Ink set and inkjet recording method

Abstract

To provide an ink set which has good wet friction fastness, color development property and feeling.SOLUTION: An ink set contains a first treatment liquid containing a water-soluble cationic resin and a first organic solvent, and a second treatment liquid containing a pigment, an anionic resin having Tg of 0°C or lower and a second organic solvent. A cationic value of the water-soluble cationic resin is 1.2 mmol / g or more and 6.2 mmol / g or less. A molecular weight of the water-soluble cationic resin is 500 or more and 4,000 or less.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to an ink set and an inkjet recording method. [Background technology]

[0002] Conventionally, exhaustion printing, in which a fabric is immersed in a bath filled with a dye, has been known as a printing method, but since it takes a long time to dye, production efficiency is low. In recent years, inkjet printing, in which an image is formed on a fabric by an inkjet method, has been widely used because it can dye in a short time and has high production efficiency. In inkjet printing, minute droplets of ink are ejected from an inkjet recording head and landed on the fabric to form an image (see, for example, Patent Documents 1 to 3).

[0003] Patent Document 1 also describes an inkjet recording fabric having an ink absorbing layer on the surface of a fiber substrate. Images and the like are formed on the inkjet recording fabric using a pigment ink with an inkjet printer or the like.

[0004] Patent Document 2 describes an inkjet recording method in which a treatment liquid containing a cationic surfactant and a cationic or nonionic polymer is inkjet recorded on a fabric to which a thermoplastic resin has been applied, and then inkjet recording is performed with an ink containing an anionic dispersant and a pigment.

[0005] Furthermore, Patent Document 3 describes an inkjet textile printing method (inkjet recording method) in which a textile printing ink composition containing a urethane resin having a crosslinkable group is applied to a fabric that has been treated with a pretreatment liquid containing a cationic organic compound. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 11-293571 [Patent Document 2] JP 2006-342455 A [Patent Document 3] JP 2018-3184 A Summary of the Invention [Problem to be solved by the invention]

[0007] For example, when recording is performed on the inkjet recording fabric described in Patent Document 1 by the inkjet recording method described in Patent Documents 2 and 3, there is room for improvement in wet friction fastness, color development, and texture.

[0008] An object of the present invention is to provide an ink set having good wet rub fastness, color development and texture, and an ink jet recording method using the ink set. [Means for solving the problem]

[0009] An ink set according to one embodiment of the present invention comprises a first treatment liquid containing a water-soluble cationic resin and a first organic solvent, and a second treatment liquid containing a pigment, an anionic resin having a Tg of 0°C or less, and a second organic solvent, wherein the water-soluble cationic resin has a cationic value of 1.2 mmol / g or more and 6.2 mmol / g or less, and a molecular weight of the water-soluble cationic resin is 500 or more and 4,000 or less.

[0010] An inkjet recording method according to one embodiment of the present invention is an inkjet recording method for forming an image on a fabric using the above-mentioned ink set, and includes a step of ejecting the first treatment liquid onto the fabric, and a step of ejecting the second treatment liquid onto the fabric. Effect of the Invention

[0011] According to the present invention, it is possible to provide an ink set having good wet rub fastness, color development, and texture, and an ink jet recording method using the ink set. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 is a schematic diagram showing the configuration of a textile printing apparatus. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] An ink set according to an embodiment of the present invention and an ink jet recording method using the ink set will be described below.

[0014] [Ink set configuration] The ink set of the present embodiment includes a first treatment liquid and a second treatment liquid.

[0015] (First treatment liquid) The first treatment liquid contains a water-soluble cationic resin and a first organic solvent.

[0016] The water-soluble cationic resin reacts or interacts with the anionic resin contained in the second treatment liquid to aggregate. This makes it easier to fix the pigment in the ink set to the fabric. The cationic value of the water-soluble cationic resin is 1.2 mmol / g or more and 6.2 mmol / g or less, and more preferably 1.2 mmol / g or more and 4.4 mmol / g or less. If the cationic value is within this range, the coagulation force of the water-soluble cationic resin contained in the first treatment liquid and the anionic resin contained in the second treatment liquid can be made appropriate.

