Recording method

Abstract

To provide a recording method which can obtain a recorded matter having good fastness and feeling, and reduces distortion of an image.SOLUTION: A recording method includes a colored ink bonding step of bonding an ink composition containing a pigment, resin particles and water onto a recording medium by an inkjet method, and forming an image region, a first treatment liquid bonding step of bonding a first treatment liquid composition containing the resin particles and water onto the recording medium by the inkjet method, and a second treatment liquid bonding step of bonding a second treatment liquid composition containing a softening agent onto the recording medium by the inkjet method, where the image region has regions having different ink bonding amounts per unit area; the first treatment liquid bonding step and the second treatment liquid bonding step are preformed on at least the whole image region; and the bonding amount of the first treatment liquid composition is 12 mL / m2 or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a recording method. [Background technology]

[0002] The inkjet method is not only used for recording images on paper, etc., but also for textile printing on fabrics, and various inkjet textile printing methods are being studied. Inkjet inks for textile printing contain coloring materials to obtain images of desired colors, and dyes and pigments are used as the coloring materials. In addition, many studies are being conducted on inks and recording methods for inkjet textile printing.

[0003] For example, Patent Document 1 discloses a textile printing device in which the ejection amount per unit area of ​​the ink and the ejection amount per unit area of ​​the pretreatment liquid are constant or different for each part of a specific region, and the ratio between them is constant for each part of the specific region. The document describes that the textile printing device can form a printed textile with excellent image density and wet rub fastness while suppressing deterioration in the tactile feel of the printed textile. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2022-003174 A Summary of the Invention [Problem to be solved by the invention]

[0005] Patent Document 1 discloses that the pretreatment liquid contains binder resin particles containing a cationic resin and water, the ink contains a pigment, an anionic dispersant and water, and the posttreatment liquid contains a lubricant and water. However, the technology described in Patent Document 1 may cause image distortion due to the binder resin particles. Therefore, there is a demand for a recording method that provides a good fastness and texture of the resulting recorded matter and reduces image distortion. [Means for solving the problem]

[0006] One aspect of the recording method according to the present invention is to a color ink application step in which an ink composition containing a pigment, resin particles, and water is applied to a recording medium by an ink jet method to form an image area; a first treatment liquid application step of applying a first treatment liquid composition containing resin particles and water to a recording medium by an inkjet method; a second treatment liquid application step of applying a second treatment liquid composition containing a softener to a recording medium by an inkjet method; having the image area has areas with different ink deposition amounts per unit area, the first treatment liquid application step and the second treatment liquid application step are performed on at least the entire image area, The amount of the first treatment liquid composition applied is 12 mL / m 2 That's all. [Brief description of the drawings]

[0007] [Figure 1] FIG. 1 is a schematic diagram showing a schematic overall configuration of a printing apparatus to which a printing method according to an embodiment of the present invention can be applied. [Diagram 2] Schematic diagram of a printing pattern in the examples. [Diagram 3] Table 1 shows the conditions and evaluation results of the examples. [Figure 4] Table 2 shows the conditions and evaluation results of the examples. [Diagram 5] Table 3 shows the conditions and evaluation results of the examples and comparative examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The following describes an embodiment of the present invention. The embodiment described below is an example of the present invention. The present invention is not limited to the following embodiment, and includes various modified forms that are implemented within the scope of the present invention. Note that not all of the configurations described below are necessarily essential configurations of the present invention.

[0009] 1. Recording method The recording method according to this embodiment includes a color ink applying step, a first treatment liquid applying step, and a second treatment liquid applying step.

[0010] 1.1.Colored ink application process In the color ink application step, an ink composition containing a pigment, resin particles, and water is applied to a recording medium by an ink jet method to form an image area.

[0011] 1.1.1. Recording medium The recording medium to which the recording method of the present embodiment can be applied is not particularly limited. The recording medium may or may not have a recording surface that absorbs ink. Therefore, the recording medium is not particularly limited, and examples thereof include liquid-absorbent recording media such as paper, film, and fabric, low-absorbent recording media such as printed paper, and non-absorbent recording media such as metal, glass, and polymer. Among these recording media, the effect is more pronounced when a soft recording medium is used. That is, among recording media, the effect is more pronounced when paper, film, fabric, printed paper, and thin metal such as aluminum foil are used.

[0012] In the recording method of the present embodiment, the effect is more prominent when a cloth is used among recording media. That is, a cloth is a medium having permeability and elasticity, and is more likely to cause image distortion, but when a cloth is used, the effect of reducing distortion can be more prominent. Moreover, it is more preferable to use a cotton cloth as the cloth for the same reason.

[0013] The fabric is not particularly limited. The material constituting the fabric is not particularly limited, and examples thereof include natural fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide, and polyurethane, and biodegradable fibers such as polylactic acid, and may be blended fibers thereof. The fabric may be any of the above-mentioned fibers in the form of woven fabric, knitted fabric, nonwoven fabric, etc., or may be blended.

[0014] The fabric may be any of the above-mentioned fibers in the form of woven fabric, knitted fabric, nonwoven fabric, etc. The basis weight of the fabric used in the present embodiment is not particularly limited, and may be 1.0 oz or more and 10.0 oz or less, preferably 2.0 oz or more and 9.0 oz or less, more preferably 3.0 oz or more and 8.0 oz or less, and even more preferably 4.0 oz or more and 7.0 oz or less. If the basis weight of the fabric is within such a range, better recording can be performed.

[0015] In this embodiment, examples of the form of the fabric include cloth, clothing, and other accessories. Fabrics include woven fabrics, knitted fabrics, nonwoven fabrics, and the like. Clothing and other accessories include sewn T-shirts, handkerchiefs, scarves, towels, carrier bags, cloth bags, curtains, sheets, bed covers, wallpaper, and other furniture, as well as fabrics before and after cutting as parts before sewing. Examples of the form of these include long rolls, cut to a predetermined size, and product shapes.

[0016] 1.1.2.Image Area The image area refers to an area on a recording medium where the ink composition is applied in a color ink application process. The shape, size, and number of the image area are arbitrary, but the image area has areas with different amounts of the ink composition applied per unit area. In other words, areas with a large amount of the ink composition and areas with a small amount of the ink composition are formed, and the entirety of these areas constitutes the image area.

[0017] 1.1.3. Ink composition The ink composition will be described below, and the method of applying the ink to a recording medium will be described later. The ink composition contains a pigment, resin particles, and water.

[0018] 1.1.3.(1) Pigments The ink composition is a so-called color ink that contains a pigment. The pigment contained in the ink composition may be, for example, a color pigment such as cyan, yellow, magenta, black, red, green, or orange, or a special color pigment such as white.

[0019] The pigment may be a mixture. The pigment has excellent storage stability such as light resistance, weather resistance, and gas resistance, and from this viewpoint, it is preferable that the pigment is an organic pigment.

[0020] Specifically, the pigment may be an insoluble azo pigment, a condensed azo pigment, an azo lake, a chelate azo pigment, or other azo pigment, a phthalocyanine pigment, a perylene and perinone pigment, an anthraquinone pigment, a quinacridone pigment, a dioxane pigment, a thioindigo pigment, an isoindolinone pigment, a polycyclic pigment such as a quinophthalone pigment, a dye chelate, a dye lake, a nitro pigment, a nitroso pigment, an aniline black, a daylight fluorescent pigment, or a carbon black. The above pigments may be used alone or in combination of two or more. Furthermore, a white pigment, a glittering pigment, or the like may be used as the pigment.

[0021] Specific examples of pigments include, but are not limited to, the following:

[0022] Examples of black pigments include Bonjetblack CW-1 (manufactured by Orient Chemical Industry Co., Ltd.), No. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, No. 2200B, etc. (all manufactured by Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, etc. (all manufactured by Carbon Columbia), Rega1 400R, Rega1 330R, Rega1 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400 (manufactured by CABOT JAPAN KK), Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, Special Black 5, Special Black 4A, Special Black 4 (all manufactured by Degussa).

[0023] Examples of yellow pigments include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 37, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 99, 108, 109, 110, 113, 114, 117, 120, 124, 128, 129, 133, 138, 139, 147, 151, 153, 154, 167, 172, and 180.

[0024] Examples of magenta pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48(Ca), 48(Mn), 57(Ca), 57:1, 88, 112, 114, 122, 123, 144, 146, 149, 150, 166, 168, 170, 171, 175, 176, 177, 178, 179, 184, 185, 187, 202, 209, 219, 224, 245, and CI Pigment Violet. 19, 23, 32, 33, 36, 38, 43, and 50.

[0025] Cyan pigments include, for example, CI Pigment Blue 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:34, 15:4, 16, 18, 22, 25, 60, 65, and 66, and CI Vat Blue 4 and 60.

[0026] In addition, pigments other than magenta, cyan, and yellow are not particularly limited, but examples thereof include CI Pigment Green 7, 10, CI Pigment Brown 3, 5, 25, 26, and CI Pigment Orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, and 63.

[0027] Examples of the white pigment include metal compounds such as metal oxides, barium sulfate, and calcium carbonate. Examples of the metal oxide include titanium dioxide, zinc oxide, silica, alumina, and magnesium oxide. In addition, the white pigment may be a particle having a hollow structure, and known particles having a hollow structure may be used.

[0028] It is preferable that the pigment can be stably dispersed in the dispersion medium, and therefore the pigment may be dispersed using a dispersant. Examples of dispersants include resin dispersants, and are selected from those that can improve the dispersion stability of the pigment in the ink composition. In addition, the pigment may be used as a self-dispersing pigment by modifying the surface of the pigment particles by oxidizing or sulfonating the pigment surface with, for example, ozone, hypochlorous acid, fuming sulfuric acid, etc. The self-dispersing pigment is not a pigment dispersed by a dispersing agent, but a self-dispersing pigment that can be dispersed without a dispersing agent, etc. The self-dispersing pigment contained in the ink composition may be, for example, a color pigment such as black, cyan, yellow, magenta, red, green, orange, or a special color pigment such as white, and can be made into a pigment that can be self-dispersed by appropriate treatment.

[0029] Examples of the resin dispersant (dispersant resin) include (meth)acrylic resins and salts thereof, such as poly(meth)acrylic acid, (meth)acrylic acid-acrylonitrile copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, vinyl acetate-(meth)acrylic acid ester copolymer, vinyl acetate-(meth)acrylic acid copolymer, and vinylnaphthalene-(meth)acrylic acid copolymer; styrene-(meth)acrylic acid copolymer, styrene-(meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-α-methylstyrene-(meth)acrylic acid copolymer, and styrene-α-methylstyrene-(meth)acrylic acid copolymer. p) Styrenic resins such as acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, and salts thereof; urethane resins and salts thereof, which are polymeric compounds (resins) containing urethane bonds formed by the reaction of an isocyanate group and a hydroxyl group and may be linear and / or branched, and may have a crosslinked structure or not; polyvinyl alcohols; vinyl naphthalene-maleic acid copolymers and salts thereof; vinyl acetate-maleic acid ester copolymers and salts thereof; and water-soluble resins such as vinyl acetate-crotonic acid copolymers and salts thereof. Among these, copolymers of a monomer having a hydrophobic functional group and a monomer having a hydrophilic functional group, and polymers made of a monomer having both a hydrophobic functional group and a hydrophilic functional group are preferred. The copolymer may be in the form of any of random copolymers, block copolymers, alternating copolymers, and graft copolymers.

[0030] Commercially available styrene-based resin dispersants include, for example, X-200, X-1, X-205, X-220, and X-228 (manufactured by Seiko PMC Corporation), Nopcosperse (registered trademark) 6100 and 6110 (manufactured by San Nopco Ltd.), Joncryl 67, 586, 611, 678, 680, 682, and 819 (manufactured by BASF), DISPERBYK-190 (manufactured by BYK Japan KK), N-EA137, N-EA157, N-EA167, N-EA177, N-EA197D, N-EA207D, and E-EN10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

[0031] Commercially available acrylic resin dispersants include BYK-187, BYK-190, BYK-191, BYK-194N, and BYK-199 (manufactured by BYK-Chemie Co., Ltd.), Aron A-210, A6114, AS-1100, AS-1800, A-30SL, A-7250, and CL-2 (manufactured by Toagosei Co., Ltd.).

[0032] Further, commercially available urethane resin dispersants include BYK-182, BYK-183, BYK-184, BYK-185 (manufactured by BYK-Chemie Co., Ltd.), TEGO Disperse710 (manufactured by Evonic Tego Chemi), Borchi (registered trademark) Gen1350 (manufactured by OMG Borschers), and the like.

