Recording method and recording apparatus

Abstract

Provided is a recording method and a recording apparatus in which the quality of an image formed by a white ink composition and the quality of an image formed by a non-white ink composition are both good. A recording method includes: a white ink adhering step of adhering a white ink composition containing a white color material to a recording medium; a non-white ink adhering step of adhering a non-white ink composition containing a non-white color material so as to overlap the white ink composition that has been adhered; a first treatment liquid adhering step of adhering a treatment liquid containing a coagulant to the recording medium in conjunction with the white ink adhering step; and a second treatment liquid adhering step of adhering a treatment liquid to the recording medium in conjunction with the non-white ink adhering step, the viscosity of the white ink composition increases by 5 times or more when the white ink composition is mixed with a 7 mass% aqueous solution of calcium formate at a mass ratio of 10:1, and the amount of treatment liquid adhered in the second treatment liquid adhering step is less than the amount of treatment liquid adhered in the first treatment liquid adhering step.

Description

[0001] Related applications Technical Field

[0002] This invention relates to a recording method and a recording apparatus. Background Technology

[0003] The recording of high-resolution images using a processing liquid method was investigated in various aspects. Additionally, an attempt was made to improve the visual recognizability of images by overlapping white and non-white images.

[0004] For example, Patent Document 1 discloses an ink assembly comprising a reaction liquid containing a coagulant, a first ink containing a white pigment, and a second ink containing a non-white pigment, wherein the reaction liquid, the first ink, and the second ink are applied to a recording medium in an overlapping manner in this order.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent document 1: Japanese Patent Application Publication No. 2015-071738.

[0008] In cases where the reactivity of the white ink composition with the processing liquid is increased to obtain excellent image quality of the white ink composition layer, the coagulation of the white ink composition components consumes the coagulant in the reaction liquid, thus preventing the components of the non-white ink composition from reacting sufficiently with the coagulant. This sometimes results in a deterioration in the image quality of the non-white ink composition. Therefore, a recording method is required that produces images with good quality from both the white ink composition and the non-white ink composition. Summary of the Invention

[0009] One embodiment of the recording method involved in this invention comprises:

[0010] The white ink adhesion process involves adhering a white ink composition containing white pigment to a recording medium.

[0011] The non-white ink adhesion process involves adhering a non-white ink composition containing a non-white pigment to the already adhered white ink composition in an overlapping manner.

[0012] The first processing liquid adhesion step, which follows the white ink adhesion step, causes the processing liquid containing a coagulant to adhere to the recording medium; and

[0013] The second processing liquid adhesion step, which follows the non-white ink adhesion step, causes the processing liquid containing a coagulant to adhere to the recording medium.

[0014] The viscosity of the white ink composition increases more than fivefold when mixed with a 7% (w / w) aqueous solution of calcium formate at a mass ratio of 10:1.

[0015] The amount of treatment liquid adhering in the second treatment liquid adhesion step is smaller than the amount of treatment liquid adhering in the first treatment liquid adhesion step.

[0016] One embodiment of the recording device involved in this invention is as follows:

[0017] The recording device comprises: an attachment mechanism for performing the white ink attachment process described above, an attachment mechanism for performing the non-white ink attachment process described above, an attachment mechanism for performing the first treatment liquid attachment process described above, and an attachment mechanism for performing the second treatment liquid attachment process described above, and the recording device executes the recording method described above. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of an example of an inkjet recording apparatus that can be used in the recording method of the implementation.

[0019] Figure 2 This is a schematic diagram of the carriage perimeter of an example of an inkjet recording apparatus that can be used in the recording method of the embodiment.

[0020] Figure 3 This is a block diagram of an example of an inkjet recording apparatus used in the recording method of an embodiment.

[0021] Figure 4 (1) Figure 4 (2) Figure 4 (3) is a schematic diagram of an example of an inkjet recording head of an inkjet recording device that can be used in the recording method of the embodiment.

[0022] Figure 5 This is a schematic diagram of another example of an inkjet recording apparatus that can be used in the recording method of the implementation.