[0017] Examples of the water-soluble cationic resin having a cationic value of 1.2 mmol / g or more and 6.2 mmol / g or less include polyamine, diallylamine hydrochloride polymer, diallylamine polymer, methyl diallylamine hydrochloride polymer, methyl diallylamine amidosulfate polymer, methyl diallylamine acetate polymer, diallyl dimethyl ammonium chloride polymer, diallyl methyl ethyl ammonium ethyl sulfate polymer, amine-epichlorohydrin condensation polymer, poly-2-hydroxypropyl dimethyl ammonium chloride, dimethylamine-ethylene diamine-epichlorohydrin condensate, and dimethylamine-ammonia-epichlorohydrin condensate.

[0018] Examples of commercially available water-soluble cationic resins include MPT-60 (Mitsubishi Pencil Co., Ltd.), Unisense KHE100L, Unisense FPA101L (all from Senka Corporation), PAS-M-1L (Nittobo Medical Co., Ltd.), PE-30, PAS-22SA-40, and PAS-J-81L (all from Yokkaichi Chemical Co., Ltd.).

[0019] The cationic value of the water-soluble cationic resin can be determined, for example, by the following method. First, an aqueous dispersion of the water-soluble cationic resin is prepared. Next, toluidine blue is added as an indicator to the aqueous dispersion of the water-soluble cationic resin. Next, titration is performed using a PVSK (potassium polyvinyl sulfate) solution as a titration reagent. The end point is when the dispersion changes color from blue to red. Finally, the cationic value of the water-soluble cationic resin is calculated from the amount of resin (solid content) in the aqueous dispersion and the titration amount of the PVSK solution.

[0020] The molecular weight of the water-soluble cationic resin is 500 or more and 4000 or less, and more preferably 600 or more and 3000 or less. If the molecular weight of the water-soluble cationic resin is less than 500, the water-soluble cationic resin migrates from the fabric, causing dye migration and staining. On the other hand, if the molecular weight of the water-soluble cationic resin is more than 4000, the water-soluble cationic resin is less likely to fuse to the fabric, and wet friction fastness is deteriorated.

[0021] From the viewpoint of yellowing weather resistance of the fabric due to heating, the water-soluble cationic resin preferably contains tertiary ammonium or quaternary ammonium. If only a series lower than tertiary is contained, yellowing may occur depending on the temperature when the fabric is heated.

[0022] Examples of the tertiary ammonium or quaternary ammonium include quaternary salts of alkylamine-epichlorohydrin adducts, quaternary salts of alkylamine-ammonia-epichlorohydrin adducts, diallyldimethylammonium chloride polymers, and polymeryldiallylamine hydrochloride polymers. From the viewpoint of weather resistance of the fabric to yellowing caused by heating, it is more preferable that the tertiary ammonium or quaternary ammonium contains quaternary ammonium.

[0023] The content of the water-soluble cationic resin in the first treatment liquid is preferably within a range of 1.5 to 18 mass %, and more preferably within a range of 3.5 to 18 mass %.

[0024] The water-soluble cationic resin may be used alone or in combination with a plurality of types. In the following examples, one type of water-soluble cationic resin is used.

[0025] The first organic solvent is not particularly limited as long as it can properly disperse the water-soluble cationic resin.

[0026] Examples of the first organic solvent include monohydric alcohols (e.g., methanol, ethanol, propanol, pentanol, hexanol, cyclohexanol, and benzyl alcohol), polyhydric alcohols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, glycerin, butylene glycol, hexanediol, pentanediol, hexanetriol, thiodiglycol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2-heptanediol, and trimethylolpropane), polyhydric alcohol ethers (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, and diene glycol monoethyl ether), and polyhydric alcohol ethers (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, and diene glycol monoethyl ether). Examples of the alkyl ethers include ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; amines (e.g., ethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, and triethylenetetramine); amides (e.g., formamide, N,N-dimethylformamide, and N,N-dimethylacetamide); heterocycles (e.g., 2-pyrrolidone, N-methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, 2-oxazolidone, and 1,3-dimethyl-2-imidazolidine); sulfoxides (e.g., dimethyl sulfoxide); and sulfones (e.g., sulfolane).

[0027] The first organic solvent preferably contains a glycol-based or diol-based solvent having a boiling point of 200° C. or higher. This makes it difficult for the first treatment liquid to dry on the conveyor belt even if it penetrates through the fabric, and therefore makes it difficult for the belt cleaning properties to deteriorate.

[0028] Examples of glycol-based or diol-based solvents with a boiling point of 200° C. or higher include 1,3-butanediol (boiling point 208° C.), 1,6-hexanediol (boiling point 223° C.), polypropylene glycol, glycerin (boiling point 290° C.), and trimethylolpropane (boiling point 295° C.).