[0033] The dispersant may be used alone or in combination of two or more. The total content of the dispersant is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 25 parts by mass, even more preferably 1 to 20 parts by mass, and even more preferably 1.5 to 15 parts by mass. By making the content of the dispersant 0.1 parts by mass or more relative to 50 parts by mass of the pigment, the dispersion stability of the pigment can be further improved. In addition, if the content of the dispersant is 30 parts by mass or less relative to 50 parts by mass of the pigment, the viscosity of the obtained dispersion can be kept low.

[0034] Among the above-listed dispersants, it is more preferable to use at least one selected from anionic dispersant resins. In this case, the weight average molecular weight of the dispersant is more preferably 500 or more. It is further preferable to use a weight average molecular weight of 5,000 or more and 100,000 or less, and more preferably a weight average molecular weight of 10,000 or more and 50,000 or less.

[0035] By using such a resin dispersant as a dispersant, the dispersion and aggregation properties of the pigment are improved, and it is possible to obtain better dispersion stability and images with better image quality.

[0036] The anionic dispersant resin is a resin that has an anionic functional group and exhibits anionic properties. Examples of the anionic functional group include a carboxyl group, a sulfo group, and a phosphate group. Among these groups, the carboxyl group is more preferable.

[0037] The dispersant resin preferably has an acid value, and the acid value is preferably 5 mgKOH / g or more, more preferably 10 to 200 mgKOH / g, even more preferably 15 to 150 mgKOH / g, still more preferably 20 to 100 mgKOH / g, and even more preferably 25 to 70 mgKOH / g.

[0038] The acid value can be measured by neutralization potentiometric titration in accordance with JIS K 0070. As a titration device, for example, "AT610" manufactured by Kyoto Electronics Manufacturing Co., Ltd. can be used.

[0039] The content of the pigment is preferably from 0.3% to 20% by mass, more preferably from 0.5% to 15% by mass, further preferably from 1% to 10% by mass, and more preferably from 2% to 7% by mass, based on the total mass of the ink composition.

[0040] The volume average particle size of the pigment particles is preferably from 10 to 300 nm, more preferably from 30 to 250 nm, even more preferably from 50 to 250 nm, particularly preferably from 70 to 200 nm, and even more preferably from 80 to 150 nm.

[0041] 1.1.3.(2) Resin particles The ink composition contains resin particles. The resin particles can further improve the adhesion of the image formed by the ink composition attached to the recording medium. Examples of the resin particles include those having anionic properties among resin particles made of urethane-based resin, acrylic-based resin (including styrene-acrylic-based resin), fluorene-based resin, polyolefin-based resin, rosin-modified resin, terpene-based resin, polyester-based resin, polyamide-based resin, epoxy-based resin, vinyl chloride-based resin, vinyl chloride-vinyl acetate copolymer, ethylene vinyl acetate-based resin, etc. Among them, urethane-based resin, acrylic resin, polyolefin-based resin, and polyester-based resin are preferred. These resin particles are often handled in the form of an emulsion, but may also be in the form of a powder. In addition, the resin particles can be used alone or in combination of two or more types.

[0042] Among these, the resin particles are preferably urethane resin, since the selection of urethane resin makes it possible to form images with even better resistance to friction.

[0043] The urethane resin is a general term for resins having a urethane bond. In addition to the urethane bond, the urethane resin may be a polyether urethane resin having an ether bond in the main chain, a polyester urethane resin having an ester bond in the main chain, or a polycarbonate urethane resin having a carbonate bond in the main chain. In addition, as the urethane-based resin, commercially available products may be used, such as Superflex 460, 460s, 500M, 840, E-4000 (trade names, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Rezamin D-1060, D-2020, D-4080, D-4200, D-6300, D-6455 (trade names, manufactured by Dainichi Seiyaku Chemicals Mfg. Co., Ltd.), Takelac WS-6021, W-512-A-6 (trade names, manufactured by Mitsui Chemicals Polyurethanes Inc.), Sancure 2710 (trade name, manufactured by LUBRIZOL), and Parmarin UA-150 (trade name, manufactured by Sanyo Chemical Industries, Ltd.).

[0044] Acrylic resin is a general term for polymers obtained by polymerizing at least an acrylic monomer such as (meth)acrylic acid or (meth)acrylic acid ester as one component, and examples thereof include resins obtained from acrylic monomers and copolymers of acrylic monomers and other monomers. Examples thereof include acrylic-vinyl resins, which are copolymers of acrylic monomers and vinyl monomers. Examples of vinyl monomers include styrene.

[0045] As the acrylic monomer, acrylamide, acrylonitrile, etc. can also be used. For the resin emulsion using an acrylic resin as a raw material, a commercially available product may be used, and may be selected from, for example, FK-854 (trade name, manufactured by Chuo Rika Kogyo Co., Ltd.), Mowinyl 952B, 718A, 6760 (trade names, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), Nipol LX852, LX874 (trade names, manufactured by Nippon Zeon Co., Ltd.), etc.

[0046] In this specification, the acrylic resin may be a styrene-acrylic resin, which will be described later. In addition, in this specification, the term "(meth)acrylic" means at least one of acrylic and methacrylic.

[0047] Styrene-acrylic resins are copolymers obtained from styrene monomer and (meth)acrylic monomer, and examples include styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylate copolymer, styrene-α-methylstyrene-acrylic acid copolymer, and styrene-α-methylstyrene-acrylic acid-acrylate copolymer. As the styrene-acrylic resin, commercially available products may be used, such as JONCRYL 62J, 7100, 390, 711, 511, 7001, 632, 741, 450, 840, 74J, HRC-1645J, 734, 852, 7600, 775, 537J, 1535, PDX-7630A, 352J, 352D, PDX-7145, 538J, 7640, 7641, 631, 790, 780, and 7610 (trade names, manufactured by BASF), Mowinyl 966A and 975N (trade names, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and Vinyblan 2586 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0048] The polyolefin resin has an olefin such as ethylene, propylene, butylene, etc. in the structural skeleton, and known resins can be appropriately selected and used. As the olefin resin, commercially available products can be used, for example, Arrowbase CB-1200, CD-1200 (product name, manufactured by Unitika Ltd.), etc. may be used.

[0049] The resin particles may be supplied in the form of an emulsion. Examples of commercially available resin emulsions include Microgel E-1002 and E-5002 (trade names of Nippon Paint Co., Ltd., styrene-acrylic resin emulsions), Boncoat 4001 (trade name of DIC Corporation, acrylic resin emulsion), Boncoat 5454 (trade name of DIC Corporation, styrene-acrylic resin emulsion), Polysol AM-710, AM-920, AM-2300, AP-4735, AT-860, and PSASE-4210E (acrylic resin emulsion). Polysol AP-7020 (styrene-acrylic resin emulsion), Polysol SH-502 (vinyl acetate resin emulsion), Polysol AD-13, AD-2, AD-10, AD-96, AD-17, AD-70 (ethylene-vinyl acetate resin emulsion), Polysol PSASE-6010 (ethylene-vinyl acetate resin emulsion) (product name, manufactured by Showa Denko K.K.), Polysol SAE1014 (product name, styrene-acrylic resin emulsion, manufactured by Zeon Co., Ltd.), Cybinol SK-200 (product name, acrylic resin emulsion, Saiden Chemical Industry Co., Ltd.), AE-120A (JSR Corporation, acrylic resin emulsion), AE373D (E-Tech Corporation, carboxy-modified styrene-acrylic resin emulsion), Seikadyne 1900W (Dainichi Seika Chemical Industry Co., Ltd., ethylene-vinyl acetate resin emulsion), Vinyblan 2682 (acrylic resin emulsion), Vinyblan 2886 (vinyl acetate-acrylic resin emulsion), Vinyblan 5202 (acetic acid acrylic resin emulsion) (Nissin Chemical Industry Co., Ltd., product name), Elitel KA-5071S, KT-8803, KT-9204, KT-8701, KT-8904, KT-0507 (product name of Unitika Ltd., polyester resin emulsion), Hi-Tec SN-2002 (product name of Toho Chemical Co., Ltd., polyester resin emulsion), Takelac W-6020, W-635, W-6061, W-605, W-635, W-6021 (product name of Mitsui Chemicals Polyurethanes, urethane resin emulsion), Superflex 870, 800, 150, 420, 460, 470, 500M, 610, 700 (product name of Daiichi Kogyo Seiyaku Co., Ltd., urethane resin emulsion),Parmarin UA-150 (manufactured by Sanyo Chemical Industries, Ltd., urethane resin emulsion), Sancure 2710 (manufactured by Lubrizol Japan, urethane resin emulsion), NeoRez R-9660, R-9637, R-940 (manufactured by Kusumoto Chemical Industries, Ltd., urethane resin emulsion), Adeka Bontiter HUX-380, 290K (manufactured by ADEKA Corporation, urethane resin emulsion), Mowinyl 966A, Mowinyl 7320 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), Joncryl 7100, 390, 711, 511, 7001, 632, 741, 450, 840, 74J, HRC-1645J, 734, 852, 7600, 775, 537J, 1535, PDX-7 The binder may be selected from 630A, 352J, 352D, PDX-7145, 538J, 7640, 7641, 631, 790, 780, 7610 (all manufactured by BASF), NK Binder R-5HN (manufactured by Shin-Nakamura Chemical Co., Ltd.), Hydran WLS-210 (non-crosslinked polyurethane: manufactured by DIC Corporation), Joncryl 7610 (manufactured by BASF), and the like.

[0050] The content of the resin particles in the ink composition is, in terms of solid content, relative to the total mass of the ink composition, from 0.1% by mass to 20% by mass, preferably from 1% by mass to 15% by mass, more preferably from 3% by mass to 7% by mass, and particularly preferably from 3% by mass to 5% by mass.

[0051] 1.1.3.(3) Water The ink composition contains water. Examples of water include pure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water, and ultrapure water from which ionic impurities have been removed as much as possible. In addition, if water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, the occurrence of bacteria and fungi can be reduced when the composition is stored for a long period of time.

[0052] The water content is 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, and even more preferably 50% by mass or more, based on the total amount of the ink composition. The water in the ink composition includes, for example, crystal water contained in the raw material and added water. By having a water content of 30% by mass or more, the ink composition can have a relatively low viscosity. The upper limit of the water content is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, based on the total amount of the ink composition. In this specification, the term "water-based composition" refers to a composition containing 30% by mass or more of water based on the total mass (100% by mass) of the composition.

[0053] 1.1.3.(4) Other Ingredients The ink composition may contain the following components: (Organic solvent) The ink composition used in the recording method according to this embodiment may contain an organic solvent. The organic solvent is preferably water-soluble. One of the functions of the organic solvent is to improve the wettability of the ink composition to the fabric and to increase the moisture retention of the ink composition. The organic solvent can also function as a penetrant.

[0054] Examples of the organic solvent include esters, alkylene glycol ethers, cyclic esters, nitrogen-containing solvents, polyhydric alcohols, etc. Examples of the nitrogen-containing solvent include cyclic amides and non-cyclic amides, etc. Examples of the non-cyclic amides include alkoxyalkylamides, etc.

[0055] Examples of the esters include glycol monoacetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether acetate, and glycol diesters such as ethylene glycol diacetate, diethylene glycol diacetate, and propylene glycol diacetate.

[0056] The alkylene glycol ether may be a monoether or diether of alkylene glycol, and is preferably an alkyl ether. Specific examples include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, and diethylene glycol monomethyl ether, and alkylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether.

[0057] Examples of the cyclic esters include cyclic esters (lactones) such as β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, and β-butyrolactone, as well as compounds in which the hydrogen of the methylene group adjacent to the carbonyl group of these cyclic esters is substituted with an alkyl group having 1 to 4 carbon atoms.

[0058] Examples of alkoxyalkylamides include 3-methoxy-N,N-dimethylpropionamide, 3-methoxy-N,N-diethylpropionamide, 3-methoxy-N,N-methylethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-diethylpropionamide, 3-ethoxy-N,N-methylethylpropionamide, 3-n-butoxy-N,N-dimethylpropionamide, 3-n-butoxy-N,N-diethylpropionamide, and 3-n-butoxy-N,N-methylethylpropionamide.

[0059] Examples of the cyclic amides include lactams, such as pyrrolidones such as 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, and 1-butyl-2-pyrrolidone.

[0060] It is also preferable to use a compound represented by the following general formula (1) as the alkoxyalkylamide.