[0023] Symbol Explanation

[0024] 1. Inkjet recording device; 2. Inkjet head; 2a, 2b, 2c, 2d, Inkjet head; 3. IR heater; 4. Platen heater; 5. Heater; 6. Cooling fan; 7. Preheater; 8. Air supply fan; 9. Carriage; 10. Recording medium; 11. Platen; 12. Ink cartridge; 13. Carriage moving mechanism; 14. Transport device; 101. Interface unit; 102. CPU; 103. Memory; 104. Unit control circuit; 111. Transport unit; 112. Carriage unit; 113. Printhead unit; 114. Drying unit; 121. Detector group; 130. Computer; CONT, Control unit; MS, Main scanning direction; SS, Sub-scanning direction; M, Recording medium. Detailed Implementation

[0025] The embodiments of the present invention will now be described. The embodiments described below are illustrative examples of the present invention. The present invention is not limited to the following embodiments and includes various modifications implemented without altering the spirit of the invention. It should be noted that not all of the configurations described below are necessarily essential components of the present invention.

[0026] 1. Recording Method

[0027] The recording method according to this embodiment includes: a white ink adhesion step, in which a white ink composition containing a white pigment is adhered to a recording medium; a non-white ink adhesion step, in which a non-white ink composition containing a non-white pigment is adhered overlappingly with the already adhered white ink composition; a first processing liquid adhesion step, in which a processing liquid containing a coagulant is adhered to the recording medium following the white ink adhesion step; and a second processing liquid adhesion step, in which a processing liquid containing a coagulant is adhered to the recording medium following the non-white ink adhesion step. Furthermore, the viscosity of the white ink composition increases by more than 5 times when the white ink composition is mixed with a 7% by mass aqueous solution of calcium formate at a mass ratio of 10:1, and the amount of processing liquid adhered in the second processing liquid adhesion step is less than the amount of processing liquid adhered in the first processing liquid adhesion step.

[0028] 1.1 White ink adhesion process

[0029] The white ink adhesion process is the process of adhering a white ink composition to a recording medium. The white ink composition will be described below. Methods for adhering to the recording medium will be described later.

[0030] The white ink composition can be any ink other than a water-based ink containing a white pigment. Examples of water-based inks include those containing, for instance, an evaporable solvent component in addition to water. Alternatively, water-based inks can be water-based resin inks containing a resin. With such inks, the solvent component dries and evaporates from the ink adhering to the recording medium, while the pigment and other components remain on the recording medium, thereby enabling recording.

[0031] 1.1.1. White pigment

[0032] The white ink composition contains a white pigment. Examples of white pigments include metal oxides, barium sulfate, calcium carbonate, and other metal compounds. Examples of metal oxides include titanium dioxide, zinc oxide, silicon dioxide, aluminum oxide, and magnesium oxide. Alternatively, the white pigment can also be composed of particles with a hollow structure; known particles can be used as hollow-structured particles.

[0033] As a white colorant, in the above examples, titanium dioxide is preferred from the viewpoint of good whiteness and abrasion resistance. A single white colorant may be used, or two or more may be used in combination.

[0034] The volume average particle size (D50) of the white pigment (also referred to as "volume average particle size") is set to be larger than the volume average particle size of the inorganic particles described later. The volume average particle size of the white pigment is preferably 30.0 nm or more and 600.0 nm or less, more preferably 100.0 nm or more and 500.0 nm or less, and even more preferably 150.0 nm or more and 400.0 nm or less. If the volume average particle size of the white pigment is within the above range, the particles are less likely to settle, resulting in good dispersion stability. Furthermore, when applied to inkjet recording devices, nozzle clogging is less likely to occur. Additionally, if the volume average particle size of the white pigment is within the above range, it can significantly improve the visual recognizability of the image.

[0035] The volume average particle size of white pigments can be measured using a particle size distribution measuring device. Examples of such devices include particle size analyzers based on the dynamic light scattering method (e.g., the "Nanotrac series" manufactured by MicrotracBEL). The volume average particle size is set as the D50 value.

[0036] It should be noted that in this specification, the term "white" when referring to white ink compositions, white pigments, etc., does not refer only to pure white. It includes any area that can be visually identified as white, including colors that are tinted or achromatic, and colors with a glossy finish. Furthermore, the names of inks or pigments include names that clearly indicate they are white, and their market names.