[0029] The first organic solvent may be used alone or in combination with a plurality of types In the following examples, a plurality of types of first organic solvents are used.

[0030] (Other Ingredients) The first treatment liquid may further contain other components in addition to those described above, as necessary, to the extent that the effects of the present invention are not impaired. Examples of the other components include water, a surfactant, a preservative, and a pH adjuster.

[0031] Examples of water include ion-exchanged water, distilled water, and pure water.

[0032] Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants.

[0033] Examples of preservatives include aromatic halogen compounds (eg, Preventol CMK), methylene dithiocyanate, halogen-containing nitrogen-sulfur compounds, and 1,2-benzisothiazolin-3-one (eg, PROXEL GXL).

[0034] (Second treatment liquid) The second treatment liquid contains a pigment, an anionic resin having a Tg of 0° C. or lower, and a second organic solvent.

[0035] The pigment may be an organic pigment or an inorganic pigment such as titanium oxide. Generally, the pigment is anionic. The pigment may be used alone or in combination with a plurality of types. In the following examples, the pigment is used alone.

[0036] Examples of organic pigments include azo, azomethine, methine, diphenylmethane, triphenylmethane, quinacridone, anthraquinone, perylene, indigo, quinophthalone, isoindolinone, isoindoline, azine, oxazine, thiazine, dioxazine, thiazole, phthalocyanine, and diketopyrrolopyrrole.

[0037] Examples of organic pigments for magenta or red include CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 48:1, CI Pigment Red 53:1, CI Pigment Red 57:1, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 139, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 202, CI Pigment Red 222, CI Pigment Violet 19.

[0038] Examples of organic pigments for orange or yellow include CI Pigment Orange 31, CI Pigment Orange 43, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 15:3, CI Pigment Yellow 17, CI Pigment Yellow 74, CI Pigment Yellow 93, CI Pigment Yellow 128, CI Pigment Yellow 94, CI Pigment Yellow 138, CI Pigment Yellow 155.

[0039] Examples of organic pigments for green or cyan include CI Pigment Blue 15, CI Pigment Blue 15:2, CI Pigment Blue 15:3, CI Pigment Blue 16, CI Pigment Blue 60, CI Pigment Green 7.

[0040] Examples of organic pigments for black include CI Pigment Black 1, CI Pigment Black 6, and CI Pigment Black 7.

[0041] The titanium oxide is preferably rutile-type titanium oxide from the viewpoint of a large refractive index and high hiding power. Commercially available examples of titanium oxide include the TR series from Fuji Titanium Industries Co., Ltd., the JR series from Teika Co., Ltd., and Typeque from Ishihara Sangyo Kaisha, Ltd.

[0042] The pigment may be a self-dispersing pigment. A self-dispersing pigment is a pigment particle whose surface is modified with a group having a hydrophilic group, and has pigment particles and hydrophilic groups bonded to the surface of the pigment particles.

[0043] Examples of hydrophilic groups include carboxy groups, sulfonic acid groups, and phosphorus-containing groups. Examples of phosphorus-containing groups include phosphoric acid groups, phosphonic acid groups, phosphinic acid groups, phosphite groups, and phosphate groups.

[0044] Commercially available examples of self-dispersing pigments include Cabot's Cab-0-Jet® 200K, 250C, 260M, and 270V (sulfonic acid group-containing self-dispersing pigments), Cab-0-Jet® 300K (carboxylic acid group-containing self-dispersing pigments), and Cab-0-Jet® 400K, 450C, 465M, 470V, and 480V (phosphate group-containing self-dispersing pigments).

[0045] The content of the pigment in the second treatment liquid is preferably within a range from 1 to 10% by mass, and more preferably within a range from 1 to 5% by mass, relative to the total amount of the second treatment liquid.

[0046] An anionic resin having a glass transition temperature Tg of 0°C or less functions as a binder for the pigment. By containing an anionic resin in the second treatment liquid, the fixation of the pigment can be improved. The glass transition temperature Tg is preferably -80°C or higher. In addition, by having a Tg of 0°C or less, the aggregates are less likely to harden, and therefore belt cleaning properties are improved.

[0047] The glass transition temperature Tg can be measured using a differential scanning calorimeter (DSC). Specifically, the glass transition temperature Tg can be read from an endothermic peak when the temperature is raised at a rate of 10°C / min in a temperature range of -100 to 200°C using a DSC.