[0061] R 1 -O-CH 2 CH 2 -(C=O)-NR 2 R 3 (1)

[0062] In the above formula (1), R 1 represents an alkyl group having 1 to 4 carbon atoms, and R 2 and R 3 each independently represents a methyl group or an ethyl group. The "alkyl group having 1 to 4 carbon atoms" can be a linear or branched alkyl group, for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, an iso-butyl group, or a tert-butyl group. The compound represented by the above formula (1) may be used alone or in combination of two or more kinds.

[0063] The function of the nitrogen-containing solvent is, for example, to improve the surface drying property and fixability of the ink composition applied to the fabric.

[0064] The content of the nitrogen-containing solvent is not particularly limited, but is about 5% by mass to 50% by mass, and preferably 10% by mass to 30% by mass, based on the total mass of the ink composition. When the content is within the above range, the fixability and surface dryness of the image (particularly the surface dryness when recorded in a high-temperature and high-humidity environment) may be further improved.

[0065] Examples of polyhydric alcohols include 1,2-alkanediols (e.g., alkanediols such as ethylene glycol, propylene glycol (also known as propane-1,2-diol), 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, and 1,2-octanediol), polyhydric alcohols (polyols) other than 1,2-alkanediols (e.g., diethylene glycol, dipropylene glycol, 1,3-propanediol, and 1,3-butanediol (also known as 1,3-butylene glycol), glycol), 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,3-butanediol, 2-ethyl-1,3-hexanediol, 3-methyl-1,5-pentanediol, 2-methylpentane-2,4-diol, trimethylolpropane, glycerin, etc.

[0066] Examples of polyhydric alcohols include alkanediols and polyols. Alkanediols are diols of alkanes having 5 or more carbon atoms. The number of carbon atoms of the alkanes is preferably 5 to 15, more preferably 6 to 10, and further preferably 6 to 8. 1,2-alkanediols are preferred.

[0067] The polyols are polyols of alkanes having 4 or less carbon atoms, or intermolecular condensation products of hydroxyl groups of polyols of alkanes having 4 or less carbon atoms. The number of carbon atoms of the alkane is preferably 2 to 3. The number of hydroxyl groups in the molecule of the polyols is 2 or more, preferably 5 or less, and more preferably 3 or less. When the polyols are the intermolecular condensation products, the number of intermolecular condensations is 2 or more, preferably 4 or less, and more preferably 3 or less. The polyhydric alcohols can be used alone or in combination of two or more.

[0068] Alkanediols and polyols can function primarily as penetrating solvents and / or moisturizing solvents, but alkanediols tend to have stronger penetrating solvent properties, while polyols tend to have stronger moisturizing solvent properties.

[0069] When the ink composition contains an organic solvent, the organic solvent may be used alone or in combination of two or more. The total content of the organic solvent relative to the total mass of the ink composition is, for example, 5% by mass or more and 50% by mass or less, preferably 10% by mass or more and 45% by mass or less, more preferably 15% by mass or more and 40% by mass or less, and even more preferably 20% by mass or more and 40% by mass or less. By having the content of the organic solvent within the above range, the balance between the wetting and spreading properties and the drying properties is better, and it is easier to form a high-quality image.

[0070] The organic solvent preferably contains a polyhydric alcohol, and more preferably contains a polyhydric alcohol having a standard boiling point of 250° C. or more. The content of the polyhydric alcohol having a standard boiling point of 250° C. or more is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, even more preferably 13% by mass or more, and particularly preferably 15% by mass or more, based on the total amount of the ink composition. There is no particular upper limit, but it is preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less. When the content of the polyhydric alcohol having a standard boiling point of 250° C. or more is within the above range, there is a tendency for the balance between moisture retention and drying properties to be excellent, and for both intermittent printing stability and friction fastness to be good.

[0071] (Surfactant) The ink composition may contain a surfactant. The surfactant has a function of adjusting the surface tension of the ink composition and, for example, adjusting the wettability with a fabric. Among the surfactants, for example, acetylene glycol surfactants, silicone surfactants, and fluorine surfactants can be preferably used.

[0072] The acetylene glycol surfactant is not particularly limited, but examples thereof include Surfynol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, and DF110D (all trade names, manufactured by Air Products & Chemicals, Inc.). , Olfin B, Y, P, A, STG, SPC, E1004, E1010, PD-001, PD-002W, PD-003, PD-004, EXP.4001, EXP.4036, EXP.4051, AF-103, AF-104, AK-02, SK-14, AE-3 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), Acetylenol E00, E00P, E40, E100 (all trade names, manufactured by Kawaken Fine Chemicals Co., Ltd.).

[0073] The silicone surfactant is not particularly limited, but a polysiloxane compound is preferred. The polysiloxane compound is not particularly limited, but for example, a polyether-modified organosiloxane is preferred. Commercially available products of the polyether-modified organosiloxane include, for example, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-348 (all trade names, manufactured by BYK Japan), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF- 615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), Silface SAG002, 005, 503A, 008 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), and the like.

[0074] As the fluorosurfactant, it is preferable to use a fluorine-modified polymer, and specific examples include BYK-3440 (manufactured by BYK Japan), Surflon S-241, S-242, S-243 (all trade names, manufactured by AGC Seimi Chemical Co., Ltd.), and Futergent 215M (manufactured by NEOS Corporation).

[0075] When the ink composition contains a surfactant, multiple types of surfactants may be contained. When the ink composition contains a surfactant, the content of the surfactant may be 0.1% by mass or more and 2% by mass or less, preferably 0.4% by mass or more and 1.5% by mass or less, and more preferably 0.5% by mass or more and 1.0% by mass or less, based on the total mass of the ink composition.

[0076] (wax) The ink composition may contain a wax. The wax has a function of imparting lubricity to an image formed by the ink composition, and therefore can reduce peeling of the image formed by the ink composition.

[0077] Examples of components constituting the wax include vegetable and animal waxes such as carnauba wax, candelilla wax, beeswax, rice wax, and lanolin; petroleum waxes such as paraffin wax, microcrystalline wax, polyethylene wax, oxidized polyethylene wax, and petrolatum; mineral waxes such as montan wax and ozokerite; synthetic waxes such as carbon wax, Hoechst wax, polyolefin wax, and stearic acid amide; natural and synthetic wax emulsions and blended waxes such as α-olefin-maleic anhydride copolymers, etc., which can be used alone or in combination. Among these, polyolefin waxes (particularly polyethylene wax and polypropylene wax) and paraffin wax are preferred from the viewpoint of their excellent effect of increasing the fixation to the soft packaging film described below.

[0078] As the wax, commercially available products can be used as they are, and examples thereof include Nopcoat PEM-17 (trade name, manufactured by San Nopco Ltd.), Chemipearl W4005 (trade name, manufactured by Mitsui Chemicals Inc.), and AQUACER 515, 539, and 593 (all trade names, manufactured by BYK Japan KK).

[0079] The wax may be supplied in the form of an emulsion or suspension. When the wax is used, the content is 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass, and even more preferably 0.5% by mass to 2% by mass, calculated as solid content, based on the total mass of the ink composition. When the wax content is within the above range, the wax can exhibit its functions well.

[0080] (Additives) The ink composition may contain, as additives, ureas, amines, sugars, etc. Examples of ureas include urea, ethylene urea, tetramethyl urea, thiourea, 1,3-dimethyl-2-imidazolidinone, etc., and betaines (trimethylglycine, triethylglycine, tripropylglycine, triisopropylglycine, N,N,N-trimethylalanine, N,N,N-triethylalanine, N,N,N-triisopropylalanine, N,N,N-trimethylmethylalanine, carnitine, acetylcarnitine, etc.).

[0081] Examples of the amines include diethanolamine, triethanolamine, triisopropanolamine, etc. The ureas and amines may function as a pH adjuster. Examples of sugars include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol (sorbitol), maltose, cellobiose, lactose, sucrose, trehalose, and maltotriose.

[0082] (pH adjuster) A pH adjuster may be added to the ink composition of the present embodiment for the purpose of adjusting the pH. The pH adjuster is not particularly limited, and may be an appropriate combination of an acid, a base, a weak acid, and a weak base. Examples of acids and bases used in such combinations include inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium dihydrogen phosphate, disodium hydrogen phosphate, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, and ammonia, organic bases such as triethanolamine, diethanolamine, monoethanolamine, tripropanolamine, triisopropanolamine, diisopropanolamine, and trishydroxymethylaminomethane (THAM), and organic acids such as adipic acid, citric acid, succinic acid, lactic acid, N,N-bis(2-hydroxyethyl)amine, and the like. Good's buffers such as N-(2-hydroxyethyl)-2-aminoethanesulfonic acid (BES), 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES), morpholinoethanesulfonic acid (MES), carbamoylmethyliminobisacetic acid (ADA), piperazine-1,4-bis(2-ethanesulfonic acid) (PIPES), N-(2-acetamido)-2-aminoethanesulfonic acid (ACES), cholamine hydrochloride, N-tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid (TES), acetamidoglycine, tricine, glycineamide, and bicine, phosphate buffer, citrate buffer, Tris buffer, and the like may also be used. Furthermore, among these, it is preferable that the pH adjuster contains, as part or all of a tertiary amine such as triethanolamine or triisopropanolamine, or a carboxyl group-containing organic acid such as adipic acid, citric acid, succinic acid, or lactic acid, since this makes it possible to obtain a more stable pH buffering effect.

[0083] (Ureas) Ureas may be used as a moisturizing agent for the ink composition. Specific examples of ureas include urea, ethylene urea, tetramethyl urea, thiourea, 1,3-dimethyl-2-imidazolidinone, etc. When ureas are contained, the content thereof may be 1% by mass or more and 10% by mass or less with respect to the total mass of the ink composition.

[0084] (Sugars) Sugars may be used to prevent the ink composition from solidifying or drying. Specific examples of sugars include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol (sorbitol), maltose, cellobiose, lactose, sucrose, trehalose, and maltotriose.

[0085] (chelating agent) A chelating agent may be used to remove unnecessary ions from the ink composition. Examples of the chelating agent include ethylenediaminetetraacetic acid and salts thereof (disodium dihydrogen ethylenediaminetetraacetate, or nitrilotriacetate, hexametaphosphate, pyrophosphate, metaphosphate, etc.) and the like.

[0086] (Preservatives, anti-mold agents) The ink composition may contain a preservative and an antifungal agent, such as sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL-2, Proxel IB, and Proxel TN (all of which are trade names manufactured by Lonza Japan), and 4-chloro-3-methylphenol (such as Preventol CMK manufactured by Bayer).

[0087] (rust inhibitor) The ink composition may contain a rust inhibitor. Preferred examples of the rust inhibitor include benzotriazole, acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite. Among these, benzotriazole is particularly preferred.

[0088] (others) The ink composition used in the recording method according to this embodiment may further contain components such as a viscosity adjuster, an antioxidant, an antifungal agent, an antioxidant, an oxygen absorber, and a dissolution aid, as necessary.

[0089] 1.1.3.(5) Properties and preparation of ink composition In that the ink composition is applied to a recording medium by an inkjet method, the viscosity of the ink composition is preferably from 1.5 mPa·s to 15 mPa·s, more preferably from 1.5 mPa·s to 7 mPa·s, and even more preferably from 1.5 mPa·s to 5.5 mPa·s at 20° C. When the ink composition is applied to a recording medium by an inkjet method, it is easy to efficiently form a predetermined image on the recording medium.

[0090] In order to ensure proper wetting and spreading of the ink composition onto a recording medium, the ink composition has a surface tension of 40 mN / m or less, preferably 38 mN / m or less, and more preferably 35 mN / m or less at 25° C. The surface tension is preferably 20 mN / m or more, and more preferably 25 mN / m or more.

[0091] The surface tension can be measured using an automatic surface tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) by checking the surface tension when a platinum plate is wetted with the composition in an environment of 25°C.

[0092] The ink composition can be obtained by mixing the above-mentioned components in any order and removing impurities by filtration, etc., as necessary. As a method for mixing each component, a method in which the materials are added in order to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stirred and mixed is preferably used. As a filtration method, centrifugal filtration, filter filtration, etc. can be performed as necessary.

[0093] 1.1.4. Method for depositing ink composition onto recording medium The ink deposition step may be performed in any manner according to the inkjet method in which the ink composition is deposited while scanning the inkjet head over the recording medium. The inkjet method performs main scanning by moving the inkjet head in a direction perpendicular to the transport direction of the recording medium to perform recording. As will be described in detail later, the ink composition and the reaction liquid composition are deposited on the same scanning area of ​​the recording medium by the same main scanning.

