on the fabric compared to other examples. On the other hand, Comparative Examples 1 to 3 exhibited poor wash fastness under at least one of the conditions of applying a large amount of ink and applying a small amount of ink.

[0125] This disclosure may be recorded in part or in whole as follows, but is not limited to.

[0126] (Note 1) A pretreatment liquid is applied to a fabric in the area containing the ink ejection region before the ink containing pigment is ejected, characterized in that,

[0127] The pretreatment solution contains resin, and the dried upper layer of the pretreatment solution after centrifugation is...

[0128] The energy storage modulus (G') at 25℃ is below 95 kPa.

[0129] The energy storage modulus (G') at 160℃ is below 47 kPa.

[0130] (Note 2) The pretreatment solution according to Note 1 contains at least one of an organic solvent and an amino acid.

[0131] The organic solvent and the amino acid have a molecular weight of 100 or higher.

[0132] (Note 3) The pretreatment solution according to Note 1 contains at least one of an organic solvent and an amino acid.

[0133] The organic solvent is at least one of organic solvents with a molecular weight of less than 120 and organic solvents with a molecular weight of more than 170.

[0134] The amino acid is at least one of the following: amino acids with a molecular weight of less than 120 and amino acids with a molecular weight of more than 170.

[0135] If the total of all components contained in the pretreatment liquid is set to 100% by weight, then the content of at least one of the organic solvent and the amino acid is 15% by weight or more.

[0136] (Appendix 4) According to the pretreatment liquid described in Appendix 1, the dried upper layer component after centrifugation

[0137] The energy storage modulus (G') at 25℃ is below 26 kPa.

[0138] The energy storage modulus (G') at 160℃ is below 12 kPa.

[0139] (Appendix 5) A pretreatment apparatus for applying a pretreatment liquid to a fabric in an area containing the ink ejection region prior to the ejection of an ink containing pigment, characterized in that,

[0140] The pretreatment apparatus includes a pretreatment application unit that applies the pretreatment liquid to the fabric, and a dried upper layer of the pretreatment liquid after centrifugal separation.

[0141] The energy storage modulus (G') at 25℃ is below 95 kPa.

[0142] The energy storage modulus (G') at 160℃ is below 47 kPa.

[0143] (Appendix 6) A pretreatment method comprising applying a pretreatment liquid to a fabric in the area containing the ink ejection region before the ink containing pigment is ejected, characterized in that,

[0144] This includes a pretreatment application step of applying the pretreatment liquid to the fabric.

[0145] The dried upper layer of the pretreatment liquid after centrifugation

[0146] The energy storage modulus (G') at 25℃ is below 95 kPa.

[0147] The energy storage modulus (G') at 160℃ is below 47 kPa.

[0148] [Industry availability]

[0149] As described above, the pretreatment solution of this disclosure can improve the wash fastness of images formed on fabrics. The application of the pretreatment solution of this disclosure is not particularly limited and can be widely used for pretreatment before forming images on various fabrics.

[0150] [Symbol Explanation]

[0151] 10 Pretreatment device 11 Pretreatment application unit

Claims

1. A pretreatment liquid applied to a fabric in an area containing the ink ejection region before the ink containing pigment is ejected, characterized in that, The pretreatment solution contains resin, and the dried upper layer of the pretreatment solution after centrifugation is... The energy storage modulus (G') at 25℃ is below 95 kPa. The energy storage modulus (G') at 160℃ is below 47 kPa.

2. The pretreatment solution according to claim 1, comprising at least one of an organic solvent and an amino acid. The organic solvent and the amino acid have a molecular weight of 100 or higher.

3. The pretreatment solution according to claim 1, comprising at least one of an organic solvent and an amino acid. The organic solvent is at least one of organic solvents with a molecular weight of less than 120 and organic solvents with a molecular weight of more than 170. The amino acid is at least one of the following: amino acids with a molecular weight of less than 120 and amino acids with a molecular weight of more than 170. If the total of all components contained in the pretreatment liquid is set to 100% by weight, then the content of at least one of the organic solvent and the amino acid is 15% by weight or more.

4. The pretreatment solution according to claim 1, wherein, The dried upper layer after centrifugation The energy storage modulus (G') at 25℃ is below 26 kPa. The energy storage modulus (G') at 160℃ is below 12 kPa.

5. A pretreatment apparatus for applying a pretreatment liquid to a fabric in an area containing the ink ejection region prior to the ejection of an ink containing pigment, characterized in that, The pretreatment apparatus includes a pretreatment application unit that applies the pretreatment liquid to the fabric, and a dried upper layer of the pretreatment liquid after centrifugal separation. The energy storage modulus (G') at 25℃ is below 95 kPa. The energy storage modulus (G') at 160℃ is below 47 kPa.

6. A pretreatment method comprising applying a pretreatment liquid to a fabric in an area containing the ink ejection region prior to the ejection of ink containing pigment, characterized in that, This includes a pretreatment application step of applying the pretreatment liquid to the fabric. The dried upper layer of the pretreatment liquid after centrifugation The energy storage modulus (G') at 25℃ is below 95 kPa. The energy storage modulus (G') at 160℃ is below 47 kPa.

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