[0048] Examples of anionic resins include polyesters, polyurethanes, polyacrylics, and polymethacrylics having acidic groups such as carboxyl groups, sulfonyl groups, and phosphorus-containing groups (phosphate groups or phosphonic acid groups).

[0049] Examples of commercially available anionic resins include the Acryset EMN series manufactured by Nippon Shokubai Co., Ltd., the NeoCryl series manufactured by Kusumoto Chemicals Co., Ltd., the Joncryl series manufactured by BASF, the Takelac series manufactured by Mitsui Chemicals, Inc., the HUX series manufactured by ADEKA Corporation, the Evaphanol series manufactured by NICCA Chemical Co., Ltd., and the Superflex series manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[0050] The anion value is preferably within the range of 10 to 60 mgKOH / g. If the anion value is less than 10 mgKOH / g, the dispersion stability of the resin in the aqueous medium may decrease. On the other hand, if the acid value is more than 60 mgKOH / g, the cationic resin may rapidly aggregate, resulting in a decrease in color development.

[0051] The anionic resin may be used alone or in combination with a plurality of types. In the following examples, the anionic resin is used alone.

[0052] The content (solid content) of the anionic resin is preferably within a range of 5 to 15% by mass with respect to the total amount of the second treatment liquid. If the content of the anionic resin is 5% by mass or more, the fixability of the pigment can be further improved. If the content of the anionic resin is 15% by mass or less, the amount of aggregates adhering to the conveyor belt does not become too large, and deterioration of belt cleaning properties can be suppressed.

[0053] The second organic solvent can be the same as the first organic solvent. The content of the organic solvent in the second treatment liquid is preferably within a range of 20 to 50% by mass with respect to the total amount of the second treatment liquid.

[0054] (Other Ingredients) The second treatment liquid may further contain other components than those described above as necessary, within the scope of not impairing the effects of the present invention. Examples of the other components include water, a surfactant, a preservative, and a pH adjuster, as in the first treatment liquid.

[0055] The total amount of the water-soluble cationic resin, pigment, and anionic resin is within a range of 1:0.8 to 1:16, and preferably within a range of 1:1.1 to 1:9.7. By keeping the total amount of the water-soluble cationic resin, pigment, and anionic resin within the above range, color development and texture can be improved.

[0056] The total amount of cations in the water-soluble cationic resin in the first treatment liquid and the second treatment liquid per area of ​​the fabric is 0.07 mmol / m 2 More than 0.43mmol / m 2 If the total amount of the cations is within the above range, the color development and texture can be improved.

[0057] (fabric) The fabric is not particularly limited. Examples of the fabric include natural fibers (including natural cellulose fibers, hemp, wool, and silk), synthetic cellulose fibers (including regenerated cellulose fibers such as rayon, and semi-synthetic cellulose fibers such as acetate), vinylon fibers, nylon fibers, acrylic fibers, polyurethane fibers, and polyester fibers.

[0058] The fabric may be any of the above-mentioned fibers in the form of woven fabric, nonwoven fabric, knitted fabric, etc. The fabric may also be a blended woven fabric or blended nonwoven fabric of two or more kinds of fibers.

[0059] (Inkjet recording method) The inkjet recording method of the present invention is an inkjet recording method for forming an image on a fabric using the above-mentioned ink set, and includes a step of ejecting a first treatment liquid and a step of ejecting a second treatment liquid onto the fabric. That is, the inkjet recording method of the present invention applies the first treatment liquid and the second treatment liquid continuously onto the fabric. The application of the first treatment liquid and the second treatment liquid is performed by carrying the fabric on a conveyor belt. The conveyor belt may be a conventional one, such as an adhesive one.

[0060] Here, "applying consecutively" means that there is no step such as a drying step between applying the first treatment liquid and the second treatment liquid to the same location. Note that it is permissible for a part of the volatile components of the first treatment liquid to volatilize by natural drying before applying the second treatment liquid.

[0061] In the present invention, the first and second treatment liquids are applied successively onto the fabric, so that the first and second treatment liquids are applied wet-on-wet, and the texture of the fabric is less likely to be damaged. This is because, in the case of wet-on-wet, the components of the treatment liquids are in high contact with each other, and so they tend to aggregate before penetrating into the yarns that make up the fabric. By aggregating before penetrating into the yarns, the fibers that make up the yarns are not bonded together, and deterioration of the texture is suppressed.