[0094] The amount of the ink composition applied in the ink application step was 5.0 (mg / inch 2 ) or more is preferable. Furthermore, 7.0 (mg / inch 2 ) or more is preferable, and 9.0 (mg / inch 2 ) or more, and 10.0 (mg / inch 2 ) or more, and 13.0 (mg / inch 2 ) or more is more preferable, and 15.0 (mg / inch 2 ) or more. In this way, a color image having even better color development can be obtained.

[0095] The upper limit is 50.0 (mg / inch 2 ) or less is preferable, and 40.0 (mg / inch 2 ) or less is more preferable, and 25.0 (mg / inch 2 ) or less is even more preferred.

[0096] 1.2. First treatment liquid application process In the first treatment liquid application step, a first treatment liquid composition containing resin particles and water is applied to the recording medium by an ink jet method. The first treatment liquid application step is performed on at least the entire image area.

[0097] 1.2.1. First treatment liquid composition The first treatment liquid composition contains resin particles (resin dispersion) and water.

[0098] 1.2.1.(1) Resin particles The resin particles are the same as those contained in the ink composition described above, so the description will be omitted. The resin particles contained in the first treatment liquid composition may be the same as or different from those contained in the ink composition. When the resin particles contained in the first treatment liquid composition are the same as those contained in the ink composition, image distortion may be further prevented.

[0099] The content of the resin particles in the first treatment liquid composition is preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more, based on the total amount of non-volatile components in the first treatment liquid composition. When the content of the resin particles in the first treatment liquid composition is in this range, a recorded matter with better abrasion fastness can be obtained.

[0100] 1.2.1.(2) Other ingredients The first treatment liquid composition may contain other components, which are the same as those described in "1.1.1.(3) Other Components," and therefore will not be described here.

[0101] In addition, the content of the color material in the first treatment liquid composition is preferably 0.1 mass % or less with respect to the total amount of the first treatment liquid composition. In other words, it is preferable that the first treatment liquid composition is not used with the intention of coloring.

[0102] 1.2.1.(3) Manufacturing and Properties The first treatment liquid composition, in that it is applied to a fabric such as a woven fabric by an inkjet method, preferably has a viscosity of 1.5 mPa·s or more and 15 mPa·s or less, more preferably 1.5 mPa·s or more and 7 mPa·s or less, and even more preferably 1.5 mPa·s or more and 5.5 mPa·s or less, at 20°C.

[0103] From the viewpoint of providing appropriate wetting and spreading properties on fabrics, the first treatment liquid composition has a surface tension of 40 mN / m or less, preferably 38 mN / m or less, more preferably 35 mN / m or less, and even more preferably 30 mN / m or less at 25° C. The surface tension is preferably 25 mN / m or more, and more preferably 28 mN / m or more. If the first treatment liquid composition has a high surface tension, it is less likely to scatter when discharged from a nozzle, is less likely to produce mist during discharge, and can provide better discharge stability.

[0104] The first treatment liquid composition is obtained by mixing the above-mentioned components in any order and removing impurities by filtration, etc., as necessary. As a method for mixing each component, a method in which materials are added sequentially to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stirred and mixed is preferably used. As a filtration method, centrifugal filtration, filter filtration, etc. can be performed as necessary.

[0105] 1.2.2. Mode of attachment The first treatment liquid application step is performed by an inkjet method. In the recording method according to the present embodiment, the amount of the first treatment liquid composition applied in the first treatment liquid application step is 12 mL / m 2 The amount of the first treatment liquid composition applied in the first treatment liquid application step was 12.5 mL / m 2 More preferably, it is 15 mL / m or more. 2 It is more preferable that the first processing liquid composition is applied to the image area at a concentration of 12 mL / m or more. 2 By applying the first treatment liquid composition in this amount, the difference in shrinkage between the image area and the area to which the first treatment liquid composition is applied becomes smaller, and image distortion can be suppressed.

[0106] 1.3. Second treatment liquid application process In the second treatment liquid application step, a second treatment liquid composition containing a softener is applied to the recording medium by an ink jet method. The second treatment liquid application step is performed on at least the entire image area,

[0107] 1.3.1. Second treatment liquid composition The second treatment liquid composition contains a softener.

[0108] 1.3.1.(1) Fabric Softener Examples of the softening agent include particles containing organopolysiloxane, fatty acid esters, dialkyldimethylammonium salts, imidazoline-type surfactants, and amphoteric surfactants.

[0109] (Particles containing organopolysiloxane) The particles containing organopolysiloxane are not particularly limited as long as they contain organopolysiloxane, and may be, for example, organopolysiloxane particles themselves, or may be particles in which organopolysiloxane is dispersed by an emulsifier or the like. The nature of the organopolysiloxane in such particles may be solid or liquid. For example, when oily organopolysiloxane is dispersed in water in the form of particles by an emulsifier, the dispersed particles correspond to particles containing organopolysiloxane.

[0110] Organopolysiloxane consists of siloxane bonds, "-Si(R 1 R 2 )-O-" skeleton, to which organic groups R 1 , R 2 Silicone is a general term for organosilicon compounds in which methyl, phenyl, vinyl, amino, and other groups are bonded as organic groups. Organopolysiloxanes can be oily, rubbery, or resinous, depending on their chemical composition and molecular weight, and are sometimes called silicone oil, silicone rubber, and silicone resin, respectively.

[0111] The organopolysiloxane used in the second treatment liquid composition of this embodiment is more preferably an oily compound. When the organopolysiloxane is an oily compound, it is easy to stably disperse the organopolysiloxane in particulate form in an aqueous matrix by the emulsification treatment described below.

[0112] The molecular structure of the organopolysiloxane is not particularly limited, and examples thereof include linear, branched, cyclic, lattice, cage, etc. When the molecular structure of the organopolysiloxane is acyclic, one or more groups selected from optionally substituted hydrocarbon groups, alkoxy groups, hydroxyl groups, hydrogen atoms, and halogens are usually bonded to the Si atoms at the ends of the molecules.

[0113] The organopolysiloxane is not particularly limited, but examples thereof include dimethylsilicone, alkyl-modified silicone, amino-modified silicone, epoxy-modified silicone, cyclic silicone, methylphenylsilicone, and the like, which can be used alone or in combination of two or more kinds.

[0114] In addition, the organopolysiloxane may be one commercially available as a silicone oil, examples of which include dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, polyether-modified silicone oil, aralkyl-modified silicone oil, fluoroalkyl-modified silicone oil, long-chain alkyl-modified silicone oil, higher fatty acid ester-modified silicone oil, higher fatty acid amide-modified silicone oil, polyether-long-chain alkyl-aralkyl-modified silicone oil, long-chain alkyl-aralkyl-modified silicone oil, phenyl-modified silicone oil, polyether-methoxy-modified silicone oil, etc.

[0115] Among the organopolysiloxanes exemplified above, nonionic silicone is more preferable. Among the organopolysiloxanes exemplified above, unmodified silicone is more preferable. Such organopolysiloxanes are chemically more stable and are less likely to cause yellowing of the formed image.

[0116] Furthermore, the organopolysiloxane is more preferably one or more selected from dimethyl silicone, methyl phenyl silicone, and methyl hydrogen silicone.

[0117] The softener is more preferably a dimethyl silicone softener. By using a dimethyl silicone softener, a printed matter having a better texture can be obtained.

[0118] Examples of commercially available silicone oils include dimethyl silicone (KF-96 series, manufactured by Shin-Etsu Chemical Co., Ltd.), methyl hydrogen type polysiloxane (KF-99 series, KF-9901, etc., manufactured by Shin-Etsu Chemical Co., Ltd.), methyl phenyl silicone (KF-50 series, etc., manufactured by Shin-Etsu Chemical Co., Ltd.), amino-modified silicone (KF-868, etc., manufactured by Shin-Etsu Silicones), silicone branched type silicone treatment agents (KF-9908, KF-9909, etc., manufactured by Shin-Etsu Chemical Co., Ltd.), Hi-Softer K-45 (manufactured by Meisei Chemical Industry Co., Ltd.), and polyester softener EX-200A, manufactured by Takamatsu Oil Co., Ltd.

[0119] The silicone has a viscosity at 25°C, for example, which is not particularly limited, but is preferably 1000 mPa·s or less, and also preferably 50 mPa·s or more, more preferably 500 mPa·s or more and 900 mPa·s or less, and even more preferably 600 mPa·s or more and 700 mPa·s or less. Furthermore, the viscosity of the base oil in the case where the silicone is emulsified and dispersed is not particularly limited, but the upper limit is preferably 1000000 mm 2 / s or less, more preferably 100000 mm 2 / s or less, the lower limit is preferably 10 mm 2 / s or more, preferably 100 mm 2 / s or more. Base oil viscosity indicates the viscosity of the base oil and is a value that measures the internal resistance of the base oil. The higher the value of the base oil viscosity, the higher the viscosity of the base oil, and the lower the value, the lower the viscosity of the base oil.

[0120] The organopolysiloxane may be blended in the form of particles emulsified using various surfactants as emulsifiers. Examples of the emulsifiers that can be used in this case include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and phospholipids.

[0121] Examples of nonionic surfactants include glycerin fatty acid esters, polyglycerin fatty acid esters, propylene glycol fatty acid esters, sorbitan fatty acid esters, and sorbitol fatty acid esters, as well as alkylene glycol adducts thereof, polyalkylene glycol fatty acid esters, sucrose fatty acid esters, polysorbate 20, polysorbate 60, polysorbate 80, polyoxyalkylene alkyl ethers, and polyoxyethylene alkylphenyl ethers.

[0122] In addition, as the nonionic surfactant, for example, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene phytosterol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene lanolin, polyoxyethylene lanolin alcohol, polyoxyethylene beeswax derivative, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, polyoxyethylene alkylphenyl formaldehyde condensate, polyoxyethylene alkyl ether phosphate (salt), and other nonionic surfactants are also suitable for use.

[0123] Examples of anionic surfactants include alkyl sulfate salts, polyoxyethylene alkyl sulfate salts, alkylbenzene sulfonates, and α-olefin sulfonates. Examples of cationic surfactants include alkyl trimethyl ammonium chloride, dialkyl dimethyl ammonium chloride, and benzalkonium chloride. Examples of amphoteric surfactants include alkyl dimethyl amino acetate betaine and alkyl amido dimethyl amino acetate betaine. Furthermore, surfactants derived from natural sources may be used, and examples of such surfactants include lecithin, lanolin, cholesterol, and saponin.

[0124] The amount of emulsifier used when emulsifying the organopolysiloxane is preferably less than 20% by mass, more preferably 15% by mass or less, and particularly preferably 10% by mass or less, of the total amount of the emulsion composition.

[0125] Furthermore, it is desirable that the average particle size of the emulsified particulate organopolysiloxane particles is 2 μm or less, preferably 1 μm or less, and more preferably in the range of 0.05 to 0.5 μm.

[0126] (Fatty acid ester) Examples of fatty acid esters include polyoxyethylene monocaprate, polyoxyethylene monocaprylate, polyoxyethylene monolaurate, polyoxyethylene monomyristate, polyoxyethylene monopalmitate, polyoxyethylene monostearate, polyoxyethylene monooleate, polyoxyethylene monoisostearate, polyoxyethylene monobehenate, polyoxyethylene dicaprate, polyoxyethylene dicaprylate, polyoxyethylene dilaurate, polyoxyethylene dimyristate, polyoxyethylene dipalmitate, polyoxyethylene distearate, polyoxyethylene dioleate, polyoxyethylene diisostearate, and polyoxyethylene dibehenate.

[0127] (Dialkyldimethylammonium salts) Examples of dialkyldimethylammonium salts include dioleoyloxytrimethylammonium propane chloride (DOTAP), dioctadecenyltrimethylammonium propane chloride (DOTMA), didecyldimethylammonium chloride, didecyldimethylammonium bromide, dicocoyldimethylammonium chloride, dicocoyldimethylammonium bromide, dilauryldimethylammonium chloride, dicetyldimethylammonium chloride, dicetyldimethylammonium bromide, distearyldimethylammonium chloride, distearyldimethylammonium bromide, dioleyldimethylammonium chloride, dibehenyldimethylammonium chloride, dibehenyldimethylammonium bromide, dialkyldimethylammonium chloride, dialkyldimethylammonium bromide, dicocoylethylhydroxyethylmonium methosulfate, dipalmitoylethylhydroxyethylmonium methosulfate, and distearoylethylhydroxyethylmonium methosulfate.