[0037] More quantitatively, "white" not only includes records such as L in CIELAB The color is 100, and it also includes L. For those with a score between 60 and 100, a and b The colors are all within ±10.

[0038] More specifically, for example, the white ink composition is preferably a composition that, when recording is performed on the surface of a transparent film recording medium in an amount sufficient to cover it, measures the brightness (L) of the recorded portion of the record using a spectrophotometer according to CIELAB. ) and chromaticity (a b The colorimetric measurements were performed within the aforementioned range. The amount of material recorded with sufficient coverage was, for example, 15 mg / 645.16 mm. 2The amount of adhesion. More preferably, 80 ≤ L ≤100、-4.5≤a ≤2、-10≤b ≤2.5. For example, the LAGJet E-1000ZC (manufactured by Lintec) can be used as a transparent thin-film recording medium. For example, the Spectrolino (trade name, manufactured by GretagMacbeth) can be used as a CIELAB-based spectrometer, with the measurement conditions set to a D50 light source, a viewing angle of 2°, a density of DIN NB, a white reference of Abs, a filter of No, and a measurement mode of Reflectance.

[0039] Typical examples of white pigments include titanium dioxide, such as Tipaque CR-50-2, CR-57, CR-58-2, CR-60-2, CR-60-3, CR-Super-70, CR-90-2, CR-95, CR953, PC-3, PF-690, PF-691, PF-699, PF-711, PF-728, PF-736, PF-737, PF-739, PF-739, PF-740, PF-742, R-980, and UT-717 (all manufactured by Ishihara Sangyo Co., Ltd.).

[0040] The content (solid component) of the white pigment in the white ink composition relative to the total mass of the white ink composition is preferably 0.5% by mass or more and 20.0% by mass or less, more preferably 1.0% by mass or more and 20.0% by mass or less, further preferably 3.0% by mass or more and 15.0% by mass or less, and even more preferably 7.0% by mass or more and 12.0% by mass or less. If the content of the white pigment is within the above range, an image with sufficient visual recognizability can be obtained.

[0041] In the recording method of this embodiment, the white pigment has the function of concealing the background of the image and improving the visual recognizability of the obtained image. When the white pigment content in the white ink composition is used for the purpose of improving the visual recognizability of the image, it can be further reduced compared to the case where the purpose is to conceal the background. Therefore, when the white ink composition is used for the purpose of improving the visual recognizability of the image, sufficient visual recognizability of the image can be obtained, and the dispersion stability of the white pigment is good, making it difficult for the white pigment to settle. From this viewpoint, the upper limit of the white pigment content in the white ink composition is preferably within the above-mentioned range, preferably 10.0% by mass or less.

[0042] The white pigment is preferably stable in the dispersion medium, and a dispersant can be used for this purpose. Examples of dispersants include resin dispersants, and the dispersant selected from those that provide good dispersion stability of the white pigment in a white ink composition containing the aforementioned white pigment. Alternatively, the surface of the pigment particles can be modified by oxidizing or sulfonating the pigment surface with substances such as ozone, hypochlorous acid, or fuming sulfuric acid, thereby using the white pigment as a self-dispersing pigment.

[0043] Examples of resin dispersants (dispersant resins) include: poly(meth)acrylic acid, (meth)acrylic acid-acrylonitrile copolymer, (meth)acrylic acid-(meth)acrylate copolymer, vinyl acetate-(meth)acrylate copolymer, vinyl acetate-(meth)acrylic acid copolymer, vinylnaphthalene-(meth)acrylic acid copolymer, and other (meth)acrylic acid resins and their salts; styrene-(meth)acrylic acid copolymer, styrene-(meth)acrylic acid-(meth)acrylate copolymer, styrene-α-methylstyrene-(meth)acrylic acid copolymer, styrene-α-methylstyrene-(meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, and other styrene-based resins and their salts; urethane resins and their salts, which are polymeric compounds (resins) containing urethane bonds formed by the reaction of isocyanate groups and hydroxyl groups, and can be linear and / or branched, regardless of whether they have a cross-linked structure; polyvinyl alcohols; vinylnaphthalene-maleic acid copolymers and their salts; vinyl acetate-maleic acid ester copolymers and their salts; and vinyl acetate-crotonic acid copolymers and their salts, etc., which are water-soluble resins. Preferably, copolymers of monomers having hydrophobic functional groups and monomers having hydrophilic functional groups, or polymers composed of monomers having both hydrophobic and hydrophilic functional groups, are used. As the form of copolymer, any form of random copolymer, block copolymer, alternating copolymer, or graft copolymer can be used.