[0062] The order of application of the first treatment liquid and the second treatment liquid is not particularly limited. From the viewpoint that the water-soluble cationic resin contained in the first treatment liquid functions as an ink receiving layer, it is preferable to apply the first treatment liquid first. The first treatment liquid and the second treatment liquid may be applied simultaneously.

[0063] The method of applying the first treatment liquid and the second treatment liquid is not particularly limited. The method of applying the first treatment liquid and the second treatment liquid may be the same or different. Examples of the application method include a spray method, a mangle method (a pad method or a dipping method), a coating method, and an inkjet method. When performing high-precision printing, the inkjet method is preferable as the application method of the first treatment liquid and the second treatment liquid.

[0064] The amount of the first treatment liquid applied is not particularly limited, and is adjusted depending on the content of the water-soluble cationic resin in the first treatment liquid, the amount of the second treatment liquid applied, the type of fabric, etc. From the viewpoint of reducing the amount of aggregates adhering to the conveyor belt, it is preferable that the amount of the first treatment liquid applied is smaller than the water retention capacity of the fabric in order to suppress the strike-through of the first treatment liquid through the fabric.

[0065] The amount of the second treatment liquid applied is not particularly limited, and can be adjusted depending on the pigment content of the second treatment liquid, the density of the image to be printed, the type of fabric, etc. From the viewpoint of reducing aggregates adhering to the conveyor belt, it is preferable that the amount of the second treatment liquid applied is smaller than the water retention capacity of the fabric in order to suppress the strike-through of the second treatment liquid through the fabric.

[0066] The inkjet recording method of the present invention preferably includes a step of drying the fabric after the step of applying the first treatment liquid and the second treatment liquid, whereby the first treatment liquid and the second treatment liquid applied to the fabric are fixed to the fabric.

[0067] The drying method is not particularly limited and may be a method using a heater, a hot air dryer, a heated roller, etc. Among them, it is preferable to use a hot air dryer and a heater to heat and dry both sides of the fabric.

[0068] The drying temperature is not particularly limited, but from the viewpoint of sufficiently removing the solvent contained in the applied treatment liquid, it is preferably 110° C. or higher, and more preferably within the range of 130 to 180° C. The drying time varies depending on the drying temperature, but is, for example, within the range of 0.5 to 10 minutes.

[0069] (Configuration of Inkjet Recording Apparatus) Next, an inkjet recording apparatus (textile printing apparatus) used in the inkjet recording method of this embodiment will be described.

[0070] FIG. 1 is a schematic diagram showing the configuration of an inkjet recording apparatus (textile printing apparatus) 1. As shown in FIG.

[0071] As shown in FIG. 1, an inkjet recording apparatus (textile printing apparatus) 1 has a belt conveying section 2, an image forming section 3, and a conveyor belt cleaning section 4.

[0072] In the belt conveying section 2, an endless conveying belt 23 of a predetermined width is stretched around a driving roller 21 and a driven roller 22 arranged in parallel with a predetermined interval. The surface (upper surface) of the conveying belt 23 stretched around the driving roller 21 and the driven roller 22 serves as a placement surface on which the fabric P is placed in close contact. An adhesive called a grounding agent may be applied to the surface of the conveying belt 23 to ensure that the fabric P is in close contact during conveyance. The driving roller 21 is driven to rotate by a sub-scanning motor (not shown).

[0073] In the belt conveying section 2, the driving roller 21 rotates at a predetermined speed in the counterclockwise direction (see the arrow) in Fig. 1 by the rotational drive of the sub-scanning motor. This causes the conveying belt 23 stretched between the driving roller 21 and the driven roller 22 to rotate and move. By this operation, the fabric P placed on the surface of the conveying belt 23 is conveyed in the direction of the arrow A in Fig. 1, which is the sub-scanning direction.

[0074] The fabric P may be in the form of a sheet cut to a predetermined size, or in the form of a long piece that is continuously unwound from a roll.

[0075] In the case of an inkjet system, the image forming unit 3 is composed of inkjet heads arranged at a predetermined interval above the surface on which the fabric P is placed on the conveyor belt 23. Each inkjet head ejects treatment liquid from a number of nozzles provided on its lower surface onto the fabric P conveyed by the conveyor belt 23, according to the inkjet recording method described above. In this way, a desired image is formed on the fabric P.