[0128] (Imidazoline surfactants) Examples of imidazoline surfactants include 1-hydroxyethyl-2-laurylimidazoline, 1-aminoethyl-2-laurylimidazoline, 1-hydroxyethyl-2-myristyl imidazoline, 1-aminoethyl-2-myristyl imidazoline, 1-hydroxyethyl-2-palmitylimidazoline, 1-aminoethyl-2-palmitylimidazoline, 1-hydroxyethyl-2-oleyl imidazoline, 1-aminoethyl-2-oleyl imidazoline, 1-hydroxyethyl-2-stearyl imidazoline, 1-aminoethyl-2-stearyl imidazoline, 2-alkyl-N-carboxymethyl imidazolinium betaine, 2-alkyl-N-carboxyethyl imidazolinium betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, and the like.

[0129] (Amphoteric surfactant) Examples of amphoteric surfactants include alkyl carboxy betaines, alkyl sulfo betaines, alkyl hydroxy sulfo betaines, alkyl amido betaines, lauryl dimethyl amine oxide, and lauric acid amido propyl dimethyl amine oxide.

[0130] The softening agent is preferably at least one selected from the group consisting of particles containing the above-mentioned organopolysiloxane, fatty acid ester, dialkyldimethylammonium salt, imidazoline surfactant, and amphoteric surfactant, which further improves the wet friction fastness of the image formed by the recording method.

[0131] Moreover, it is more preferable that the softener is at least one selected from particles containing organopolysiloxane, whereby the second treatment liquid composition can impart a water repellent effect to the fibers of the recording medium, thereby further improving the wet friction fastness of the image of the recorded matter.

[0132] Furthermore, when particles containing organopolysiloxane are selected as a softening agent, it is more preferable that the organopolysiloxane is nonionic, which can reduce yellowing of the recorded matter.

[0133] The content of the softener in the second treatment liquid composition is preferably 60% by mass or more, more preferably 65% ​​by mass or more, and even more preferably 70% by mass or more, based on the total amount of non-volatile components in the second treatment liquid composition. When the content of the softener in the second treatment liquid composition is within this range, a recorded matter with an even better texture can be obtained.

[0134] The content of the softener is more preferably from 8% by mass to 15% by mass, even more preferably from 9% by mass to 14% by mass, and particularly preferably from 12% by mass to 14% by mass, based on the total amount of the second treatment liquid composition. When the content of the softener in the second treatment liquid composition is within this range, a recorded matter with an even better texture can be obtained.

[0135] 1.3.1.(2) Other ingredients The second treatment liquid composition may contain other components, which are the same as those described in "1.1.1.(3) Other Components", and therefore will not be described here.

[0136] In addition, the content of the color material in the second treatment liquid composition is preferably 0.1 mass % or less with respect to the total amount of the second treatment liquid composition. In other words, it is preferable that the second treatment liquid composition is not used with the intention of coloring.

[0137] 1.3.1.(3) Manufacturing and Properties The second treatment liquid composition, in that it is applied to a fabric such as a woven fabric by an inkjet method, preferably has a viscosity of 1.5 mPa·s or more and 15 mPa·s or less, more preferably 1.5 mPa·s or more and 7 mPa·s or less, and even more preferably 1.5 mPa·s or more and 5.5 mPa·s or less, at 20°C.

[0138] From the viewpoint of providing appropriate wetting and spreading properties on fabrics, the second treatment liquid composition has a surface tension of 40 mN / m or less, preferably 38 mN / m or less, more preferably 35 mN / m or less, and even more preferably 30 mN / m or less at 25° C. The surface tension is preferably 25 mN / m or more, and more preferably 28 mN / m or more. If the second treatment liquid composition has a high surface tension, it is less likely to scatter when ejected from a nozzle, is less likely to produce mist during ejection, and ejection stability can be improved.

[0139] The second treatment liquid composition can be obtained by mixing the above-mentioned components in any order and removing impurities by filtration, etc., as necessary. As a method for mixing each component, a method in which materials are added sequentially to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stirred and mixed is preferably used. As a filtration method, centrifugal filtration, filter filtration, etc. can be performed as necessary.

[0140] 1.3.2. Mode of attachment The second treatment liquid application step is carried out by an inkjet method. The amount of the second treatment liquid composition applied in the second treatment liquid application step is 2 g / m 2 More than 50g / m 2 Less than 5 g / m is preferable. 2 More than 25g / m 2 Less than 10 g / m is more preferable. 2 More than 15g / m 2 The following is even more preferred:

[0141] 1.4. Relationship between resin particle content in each composition When the content of the resin particles in the ink composition is 4 mass % or more and 8 mass % or less relative to the total amount of the ink composition, and the content of the resin particles in the first treatment liquid composition is 10 mass % or more and 15 mass % or less relative to the total amount of the first treatment liquid composition, it is easy to reduce the difference in shrinkage between the image area and the area where the first treatment liquid composition is applied, and image distortion is further easy to suppress.

[0142] 1.5. Amount of each treatment solution applied Within the image area, the difference between the area where the total of the applied amount of the ink composition and the applied amount of the first treatment liquid composition per unit area is maximum and the area where the total is minimum is 20 mL / m 2 Preferably, it is 17 mL / m or less. 2 More preferably, it is 13 mL / m or less. 2 More preferably, it is 10 mL / m or less. 2 In this way, the total amount of adhesion of the ink composition and the first treatment liquid composition becomes roughly the same within the image region, and image distortion can be further suppressed.

[0143] Furthermore, the amount of the second treatment liquid composition applied is preferably at least 1 / 2, more preferably at least 1 time, and even more preferably at least 1.3 times, the amount of the first treatment liquid composition applied, thereby obtaining a recorded matter with an even better texture.

[0144] 1.6.Other processes The recording method of this embodiment may further include a reaction liquid applying step of applying to the recording medium a reaction liquid composition that contains an aggregating agent that aggregates the components in the ink composition.

[0145] 1.6.1. Reaction solution attachment process When the method includes the reaction liquid application step, a reaction liquid composition containing an aggregating agent that aggregates the components in the ink composition is applied to a recording medium in this step, thereby forming an image with excellent color development.

[0146] The reaction liquid composition contains an aggregating agent that aggregates the components of the ink composition. The aggregating agent has the effect of aggregating the pigment and resin particles by reacting with components such as the pigment contained in the ink composition and the resin particles contained in the ink composition and the first treatment liquid composition. Such aggregation can, for example, enhance the color development of the pigment, enhance the fixation of the resin particles, and / or increase the viscosity of the ink.

[0147] 1.6.1.(1) Flocculants The flocculant is not particularly limited, but may be metal salt, inorganic acid, organic acid, cationic compound, etc., and the cationic compound may be cationic resin (cationic polymer), cationic surfactant, etc. Among these, the metal salt is preferably polyvalent metal salt, and the cationic compound is preferably cationic resin. Therefore, the flocculant is preferably selected from polyvalent metal salt, organic acid, and cationic polymer, in that the color development, image quality, abrasion resistance, gloss, etc. obtained are more excellent.

[0148] The metal salt is preferably a polyvalent metal salt, but metal salts other than polyvalent metal salts can also be used. Among these flocculants, it is preferable to use at least one selected from metal salts and organic acids because of their excellent reactivity with the components contained in the ink. Furthermore, among cationic compounds, it is preferable to use cationic resins because they are easily dissolved in the treatment liquid. It is also possible to use multiple types of flocculants in combination.

[0149] A polyvalent metal salt is a compound composed of a divalent or higher metal ion and an anion. Examples of divalent or higher metal ions include calcium, magnesium, copper, nickel, zinc, barium, aluminum, titanium, strontium, chromium, cobalt, and iron ions. Among the metal ions that compose these polyvalent metal salts, at least one of calcium ions and magnesium ions is preferred because they have excellent coagulation properties for the ink components.

[0150] The anion constituting the polyvalent metal salt is an inorganic ion or an organic ion. That is, the polyvalent metal salt in the present invention is composed of an inorganic ion or an organic ion and a polyvalent metal. Examples of such inorganic ions include chloride ions, bromide ions, iodide ions, nitrate ions, sulfate ions, hydroxide ions, etc. Examples of organic ions include organic acid ions, such as carboxylate ions.

[0151] The polyvalent metal compound is preferably an ionic polyvalent metal salt, and in particular, when the polyvalent metal salt is a magnesium salt or a calcium salt, the stability of the treatment solution is improved. The counter ion of the polyvalent metal may be either an inorganic acid ion or an organic acid ion.

[0152] Specific examples of the polyvalent metal salt include calcium carbonate, such as heavy calcium carbonate and light calcium carbonate, calcium nitrate, calcium chloride, calcium sulfate, magnesium sulfate, calcium hydroxide, magnesium chloride, magnesium carbonate, barium sulfate, barium chloride, zinc carbonate, zinc sulfide, aluminum silicate, calcium silicate, magnesium silicate, copper nitrate, calcium formate, calcium acetate, magnesium acetate, and aluminum acetate. These polyvalent metal salts may be used alone or in combination of two or more. Among these, at least one of calcium formate, magnesium sulfate, calcium nitrate, and calcium chloride is preferred, since sufficient solubility in water can be ensured and traces left by the treatment liquid are reduced (the traces become less noticeable), and calcium formate and calcium nitrate are more preferred. Note that these metal salts may have hydration water in the raw material form.

[0153] Examples of metal salts other than polyvalent metal salts include monovalent metal salts such as sodium salts and potassium salts, for example, sodium sulfate and potassium sulfate.

[0154] Suitable examples of organic acids include poly(meth)acrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, tartaric acid, lactic acid, sulfonic acid, orthophosphoric acid, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, or derivatives of these compounds, or salts thereof. Organic acids may be used alone or in combination of two or more. Salts of organic acids that are metal salts are included in the above metal salts.

[0155] Examples of inorganic acids include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, etc. The inorganic acids may be used alone or in combination of two or more kinds.

[0156] Examples of cationic resins (cationic polymers) include cationic acrylic resins, cationic urethane resins, cationic olefin resins, cationic amine resins, cationic surfactants, etc. The cationic polymer is preferably water-soluble.

[0157] As the cationic acrylic resin, commercially available products can be used, such as Superflex (registered trademark) 620 and 650 from Daiichi Kogyo Seiyaku Co., Ltd., Parasurf UP-22 from Ohara Palladium Chemical Co., Ltd., Permarin (registered trademark) UC-20 from Sanyo Chemical Industries, Ltd., Arrowbase (registered trademark) CB-1200 and CD-1200 from Unitika Co., Ltd., Vinyblan (registered trademark) 2687 from Nissin Chemical Industry Co., Ltd., and Mowinyl 7820 from Japan Coating Resins Co., Ltd.

[0158] As the cationic urethane-based resin, commercially available products can be used, such as HYDRAN CP-7010, CP-7020, CP-7030, CP-7040, CP-7050, CP-7060, and CP-7610 (trade names, manufactured by Dainippon Ink and Chemicals, Inc.), SUPERFLEX 500M, 600, 610, 620, 630, 640, and 650 (trade names, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), and urethane emulsions WBR-2120C and WBR-2122C (trade names, manufactured by Taisei Fine Chemical Co., Ltd.).

[0159] The cationic olefin resin has an olefin such as ethylene or propylene in the structural skeleton, and known resins can be appropriately selected and used. The cationic olefin resin may be in an emulsion state dispersed in a solvent including water or an organic solvent. As the cationic olefin resin, a commercially available product can be used, and examples thereof include Arrowbase CB-1200 and CD-1200 (trade names, manufactured by Unitika Ltd.).

[0160] The cationic amine resin (cationic polymer) may be any resin having an amino group in its structure, and known resins may be appropriately selected and used. For example, polyamine resins, polyamide resins, polyallylamine resins, etc. may be mentioned. Polyamine resins are resins having amino groups in their main skeletons. Polyamide resins are resins having amide groups in their main skeletons. Polyallylamine resins are resins having a structure derived from allyl groups in their main skeletons.