[0044] Commercially available dispersants for styrene resins include, for example: X-200, X-1, X-205, X-220, X-228 (manufactured by Starlight PMC); Nopcosperse (registered trademark) 6100, 6110 (manufactured by SanNopco Co., Ltd.); Joncryl 67, 586, 611, 678, 680, 682, 819 (manufactured by BASF); DISPERBYK-190 (manufactured by BYK Chemie Japan Co., Ltd.); N-EA137, N-EA157, N-EA167, N-EA177, N-EA197D, N-EA207D, E-EN10 (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.), etc.

[0045] In addition, commercially available dispersants for acrylic resins include: BYK-187, BYK-190, BYK-191, BYK-194N, BYK-199 (manufactured by BYK Chemie Co., Ltd.); AronA-210, A6114, AS-1100, AS-1800, A-30SL, A-7250, CL-2 (manufactured by Toa Synthetic Co., Ltd.), etc.

[0046] Furthermore, commercially available products as urethane-based resin dispersants include: BYK-182, BYK-183, BYK-184, BYK-185 (manufactured by BYK Chemie Co., Ltd.), TEGO Disperse 710 (manufactured by Evonic Tego Chemi Co., Ltd.), and Borchi (registered trademark) Gen1350 (manufactured by OMG Borschers Co., Ltd.).

[0047] The dispersant can be used alone or in combination with two or more. The total content of the dispersant relative to 50 parts by weight of the white pigment is preferably 0.1 parts by weight or more and 30 parts by weight or less, more preferably 0.5 parts by weight or more and 25 parts by weight or less, further preferably 1 part by weight or more and 20 parts by weight or less, and even more preferably 1.5 parts by weight or more and 15 parts by weight or less. By making the content of the dispersant relative to 50 parts by weight of the white pigment 0.1 parts by weight or more, the dispersion stability of the white pigment can be further improved. Furthermore, if the content of the dispersant relative to 50 parts by weight of the white pigment is 30 parts by weight or less, the viscosity of the resulting dispersion can be reduced to a lower value.

[0048] In the dispersants exemplified above, at least one selected from anionic dispersant resins is further preferred. Furthermore, in this case, the weight-average molecular weight of the dispersant is more preferably 500 or more. More preferably, it is 5000 or more and 100000 or less, more preferably 10000 or more and 500000 or less.

[0049] By using such a resin dispersant as a dispersant, the dispersion and aggregation of white pigments are improved, resulting in images with better dispersion stability and image quality. Furthermore, it readily increases the viscosity of the white ink composition (described later) by more than 5 times, which is therefore preferable.

[0050] Anionic dispersant resins are resins that possess anionic functional groups and exhibit anionic properties. Examples of anionic functional groups include carboxyl, sulfonyl, and phosphate groups. Among these groups, carboxyl is more preferred.

[0051] The dispersant resin preferably has an acid value of 5 mg KOH / g or higher, more preferably 10–200 mg KOH / g, and even more preferably 15–150 mg KOH / g. Furthermore, 20–100 mg KOH / g is preferred, and more preferably 25–70 mg KOH / g. In this case, the thickening rate of the white ink composition (described later) is easily increased by 5 times or more, which is therefore preferable.

[0052] The acid value can be determined according to JIS K0070 using the neutralization potential difference titration method. For example, the "AT610" manufactured by Kyoto Electronics Industry Co., Ltd. can be used as the titration apparatus.

[0053] 1.1.2. Other ingredients

[0054] White ink compositions may contain, in addition to white pigment, water, resin particles, organic solvents, surfactants, waxes, additives, resin dispersants, preservatives, fungicides, rust inhibitors, chelating agents, viscosity modifiers, antioxidants, and other components. These will be described in turn below.