[0076] The image forming unit 3 may be of a shuttle type mounted on a carriage and reciprocating in a main scanning direction perpendicular to the conveying direction of the intermittently conveyed fabric P. In this case, the conveyor belt 23 is controlled by the rotational drive of the drive roller 21 so as to perform an intermittent operation of repeating a standby state and a driving state during image formation. The image forming unit 3 may also be of a line type fixedly suspended across the width direction of the conveyor belt 23 and forming an image by ejecting ink droplets onto the continuously conveyed fabric P. In this case, the conveyor belt 23 is controlled by the rotational drive of the drive roller 21 so as to perform a continuous moving (rotating) operation during image formation.

[0077] The conveyor belt cleaning unit 4 is disposed below the belt conveying unit 2. In the conveyor belt cleaning unit 4, a plurality of cleaning means and the like are provided in order along the moving direction of the conveyor belt 23.

[0078] The conveyor belt cleaning unit 4 shown in FIG. 1 includes a water sprinkling pipe 41, a brush roller 42, a cleaning blade 43, a cleaning sponge 44, and a heating unit 45.

[0079] The water sprinkling pipe 41 is suspended across the entire width of the conveyor belt 23. A large number of nozzles (not shown) are arranged in the water sprinkling pipe 41 along the length direction at a portion facing the surface of the conveyor belt 23. A cleaning liquid is supplied to the water sprinkling pipe 41 through a water sprinkling tube 41a by driving a water sprinkling pump (not shown). The water sprinkling pipe 41 sprays the supplied cleaning liquid from the nozzles toward the surface of the conveyor belt 23, thereby cleaning foreign matter adhering to the surface of the conveyor belt 23.

[0080] The brush roller 42 is formed in a roller shape by planting a plurality of brush bundles, each of which is a bundle of brush bristles, around a rotating shaft that is stretched across the entire width of the conveyor belt 23. The tip of the brush bundle is always in contact with the surface of the conveyor belt 23 downstream of the water sprinkling position of the water sprinkling pipe 41 in the rotation direction of the conveyor belt 23. The brush roller 42 rotatably contacts the surface of the conveyor belt 23 and removes foreign matter such as aggregates remaining on the surface of the conveyor belt 23. Specifically, the brush roller 42 rotates at a predetermined speed in the same direction as the rotation direction of the drive roller 21 based on the power of a brush drive unit (not shown). As a result, the brush roller 42 moves in a direction opposite to the moving direction of the conveyor belt 23 and rubs the surface of the conveyor belt 23 with the tip of the brush bundle. With this operation, the brush roller 42 removes foreign matter washed by the water sprinkling of the cleaning liquid by the water sprinkling pipe 41 on the upstream side of the moving direction of the conveyor belt 23.

[0081] A cleaning tub (not shown) for storing cleaning liquid may be provided below the brush roller 42. In this case, the lower part of the brush roller 42 is partially immersed in the cleaning liquid, and the cleaning liquid is stirred up during rotation, thereby enhancing the effect of removing foreign matter. The cleaning liquid in the cleaning tub may be supplied to the water sprinkler pipe 41 via a water sprinkler tube 41a. In this case, the cleaning liquid sprayed and dripped onto the surface of the conveyor belt 23 is stored again in the cleaning tub and reused.

[0082] The cleaning blade 43 is provided downstream of the brush roller 42 in the rotation direction of the conveyor belt 23. The cleaning blade 43 is formed in a flat plate shape using, for example, an elastic material such as rubber, a PET sheet, or a straight brush, and is stretched across the entire width of the conveyor belt 23. The cleaning blade 43 is configured so that its tip can come into contact with or be separated from the surface of the conveyor belt 23. The cleaning blade 43 comes into contact with the surface of the conveyor belt 23 and removes foreign matter and cleaning liquid remaining on the surface of the conveyor belt 23 by scraping them off.

[0083] The cleaning sponge 44 is a porous body having water absorption properties, such as a sponge, and is stretched across the entire width of the conveyor belt 23. The surface of the cleaning sponge 44 is configured so as to be able to come into contact with or separate from the surface of the conveyor belt 23 downstream of the cleaning blade 43 in the rotation direction of the conveyor belt 23. By coming into contact with the surface of the conveyor belt 23, the cleaning sponge 44 absorbs and wipes off the cleaning liquid remaining on the surface of the conveyor belt 23.

[0084] The heating unit 45 is a belt heater, and is provided downstream of the cleaning sponge 44 and upstream of the driven roller 22 in the rotation direction of the conveyor belt 23. The heating unit 45 heats and evaporates the cleaning liquid remaining on the surface of the conveyor belt 23. EXAMPLES

[0085] The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the following examples, unless otherwise specified, the operations were performed at room temperature (25°C). Furthermore, unless otherwise specified, "%", "ppm" and "parts" mean "% by mass", "ppm by mass" and "parts by mass", respectively.