[0161] Examples of cationic polyamine resins include Unisense KHE103L (hexamethylenediamine / epichlorohydrin resin, 1% aqueous solution with a pH of about 5.0, viscosity of 20 to 50 (mPa s), and a solids concentration of 50% by mass) and Unisense KHE104L (dimethylamine / epichlorohydrin resin, 1% aqueous solution with a pH of about 7.0, viscosity of 1 to 10 (mPa s), and a solids concentration of 20% by mass), both manufactured by Senka Corporation. Further, specific examples of commercially available cationic polyamine resins include FL-14 (manufactured by SNF Co., Ltd.), Arafix 100, 251S, 255, 255LOX (manufactured by Arakawa Chemical Co., Ltd.), DK-6810, 6853, 6885; WS-4010, 4011, 4020, 4024, 4027, 4030 (manufactured by Seiko PMC Co., Ltd.), and Papiogene P-105 (manufactured by Senka Co., Ltd.). , Sumirez Resin 650(30), 675A, 6615, SLX-1 (manufactured by Taoka Chemical Co., Ltd.), Catiomaster (registered trademark) PD-1, 7, 30, A, PDT-2, PE-10, PE-30, DT-EH, EPA-SK01, TMHMDA-E (manufactured by Yokkaichi Synthetic Co., Ltd.), Jetfix 36N, 38A, 5052 (manufactured by Satoda Chemical Co., Ltd.).

[0162] The polyamine resin may also be a polyallylamine resin. Examples of the polyallylamine resin include polyallylamine hydrochloride, polyallylamine amide sulfate, allylamine hydrochloride-diallylamine hydrochloride copolymer, allylamine acetate-diallylamine acetate copolymer, allylamine acetate-diallylamine acetate copolymer, allylamine hydrochloride-dimethylallylamine hydrochloride copolymer, allylamine-dimethylallylamine copolymer, polydiallylamine hydrochloride, polymethyldiallylamine hydrochloride, polymethyldiallylamine amide sulfate, polymethyldiallylamine acetate, polydiallyldimethylammonium chloride, diallylamine acetate-sulfur dioxide copolymer, diallylmethylethylammonium ethyl sulfate-sulfur dioxide copolymer, methyldiallylamine hydrochloride-sulfur dioxide copolymer, diallyldimethylammonium chloride-sulfur dioxide copolymer, diallyldimethylammonium chloride-acrylamide copolymer, and the like.

[0163] Examples of cationic surfactants include primary, secondary, and tertiary amine salt compounds, alkylamine salts, dialkylamine salts, aliphatic amine salts, benzalkonium salts, quaternary ammonium salts, quaternary alkylammonium salts, alkylpyridinium salts, sulfonium salts, phosphonium salts, onium salts, and imidazolinium salts.

[0164] A plurality of types of these flocculants may be used. Among these flocculants, if a flocculant is selected from polyvalent metal salts, organic acids, and cationic polymers, the flocculation action of the pigment and resin particles is more excellent, so that an image of higher quality (particularly with good color development) can be formed.

[0165] The total content of the flocculant in the reaction liquid composition is not limited, but is, for example, from 0.1% by mass to 15% by mass, preferably from 1% by mass to 10% by mass, and more preferably from 2% by mass to 10% by mass, relative to the total mass of the reaction liquid composition.

[0166] 1.6.1.(2) Other Ingredients The reaction liquid composition may contain water, a moisturizer, a polyhydric alcohol, other solvents, a surfactant, and additives. Of these, the water, moisturizer, other solvents, surfactant, and additives are the same as those in the ink composition described above, so the description thereof will be omitted.

[0167] In addition, the content of the coloring material in the reaction liquid composition is preferably 0.1% by mass or less based on the total amount of the reaction liquid composition. In other words, it is preferable that the reaction liquid composition is not used with the intention of coloring.

[0168] 1.6.1.(3) Properties and preparation of reaction liquid composition Since the reaction liquid composition is applied to a recording medium by an inkjet method, the viscosity of the reaction liquid composition is preferably from 1.5 mPa·s to 15 mPa·s, more preferably from 1.5 mPa·s to 7 mPa·s, and even more preferably from 1.5 mPa·s to 5.5 mPa·s at 20° C. When the reaction liquid composition is applied to a recording medium by an inkjet method, it is easy to efficiently form a predetermined image on the recording medium.

[0169] In order to ensure that the reaction liquid composition has appropriate wetting and spreading properties on a recording medium, the surface tension at 25° C. is 40 mN / m or less, preferably 38 mN / m or less, and more preferably 35 mN / m or less. The surface tension is preferably 20 mN / m or more, and more preferably 25 mN / m or more.

[0170] The surface tension can be measured using an automatic surface tensiometer CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) by checking the surface tension when a platinum plate is wetted with the composition in an environment of 25°C.

[0171] The reaction liquid composition can be obtained by mixing the above-mentioned components in any order and removing impurities by filtration, etc., as necessary. As a method for mixing each component, a method in which materials are added sequentially to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stirred and mixed is preferably used. As a filtration method, centrifugal filtration, filter filtration, etc. can be performed as necessary.

[0172] 1.6.1.(4) Method for applying the reaction liquid composition to fabric The reaction liquid depositing step may be performed in any manner according to the inkjet method in which the reaction liquid composition is deposited while scanning the inkjet head over the recording medium. The inkjet method is a method of performing main scanning in which the inkjet head is moved in a direction perpendicular to the transport direction of the recording medium to perform recording. As will be described in detail later, the ink composition and the reaction liquid composition are deposited on the same scanned area of ​​the fabric by the same main scanning.

[0173] In the reaction liquid application step, the amount of polyvalent metal salt in the reaction liquid composition applied to the recording medium was 0.3 (mg / inch 2 In the reaction solution application step, the amount of the polyvalent metal salt applied to the recording medium is preferably 0.5 (mg / inch 2 ) or more is more preferable, and 0.9 (mg / inch 2 By setting the adhesion amount to this range, even when the ink composition and the reaction liquid composition are adhered to the same scanning region of the recording medium by the same main scanning, the components of the ink composition and other compositions can be favorably aggregated, and color development can be favorable.

[0174] On the other hand, the adhesion amount of polyvalent metal salts was 1.7 (mg / inch 2 ) or less, and 1.5 (mg / inch 2 ) or less, and more preferably 1.0 (mg / inch 2 ) or less. This makes it possible to improve the color development of the image.

[0175] The upper limit is 25.0 (mg / inch 2 ) or less is preferable, and 18.0 (mg / inch 2 ) or less is more preferable, and 15.0 (mg / inch 2 ) or less is even more preferred.

[0176] The above-mentioned amount of the reaction liquid composition adhered is that in the recording region where the reaction liquid composition and the ink composition are adhered in an overlapping manner in the recording method of this embodiment. The maximum amount of the reaction liquid composition adhered in the region may be set to the above-mentioned range, which is preferable.

[0177] 1.6.2.Drying process The recording method of the present embodiment may further include a step of heating and drying the recording medium. In the case where this step is included, image distortion may occur more easily, but the effect of the recording method of the present embodiment of reducing distortion will be more pronounced.

[0178] The drying step can be carried out by a drying mechanism. Examples of the drying step using a drying mechanism include a means for blowing room temperature air or hot air to the recording medium (air blowing type), a means for irradiating the recording medium with radiation (infrared rays, etc.) that generates heat (radiation type), a member that contacts the recording medium and transfers heat to the fabric (conduction type), and a combination of two or more of these means. When a drying step is included, it is preferably carried out by a drying mechanism that heats the recording medium. When a drying mechanism that heats the recording medium is used as the drying mechanism, it is particularly called a heating step.

[0179] The surface temperature of the recording medium when each composition is applied is preferably 45° C. or less, more preferably 20° C. or more and 45° C. or less. Also, it is preferably 27.0° C. or more and 40° C. or less, more preferably 28° C. or more and 30° C. or less. This temperature is the surface temperature of the part of the recording surface of the recording medium that receives the liquid in the application process, and is the maximum temperature in the application process in the recording area. If the surface temperature is within the above range, it is more preferable in terms of image quality, abrasion resistance, and reduced clogging.

[0180] When the recording medium is a fabric, the heating method is not particularly limited, but examples thereof include a heat press method, a normal pressure steam method, a high pressure steam method, and a thermofix method. The heat source for heating is not particularly limited, but examples thereof include an infrared lamp. The heating temperature is preferably a temperature at which the resin particles in the ink are fused and the medium such as water vaporizes. For example, it is preferably 120°C or more and 200°C or less, and more preferably 150°C or more and 160°C or less. Here, the heating temperature in the heating step refers to the surface temperature of the image formed on the fabric, which is the fabric. The heating time is not particularly limited, but for example, it is 30 seconds or more and 20 minutes or less.

[0181] 1.7.Effects According to the recording method of the present embodiment, since the ink composition contains resin particles, a recorded matter having good resistance to friction can be obtained. 2 By applying the above amount, the difference in shrinkage between the image area and the area to which the first treatment liquid composition is applied is reduced, and image distortion can be suppressed. Furthermore, by further applying the second treatment liquid composition, the texture of the recorded matter can be improved.

[0182] 2. An example of a recording device An example of an inkjet textile printing apparatus (recording apparatus) equipped with an inkjet head that can be used in the recording method according to this embodiment will be described with reference to FIG.

[0183] In Fig. 1, the scale of each layer and each component is different from the actual scale so that each layer and each component can be recognized. For convenience of explanation, Fig. 1 illustrates three mutually perpendicular axes, the X-axis, the Y-axis, and the Z-axis, with the tip side of the arrow showing the axial direction being the "+ side" and the base side being the "- side". The direction parallel to the X-axis is called the "X-axis direction", the direction parallel to the Y-axis is called the "Y-axis direction", and the direction parallel to the Z-axis is called the "Z-axis direction".

[0184] 2.1.Overall schematic structure 1 is a schematic diagram showing a schematic overall configuration of a recording device 100. First, the overall configuration of the recording device 100 will be described with reference to FIG.

[0185] 1, the recording device 100 includes a medium transport unit 20, a medium contact unit 60, a belt support unit 91, a printing unit 40, a heating unit 27, a cleaning unit 50, and the like. In the recording device 100, at least one of the medium contact unit 60 and the belt support unit 91 corresponds to a heating unit that heats the endless belt 23. The recording device 100 also includes a control unit 1 that controls each of these units. Each unit of the recording device 100 is attached to a frame unit 90.

[0186] When a heating unit for heating the endless belt is provided, it is sufficient that the heating unit is located upstream of the printing unit 40 in the transport direction, and may be located at a location different from the medium contact unit 60 and the belt support unit 91. For example, the heating unit may be located upstream of the medium contact unit 60 in the transport direction. With this configuration, the heating unit can also dry the endless belt 23 that becomes wet during cleaning. The heating unit may also heat the endless belt without contacting the endless belt.

[0187] The medium transport unit 20 transports the fabric 95 in a transport direction. The medium transport unit 20 includes a medium supply unit 10, transport rollers 21 and 22, an endless belt 23, a belt rotation roller 24, a belt drive roller 25 as a drive roller, transport rollers 26 and 28, and a medium recovery unit 30.

[0188] 2.2. Media transport section First, the transport path of the fabric 95 from the medium supply unit 10 to the medium recovery unit 30 will be described. In Fig. 1, the direction along the direction in which gravity acts is defined as the Z-axis direction, the direction in which the fabric 95 is transported in the printing unit 40 is defined as the +X-axis direction, and the width direction of the fabric 95 that intersects with both the Z-axis direction and the X-axis direction is defined as the Y-axis direction. The positional relationship along the transport direction of the fabric 95 or the movement direction of the endless belt 23 is also referred to as the "upstream side" and the "downstream side".

[0189] The medium supply unit 10 supplies the fabric 95 on which an image is to be formed to the printing unit 40. The medium supply unit 10 has a supply shaft 11 and a bearing unit 12. The supply shaft 11 is formed in a cylindrical or columnar shape and is provided so as to be rotatable in the circumferential direction. A strip-shaped fabric 95 is wound in a roll around the supply shaft 11. The supply shaft 11 is detachably attached to the bearing unit 12. As a result, the fabric 95, which has been wound around the supply shaft 11 in advance, can be attached to the bearing unit 12 together with the supply shaft 11.

[0190] The bearings 12 rotatably support both axial ends of the supply shaft 11. The medium supply unit 10 has a rotation drive unit (not shown) that rotates the supply shaft 11. The rotation drive unit rotates the supply shaft 11 in the direction in which the fabric 95 is fed out. The operation of the rotation drive unit is controlled by the control unit 1. The transport rollers 21 and 22 relay the fabric 95 from the medium supply unit 10 to the endless belt 23.

[0191] The endless belt 23 is held between at least two rollers that rotate the endless belt 23, and the endless belt 23 rotates to support and transport the fabric 95 in the transport direction (+X-axis direction). More specifically, the endless belt 23 is a seamless belt formed by connecting both ends of a strip-shaped belt without any seams, and is hung between two rollers, a belt rotating roller 24 and a belt driving roller 25.

[0192] The endless belt 23 is held under a predetermined tension so that the portion between the belt rotating roller 24 and the belt driving roller 25 is horizontal. An adhesive 29 for adhering the fabric 95 is applied to the surface (support surface) 23a of the endless belt 23. That is, the endless belt 23 has an adhesive layer made of the adhesive 29. The fabric 95 is attached to the endless belt 23 via the adhesive 29. The endless belt 23 supports (holds) the fabric 95, which is supplied from the transport roller 22 and adhered to the adhesive 29 at the medium contacting section 60 described below.

[0193] It is preferable that adhesive 29 has an adhesiveness that increases when heated. By using adhesive 29 whose adhesiveness increases when heated, fabric 95 can be well adhered to the adhesive layer. An example of such adhesive 29 is a hot melt adhesive containing thermoplastic elastomer SIS (styrene-isoprene-styrene) as a main component.

[0194] The belt rotating roller 24 and the belt driving roller 25 support the inner peripheral surface 23b of the endless belt 23. Between the belt rotating roller 24 and the belt driving roller 25, there are provided a contact portion 69, a belt support portion 91, and a platen 46, which support the endless belt 23. The contact portion 69 is provided in an area facing a pressing portion 61, which will be described later, across the endless belt 23, the platen 46 is provided in an area facing a printing portion 40 across the endless belt 23, and the belt support portion 91 is provided between the contact portion 69 and the platen 46. The contact portion 69, the belt support portion 91, and the platen 46 support the endless belt 23, and therefore it is possible to suppress vibration of the endless belt 23 that accompanies the movement of the endless belt 23.

[0195] The belt driving roller 25 is a driving unit that rotates the endless belt 23 to transport the fabric 95 in the transport direction, and has a motor (not shown) that rotates the belt driving roller 25. The belt driving roller 25 is provided downstream of the printing unit 40 in the transport direction of the fabric 95, and the belt rotating roller 24 is provided upstream of the printing unit 40. When the belt driving roller 25 is driven to rotate, the endless belt 23 rotates in accordance with the rotation of the belt driving roller 25, and the belt rotating roller 24 rotates due to the rotation of the endless belt 23. The fabric 95 supported by the endless belt 23 is transported in the transport direction (+X axis direction) due to the rotation of the endless belt 23, and an image is formed on the fabric 95 in the printing unit 40 described later.

[0196] 1, the fabric 95 is supported on the side (+Z axis side) where the surface 23a of the endless belt 23 faces the printing unit 40, and the fabric 95 is transported together with the endless belt 23 from the belt rotation roller 24 side to the belt drive roller 25 side. Moreover, on the side (-Z axis side) where the surface 23a of the endless belt 23 faces the cleaning unit 50, only the endless belt 23 moves from the belt drive roller 25 side to the belt rotation roller 24 side.

[0197] The transport roller 26 peels the fabric 95 on which the image has been formed from the adhesive 29 of the endless belt 23. The transport rollers 26 and 28 relay the fabric 95 from the endless belt 23 to the medium recovery unit 30.

[0198] The medium recovery unit 30 recovers the fabric 95 transported by the medium transport unit 20. The medium recovery unit 30 has a winding shaft unit 31 and a bearing unit 32. The winding shaft unit 31 is formed in a cylindrical or columnar shape and is provided so as to be rotatable in the circumferential direction. A strip-shaped fabric 95 is wound in a roll around the winding shaft unit 31. The winding shaft unit 31 is detachably attached to the bearing unit 32. This allows the fabric 95 wound around the winding shaft unit 31 to be removed together with the winding shaft unit 31.

[0199] The bearings 32 rotatably support both axial ends of the winding shaft 31. The medium recovery unit 30 has a rotation drive unit (not shown) that rotates the winding shaft 31. The rotation drive unit rotates the winding shaft 31 in the direction in which the fabric 95 is wound. The operation of the rotation drive unit is controlled by the control unit 1.

[0200] Next, the heating section, the printing section 40, the heating unit 27, and the cleaning unit 50, which are provided along the medium transport section 20, will be described.

[0201] 2.3. Heating section At least one of the contact portion 69 and the belt support portion 91 is preferably provided with a heater for heating the endless belt 23. The heater constitutes a heating portion. When a heater is provided in the contact portion 69, the pressing portion 61 can apply a pressing force and heat to the endless belt 23, which is preferable in that the adhesion of the fabric 95 to the endless belt 23 can be improved. Therefore, when a heater is provided in either the contact portion 69 or the belt support portion 91, it is more preferable to provide the heater in the contact portion 69.

[0202] The heating section heats the adhesive layer to soften it and make it sticky, thereby improving the adhesion between the adhesive layer and the fabric 95. This prevents the fabric 95 from moving on the endless belt 23, and allows for good conveyance accuracy.

[0203] When a heater is provided on at least one of the contact portion 69 and the belt support portion 91 and the endless belt 23 is heated, the temperature of the surface 23a of the endless belt 23 is preferably 80 degrees or less, more preferably 70 degrees or less, and even more preferably 60 degrees or less. When the temperature of the surface 23a of the endless belt 23 is within the above range, the reactivity of the resin particles contained in the ink composition may be suppressed, and the belt may be more easily washed. The lower limit of the temperature of the surface 23a of the endless belt 23 may be any temperature that exhibits the adhesiveness of the adhesive layer, and is preferably 30 degrees or more, more preferably 35 degrees or more, and even more preferably 40 degrees or more. The temperature of the surface 23a of the endless belt 23 can be measured, for example, by a radiation thermometer, a contact thermometer, or the like, and is more preferably measured by a radiation thermometer.

[0204] When a heater is provided on at least one of the contact portion 69 and the belt support portion 91, a temperature detection portion (not shown) for detecting the surface temperature of the endless belt 23 may be provided. As the temperature detection portion, for example, a thermocouple or the like may be used. This allows the control portion 1 to control the heater based on the temperature detected by the temperature detection portion, thereby making it possible to keep the endless belt 23 at a predetermined temperature. Note that the temperature detection portion may be a non-contact thermometer that uses infrared rays.

[0205] 2.4.Printing Department Printing unit 40 is disposed above (on the +Z axis side) the arrangement position of endless belt 23, and performs printing on fabric 95 placed on surface 23a of endless belt 23. Printing unit 40 has an inkjet head 42, a carriage 43 on which inkjet head 42 is mounted, a carriage moving unit 45 that moves carriage 43 in the width direction (Y axis direction) of fabric 95 that intersects with the transport direction, and the like.

[0206] The inkjet head 42 is a means for spraying and adhering the liquid composition supplied from a liquid cartridge (not shown) from a plurality of nozzles to the fabric 95 under the control of the control unit 1. The inkjet head 42 is provided with a plurality of nozzles for ejecting the liquid composition onto the fabric 95 to which the liquid composition is to be adhered, and adhering the liquid composition to the fabric 95. These plurality of nozzles are arranged in a row to form a nozzle row, and the nozzle rows are individually arranged corresponding to the liquid compositions. The liquid composition is supplied from each liquid cartridge to the inkjet head 42, and is ejected as droplets from the nozzles by an actuator (not shown) in the inkjet head 42. The ejected droplets of the liquid composition land on the fabric 95, and an image, text, pattern, color, or the like is formed in the printing area of ​​the fabric 95.

[0207] The liquid composition referred to here may be the softening liquid composition, coating liquid composition, ink composition, or reaction liquid composition described above. The types and numbers of these liquid compositions may be appropriately determined.

[0208] In the inkjet head 42, a piezoelectric element is used as an actuator, which is a driving means, but the invention is not limited to this method. For example, an electromechanical conversion element that displaces a vibration plate as an actuator by electrostatic adsorption, or an electrothermal conversion element that ejects a liquid composition or the like as droplets by bubbles generated by heating may be used.

[0209] The carriage moving part 45 is provided above (on the +Z-axis side of) the endless belt 23. The carriage moving part 45 has a pair of guide rails 45a, 45b extending along the Y-axis direction. The inkjet head 42 is supported by the guide rails 45a, 45b in a state in which the inkjet head 42 can move back and forth together with the carriage 43 along the Y-axis direction.

[0210] The carriage moving unit 45 includes a moving mechanism and a power source (not shown). As the moving mechanism, for example, a mechanism combining a ball screw and a ball nut, a linear guide mechanism, or the like can be adopted. Furthermore, the carriage moving unit 45 has a motor (not shown) as a power source for moving the carriage 43 along the guide rails 45a and 45b. As the motor, various motors such as a stepping motor, a servo motor, and a linear motor can be adopted. When the motor is driven under the control of the control unit 1, the inkjet head 42 moves along the Y-axis direction together with the carriage 43.

[0211] 2.5. Heating unit The heating unit 27 may be provided between the transport roller 26 and the transport roller 28. The heating unit 27 heats the ink composition, the softening liquid composition, and the coating liquid composition discharged onto the fabric 95. This tends to allow the reaction of the resin particles contained in the ink composition to proceed sufficiently. By causing the resin particles to react sufficiently, an image with good friction fastness may be formed. The heating unit 27 may be used for the purpose of drying the fabric 95. The heating unit 27 includes, for example, an IR heater, and by driving the IR heater, the ink composition and the coating liquid composition discharged onto the fabric 95 can be reacted in a short time. This allows the belt-shaped fabric 95 on which an image or the like is formed to be wound around the winding shaft 31.

[0212] 2.6.Cleaning unit The cleaning unit 50 is disposed between the belt rotation roller 24 and the belt drive roller 25 in the X-axis direction. The cleaning unit 50 has a cleaning section 51, a pressing section 52, and a moving section 53. The moving section 53 moves the cleaning unit 50 together along the floor surface 99 and fixes it at a predetermined position.

[0213] The pressing unit 52 is, for example, an elevating device composed of an air cylinder 56 and a ball bush 57, and brings the cleaning unit 51 provided on the upper part of the pressing unit 52 into contact with the surface 23a of the endless belt 23. The cleaning unit 51 is hung between the belt rotating roller 24 and the belt driving roller 25 with a predetermined tension applied, and cleans the surface (support surface) 23a of the endless belt 23 moving from the belt driving roller 25 toward the belt rotating roller 24 from below (in the -Z axis direction).

[0214] The cleaning unit 51 has a cleaning tank 54, a cleaning roller 58, and a blade 55. The cleaning tank 54 is a tank that stores a cleaning liquid used to clean ink and foreign matter adhering to the surface 23a of the endless belt 23, and the cleaning roller 58 and the blade 55 are provided inside the cleaning tank 54. As the cleaning liquid, for example, water or a water-soluble solvent (such as an alcohol aqueous solution) can be used, and a surfactant or an antifoaming agent may be added as necessary.

[0215] When the cleaning roller 58 rotates, a cleaning liquid is supplied to the surface 23a of the endless belt 23, and the cleaning roller 58 slides against the endless belt 23. As a result, the ink composition and fibers of the fabric 95 adhering to the endless belt 23 are removed by the cleaning roller 58.

[0216] The blade 55 can be made of a flexible material such as silicone rubber. The blade 55 is provided downstream of the cleaning roller 58 in the conveying direction of the endless belt 23. The cleaning liquid remaining on the surface 23a of the endless belt 23 is removed by sliding between the endless belt 23 and the blade 55.

[0217] With such a recording device 100, the recording method of this embodiment can be easily carried out.

[0218] 3. Examples and Comparative Examples The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the following, "parts" and "%" are based on mass unless otherwise specified. The evaluation was performed in an environment of a temperature of 25°C and a relative humidity of 40.0%, unless otherwise specified.

[0219] 3.1. Preparation of each composition A reaction liquid composition, an ink composition, a first treatment liquid composition, and a second treatment liquid composition were prepared as follows. Each component was placed in a container so as to have the composition shown in Table 1, and mixed and stirred for 2 hours with a magnetic stirrer, and then filtered through a membrane filter with a pore size of 5 μm to obtain a reaction liquid composition, an ink composition, a first treatment liquid composition, and a second treatment liquid composition used in the examples and comparative examples. The values ​​in the tables indicate the solid content.