[0086] [Preparation of the first and second processing liquids] The components shown in Tables 1 and 2 were mixed to prepare first treatment liquids (1-1 to 1-14) and second treatment liquids (2-1 to 2-5), respectively.

[0087] The details of each component are shown in Tables 1 and 2 and below.

[0088] The water-soluble cationic resins used were MPT-60 (Mitsubishi Pencil Co., Ltd.), Unisense KHE100L, Unisense FPA101L (all from Senka Corporation), PAS-M-1L (methyldiallylamine hydrochloride polymer) (Nittobo Medical Co., Ltd.), PE-30 (dimethylamine-ethylenediamine-epichlorohydrin copolymer), PAS-22SA-40 (methyldiallylamine amidosulfate polymer), and PAS-J-81L (methyldiallylamine hydrochloride polymer) (all from Yokkaichi Chemical Co., Ltd.).

[0089] The anionic acrylic resins used were EMN-325E and EF-021 (Nihon Shokubai Co., Ltd.), while the anionic urethane resins used were Superflex 150, Superflex 470 (Daiichi Kogyo Co., Ltd.), and Evaphanol HA-207 (Nicca Chemical Co., Ltd.).

[0090] Cabo-Jet-4637M (Cabot Corporation) was used as the pigment dispersion. E1010 (Nissin Chemical Industry Co., Ltd.) was used as the activator (acetylene glycol surfactant). Proxcel GXL(S) (Lonza Corporation) was used as the preservative.

[0091] [Table 1]

[0092] [Table 2]

[0093] [Textile image formation] As the fabric, cotton satin (100% cotton: product name 60 cotton satin, manufactured by Okadaya Co., Ltd.) was prepared.

[0094] The prepared first and second treatment liquids were introduced into a simple printing tester equipped with an inkjet head KM1024i (Konica Minolta, Inc.), and the first and second treatment liquids were continuously applied in this order onto the fabric by the inkjet method, and then dried to obtain a printed image. The first and second treatment liquid layer-forming liquids were ejected from the inkjet head at 540 dpi in the main scan direction and 720 dpi in the sub-scan direction. dpi represents the number of ink droplets (dots) per 2.54 cm. The ejection frequency was 22.4 kHz. The product was then dried at 150°C for 3 minutes in a belt-transporting dryer to obtain a 100% solid printed image of 200 mm x 200 mm. The adhesion amounts of the first and second treatment liquids were each 15 g / m 2 and 30 g / m 2 These adhesion amounts were each determined from the amount of the treatment liquid discharged.

[0095] [Evaluation of color development] The surface reflectance of the printed solid image was measured using a spectrophotometer CM-25d (Konica Minolta, Inc.) and the K / S value at 540 nm was calculated. The K / S value is an index of surface color density defined by the following formula. Kubelka-Munk formula: K / S=(1-R)2 / 2R (K: light absorption coefficient, S: light scattering coefficient, R: surface reflectance) The higher the K / S value, the higher the color density, and the lower the K / S value, the lower the color density. Based on the calculated K / S value, the color development was evaluated according to the following criteria. In the following criteria, A and B were considered to be within the acceptable range. Evaluation criteria A: K / S value is 5.0 or more B: K / S value is 4.0 or more and less than 5.0 C: K / S value is 3.0 or more and less than 4.0 D: K / S value is less than 3.0

[0096] [Evaluation of wet rub fastness] The wet rub fastness of the image formed on the fabric was evaluated using a crock meter (rubbing tester type I) in accordance with the wet test of JIS L 0849.

[0097] Specifically, a 100 mm x 100 mm area of ​​the formed image was rubbed back and forth 100 times with a white cotton cloth for rubbing under a load of 200 g. The white cotton cloth used for rubbing was a white cotton cloth that had been moistened with water to a moist state of about 100%. After rubbing, color transfer to the white cotton cloth for rubbing was observed, and the wet rubbing fastness was evaluated according to the following criteria. In the following criteria, A and B were considered to be within the acceptable range. Evaluation criteria A: There is almost no color transfer. B: There is some color transfer, but it is within the acceptable range. C: Color transfer is observed and exceeds the acceptable range. D: There is significant color transfer, exceeding the acceptable range.