[0220] The abbreviations and product names shown in Table 1 will be explained further below. E1010: Olfin E1010: Acetylene glycol surfactant manufactured by Nissin Chemical Industry Co., Ltd. MgSO4: Magnesium sulfate (polyvalent metal salt) CW-1: Bonjetblack CW-1 (Orient Chemical Industry Co., Ltd.) pigment dispersion Superflex 500M: urethane resin emulsion manufactured by Daiichi Kogyo Seiyaku Co., Ltd. - Hi-Softer K-45: Dimethyl silicone fabric softener manufactured by Meisei Chemical Industry Co., Ltd. EX-200A: Polyester fabric softener manufactured by Takamatsu Oil Co., Ltd.

[0221] 3.2.Evaluation Methodology 3.2.1. Printing test A square pattern of 30 cm on each side was printed using the ink composition (black ink). The duty was set to be different at both ends of the pattern, and the duty was controlled evenly to enable gradation printing. The deposition amount (mL / m) shown in Tables 1 to 3 was used.2 ) was printed. Figure 2 shows a schematic diagram of a square pattern formed by the ink composition. As shown in Figure 2, the side with a small duty is called end A, and the side with a large duty is called end B.

[0222] The duty of the first treatment liquid composition was set so as to be able to be controlled in the same manner as the ink composition, and the deposition amount (mL / m 2 ) The adhesion amounts in Tables 1 to 3 are the adhesion amounts at each end.

[0223] In both cases, the amount of ink deposited when printed at 100% duty was 24.3 mL / m 2 It was set to be.

[0224] In addition, in Examples 8 and 17, in which the reaction liquid composition was used, the deposition amount (duty) was made uniform over the entire image area. Also, in the examples in which the second treatment liquid composition was used, the deposition amount (duty) was made uniform over the entire image area.

[0225] The type of fabric used was 100% cotton in Examples 16 and 17, and blended fabric (PES 35%, cotton / polyester blend) was used in all other examples.

[0226] In each example, printing evaluation was carried out using a modified ML-8000 machine, using the compositions shown in Tables 1 to 3. The printing resolution was 1200×1200 dpi.

[0227] The drying temperature (fabric surface temperature) was 135°C in Example 14 and 165°C in Example 15. It was 150°C in all other examples. The drying time was 2 minutes in all examples. The drying means was a gas oven in Examples 13 and 17, and an IR heater in the other examples.

[0228] 3.2.2. Evaluation of color development Printing evaluation was performed using a modified ML-8000. The printing resolution was 1200 x 1200 dpi, and an image with a duty of 100% was printed separately using the composition used in each example, and the OD value was measured after drying at 160°C for 3 minutes. Evaluation was performed according to the following criteria, and the results are shown in the table. AA:OD value is 1.55 or more A:OD value is 1.50 or more and less than 1.55 B:OD value is less than 1.50

[0229] 3.2.3.Evaluation of Image Distortion The length of end A of the pattern obtained in each example was compared with the length of end B. Evaluation was performed according to the following criteria, and the results are shown in the table. AA: The difference in length is less than 0.5% of the length of end A A: The difference in length is 0.5% or more but less than 1% of the length of end A B: The difference in length is 1% or more but less than 3% of the length of end A. C: The difference in length is 3% or more of the length of end A

[0230] 3.2.4. Evaluation of wet rubbing fastness The prints of each example were evaluated according to the standard of ISO 105 X12. The evaluation was based on the following criteria, and the results are shown in the table. AA: 3-4 grade or higher A: Level 3 B:2-3 grade C: Level 2 or below

[0231] 3.2.5. Evaluation of texture The shear hardness (gf / cm / deg) of each printed matter was evaluated using a tensile shear tester KES-FB1-A manufactured by Kato Tech Co., Ltd. The evaluation was based on the following criteria, and the results are shown in the table. AA: Shear hardness less than 6 (gf / cm / deg) A: Shear hardness is 6 (gf / cm / deg) or more and less than 8 (gf / cm / deg) B: Shear hardness is 8 (gf / cm / deg) or more and less than 10 (gf / cm / deg) C: Shear hardness is 10 (gf / cm / deg) or more In addition, in Example 7, "AA※ " indicates that the condition is good, but some slime is formed.

[0232] 3.3.Evaluation Results Looking at each table, it can be seen that the method includes a colored ink applying step of applying an ink composition containing a pigment, resin particles, and water to a recording medium by an inkjet method to form an image area, a first treatment liquid applying step of applying a first treatment liquid composition containing resin particles and water to the recording medium by an inkjet method, and a second treatment liquid applying step of applying a second treatment liquid composition containing a softener to the recording medium by an inkjet method, the image area has areas with different ink application amounts per unit area, the first treatment liquid applying step and the second treatment liquid applying step are performed on at least the entire image area, and the application amount of the first treatment liquid composition is 12 mL / m 2 As described above, it was found that the recorded matter obtained by the recording method of each of the Examples had good robustness and texture, and image distortion was reduced.

[0233] The present invention includes configurations that are substantially the same as the configurations described in the embodiments, for example, configurations with the same functions, methods, and results, or configurations with the same purpose and effects. The present invention also includes configurations in which non-essential parts of the configurations described in the embodiments are replaced. The present invention also includes configurations that achieve the same effects as the configurations described in the embodiments, or configurations that can achieve the same purpose. The present invention also includes configurations in which publicly known technology is added to the configurations described in the embodiments.

[0234] The following can be derived from the above-described embodiment and modified examples.

[0235] The recording method is a color ink application step in which an ink composition containing a pigment, resin particles, and water is applied to a recording medium by an ink jet method to form an image area; a first treatment liquid application step of applying a first treatment liquid composition containing resin particles and water to a recording medium by an inkjet method; a second treatment liquid application step of applying a second treatment liquid composition containing a softener to a recording medium by an inkjet method; having the image area has areas with different ink deposition amounts per unit area, the first treatment liquid application step and the second treatment liquid application step are performed on at least the entire image area, The amount of the first treatment liquid composition applied is 12 mL / m 2 That's all.

[0236] According to this recording method, since the ink composition contains resin particles, a recorded matter having good resistance to friction can be obtained. 2 By applying the above amount, the difference in shrinkage between the image area and the area to which the first treatment liquid composition is applied is reduced, and image distortion can be suppressed. Furthermore, by further applying the second treatment liquid composition, the texture of the recorded matter can be improved.

[0237] In the above recording method, The content of the resin particles in the first treatment liquid composition may be 80 mass % or more with respect to the total amount of non-volatile components in the first treatment liquid composition.

[0238] This recording method provides a recording having better resistance to abrasion.

[0239] In the above recording method, The content of the softener in the second treatment liquid composition may be 60 mass % or more based on the total amount of non-volatile components in the second treatment liquid composition.

[0240] According to this recording method, a recorded matter with a better texture can be obtained.

[0241] In the above recording method, Within the image region, the difference between an area where the total of the applied amount of the ink composition and the applied amount of the first treatment liquid composition per unit area is maximum and an area where the total of the applied amount of the ink composition and the applied amount of the first treatment liquid composition per unit area is minimum is 10 mL / m 2 It may be the following.

[0242] According to this recording method, the total amount of adhesion of the ink composition and the first treatment liquid composition becomes roughly the same within the image area, so that image distortion can be further suppressed.

[0243] In the above recording method, The amount of the second treatment liquid composition applied may be half or more of the amount of the first treatment liquid composition applied.

[0244] According to this recording method, a recorded matter with a better texture can be obtained.

[0245] In the above recording method, The softener may be a dimethyl silicone softener.

[0246] According to this recording method, a recorded matter with a better texture can be obtained.

[0247] In the above recording method, The content of the softener may be 8% by mass or more and 15% by mass or less with respect to the total amount of the second treatment liquid composition.

[0248] According to this recording method, a recorded matter with a better texture can be obtained.

[0249] In the above recording method, The method may further include a reaction liquid deposition step of depositing a reaction liquid composition containing an aggregating agent that aggregates components in the ink composition onto a recording medium.

[0250] According to this recording method, a recorded matter with even better color development can be obtained.

[0251] In the above recording method, The content of the resin particles in the ink composition may be 4% by mass or more and 8% by mass or less with respect to the total amount of the ink composition, and the content of the resin particles in the first treatment liquid composition may be 10% by mass or more and 15% by mass or less with respect to the total amount of the first treatment liquid composition.

[0252] According to this recording method, it is easy to reduce the difference in shrinkage between the image area and the area to which the first treatment liquid composition is applied, and it is easy to further suppress image distortion.

[0253] In the above recording method, The method may further include a step of drying by heating.

[0254] According to this recording method, in cases where image distortion is likely to occur due to heating and drying, the effect of reducing distortion can be more significantly achieved.

[0255] In the above recording method, In the heat drying, the recording medium may be heated so that the surface temperature becomes 150° C. or higher and 160° C. or lower.

[0256] According to this recording method, in cases where image distortion is likely to occur due to heating and drying, the effect of reducing distortion can be more significantly achieved.

[0257] In the above recording method, The recording medium may be a fabric.

[0258] According to this recording method, when recording on fabric, which is more susceptible to image distortion, the effect of reducing distortion can be more prominent.

[0259] In the above recording method, The recording medium may be a cotton fabric.

[0260] According to this recording method, when recording on cotton fabric, which is more susceptible to image distortion, the effect of reducing distortion can be more prominent. [Explanation of symbols]

[0261] 1...control section, 10...medium supply section, 11...supply shaft section, 12...bearing section, 20...medium transport section, 21...transport roller, 22...transport roller, 23...endless belt, 23a...surface, 23b...inner surface, 24...belt rotation roller, 25...belt drive roller, 26...transport roller, 27...heating unit, 28...transport roller, 29...adhesive, 30...medium recovery section, 31...winding shaft section, 32...bearing section, 40...printing section, 43...carriage 45...carriage moving part, 45a...guide rail, 45b...guide rail, 46...platen, 50...cleaning unit, 51...cleaning part, 52...pressing part, 53...moving part, 54...cleaning tank, 55...blade, 56...air cylinder, 57...ball bushing, 58...cleaning roller, 60...medium contact part, 61...pressing part, 69...contact part, 90...frame part, 91...belt support part, 95...fabric, 99...floor surface, 100...recording device

Claims

1. a color ink application step in which an ink composition containing a pigment, resin particles, and water is applied to a recording medium by an ink jet method to form an image area; a first treatment liquid application step of applying a first treatment liquid composition containing resin particles and water to a recording medium by an inkjet method; a second treatment liquid application step of applying a second treatment liquid composition containing a softener to a recording medium by an inkjet method; having the image area has areas with different ink deposition amounts per unit area, the first treatment liquid application step and the second treatment liquid application step are performed on at least the entire image area, The amount of the first treatment liquid composition applied is 12 mL / m ２ That's it for the recording method.

2. In claim 1, A recording method, wherein a content of the resin particles in the first treatment liquid composition is 80% by mass or more with respect to a total amount of non-volatile components in the first treatment liquid composition.

3. In claim 1, A recording method, wherein the content of the softener in the second treatment liquid composition is 60% by mass or more based on the total amount of non-volatile components in the second treatment liquid composition.

4. In any one of claims 1 to 3, Within the image region, the difference between an area where the total of the adhesion amount of the ink composition and the adhesion amount of the first treatment liquid composition per unit area is maximum and an area where the total of the adhesion amount of the ink composition and the adhesion amount of the first treatment liquid composition per unit area is minimum is 10 mL / m ２ The recording method is as follows.

5. In any one of claims 1 to 3, A recording method, wherein the amount of the second treatment liquid composition applied is at least half of the amount of the first treatment liquid composition applied.

6. In any one of claims 1 to 3, The recording method, wherein the softener is a dimethyl silicone softener.

7. In any one of claims 1 to 3, A recording method, wherein the content of the softener is 8% by mass or more and 15% by mass or less with respect to the total amount of the second treatment liquid composition.

8. In any one of claims 1 to 3, The recording method further comprises a reaction liquid applying step of applying to a recording medium a reaction liquid composition containing an aggregating agent that aggregates components in the ink composition.

9. In any one of claims 1 to 3, a content of the resin particles in the ink composition is 4% by mass or more and 8% by mass or less with respect to a total amount of the ink composition, and a content of the resin particles in the first treatment liquid composition is 10% by mass or more and 15% by mass or less with respect to a total amount of the first treatment liquid composition.

10. In any one of claims 1 to 3, The recording method further comprises a step of drying by heating.

11. In claim 8, The recording method, wherein the heating and drying step heats the recording medium so that the surface temperature of the recording medium becomes 150° C. or higher and 160° C. or lower.

12. In any one of claims 1 to 3, The recording method, wherein the recording medium is a fabric.

13. In claim 12, The recording method, wherein the recording medium is a cotton fabric.

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