[0098] [Evaluation of texture] Sensory evaluation of the texture of the printed fabric was carried out by five people. The texture of the fabric was evaluated according to the following criteria based on the number of people who felt that the printed fabric was harder than the unprinted fabric. In the following criteria, A and B were considered to be within the acceptable range. Evaluation criteria A: The number of people who felt that the fabric became harder after printing ranged from 0 to 1. B: Two or three people felt that the fabric became harder after printing. C: Four people felt that the fabric became harder after printing. D: Five people felt that the fabric became stiffer after printing.

[0099] Table 3 shows the first and second treatment liquids used, as well as the evaluation results of color development, wet rubbing fastness, and texture.

[0100] [Table 3]

[0101] As shown in Table 3, the color development, wet rub fastness and texture were good in Examples 1 to 8, in which the cationic value of the water-soluble cationic resin was 1.2 mmol / g or more and 6.2 mmol / g or less and the molecular weight of the water-soluble cationic resin was 500 or more and 4000 or less. Moreover, the color development, wet rub fastness and texture were even better in Examples 1 to 3, in which the cationic value of the water-soluble cationic resin was 1.2 mmol / g or more and 5.5 mmol / g or less and the molecular weight of the water-soluble cationic resin was 500 or more and 1500 or less and the glass transition temperature [Tg] of the anionic resin was -29°C or less.

[0102] On the other hand, in Comparative Examples 1 and 2, which contained an anionic resin with a glass transition temperature of more than 0°C, the texture was poor. This is believed to be due to a decrease in the fixability of the pigment. In Comparative Examples 1 to 6, in which the molecular weight of the water-soluble cationic resin was more than 4000, the wet friction fastness was poor. This is believed to be due to the water-soluble cationic resin being less likely to fuse to the fabric. In Comparative Examples 1 and 5, in which the cationic value of the water-soluble cationic resin was not within the range of 1.2 mmol / g or more and 6.2 mmol / g or less, the color development was poor. This is believed to be due to the water-soluble cationic resin contained in the first treatment liquid and the anionic resin contained in the second treatment liquid not being appropriately aggregated.

[0103] (effect) As described above, according to the present invention, when the glass transition temperature of the anionic resin is 0° C. or lower, the cationic value of the water-soluble cationic resin is 1.2 mmol / g or more and 6.2 mmol / g or less, and the molecular weight of the water-soluble cationic resin is 500 or more and 4,000 or less, the color development, wet friction fastness and texture are good. [Industrial Applicability]

[0104] The ink set and inkjet recording method according to the present invention provide an ink set and inkjet recording method that are excellent in the various properties required during image formation and that can form good images. [Explanation of symbols]

[0105] 1. Textile printing equipment 2 Belt conveyor 3. Image forming section 4. Conveyor belt cleaning section 21 Drive roller 22 Driven roller 23 Conveyor belt 41 Watering Pipe 41a Watering tube 42 Brush Roller 43 Cleaning blade 44 Cleaning Sponge 45 Heating section

Claims

1. a first treatment liquid containing a water-soluble cationic resin and a first organic solvent; a second treatment liquid containing a pigment, an anionic resin having a glass transition temperature of 0° C. or lower, and a second organic solvent; The cationic value of the water-soluble cationic resin is 1.2 mmol / g or more and 6.2 mmol / g or less, The molecular weight of the water-soluble cationic resin is 500 or more and 4000 or less. Ink set.

2. The ink set according to claim 1 , wherein the water-soluble cationic resin contains a tertiary ammonium or a quaternary ammonium.

3. The ink set according to claim 1 , wherein the first organic solvent and the second organic solvent each contain a glycol-based or diol-based solvent having a boiling point of 200° C. or higher.

4. The ink set according to claim 1 , wherein the anionic resin comprises a urethane resin.

5. 2. The ink set according to claim 1, wherein a ratio of the water-soluble cationic resin to a total amount of the pigment and the anionic resin is within a range of 1:0.8 to 1:

16.

6. An inkjet recording method for forming an image on a fabric by using the ink set according to claim 1, comprising the steps of: Injecting the first treatment liquid onto a fabric; ejecting the second treatment liquid; An inkjet recording method comprising the steps of:

7. The total amount of cations in the water-soluble cationic resin in the first treatment liquid and the second treatment liquid per area of ​​the fabric is 0.07 mmol / m ２ 0.43 mmol / m or more ２ The inkjet recording method according to claim 6, wherein:

Images