[0055] (water)

[0056] The white ink composition used in the recording method according to this embodiment may contain water. The white ink composition is preferably an aqueous white ink composition. Aqueous means a composition containing water as one of the main solvent components. This allows for recording with reduced environmental impact and less odor.

[0057] Water can be included as the main solvent component of the white ink composition, and is a component that evaporates and dissipates through drying. The water is preferably pure water or ultrapure water, such as ion-exchanged water, ultrafiltered water, reverse osmosis water, or distilled water, which has been thoroughly purified to remove ionic impurities. Furthermore, if water sterilized by ultraviolet irradiation or the addition of hydrogen peroxide is used, the growth of mold or bacteria can be inhibited during long-term storage of the ink, which is therefore preferred. The water content relative to the total amount of the white ink composition is preferably 45% by mass or more, more preferably 50% by mass or more and 98% by mass or less, and even more preferably 55% by mass or more and 95% by mass or less.

[0058] (Resin particles)

[0059] The white ink composition may contain resin particles. That is, the white ink composition may be a white water-based resin ink. Resin particles can further improve the adhesion of the image formed by the white ink composition adhering to the recording medium. Examples of resin particles include those composed of urethane-based resins, acrylic resins (including styrene-acrylic resins), fluorene-based resins, polyolefin-based resins, rosin-modified resins, terpene-based resins, polyester-based resins, polyamide-based resins, epoxy-based resins, vinyl chloride-based resins, vinyl chloride-vinyl acetate copolymers, and ethylene vinyl acetate-based resins. Uranethane-based resins, acrylic resins, polyolefin resins, and polyester resins are preferred. These resin particles are mostly processed in emulsion form, but may also be in powder form. Furthermore, one or more resin particles can be used alone or in combination.

[0060] Urea-based resins refer to a general term for resins containing urethane bonds. For urethane-based resins, we can use polyether-type urethane resins, which contain ether bonds in addition to urethane bonds in their main chain; polyester-type urethane resins, which contain ester bonds in addition to urethane bonds in their main chain; and polycarbonate-type urethane resins, which contain carbonate bonds in addition to urethane bonds in their main chain. In addition, commercially available products can be used as urethane-based resins, such as SUPERFLEX460, 460s, 840, E-4000 (trade name, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.), Resamine D-1060, D-2020, D-4080, D-4200, D-6300, D-6455 (trade name, manufactured by Daiichi Seika Kogyo Co., Ltd.), TakelacWS-6021, W-512-A-6 (trade name, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.), SunCure2710 (trade name, manufactured by LUBRIZOL Co., Ltd.), and PermarinUA-150 (trade name, manufactured by Sanyo Chemical Co., Ltd.).

[0061] Acrylic resins are a general term for polymers obtained by polymerizing acrylic monomers such as (meth)acrylic acid and (meth)acrylates as at least one component. Examples include resins obtained from acrylic monomers, or copolymers of acrylic monomers with monomers other than those monomers. For example, acrylic-vinyl resins, which are copolymers of acrylic monomers and vinyl monomers, are examples. Additionally, styrene is an example of a vinyl monomer.

[0062] Acrylamide and acrylonitrile can also be used as acrylic monomers. For resin emulsions using acrylic resins as raw materials, commercially available products can be used, such as FK-854 (trade name, manufactured by Chuo Riko Kogyo Co., Ltd.), Mowinyl 952B, 718A (trade name, manufactured by Nippon Synthetic Chemical Co., Ltd.), Nipol LX852, and LX874 (trade name, manufactured by Zeon Corporation of Japan).

[0063] It should be noted that, in this specification, acrylic resin may also be the styrene acrylic resin described later. Furthermore, in this specification, the term (meth)acrylic acid means at least one of acrylic acid and methacrylic acid.

[0064] Styrene-acrylic resins are copolymers obtained from styrene monomers and (meth)acrylic monomers, including: styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylate copolymers, styrene-α-methylstyrene-acrylic acid copolymers, styrene-α-methylstyrene-acrylic acid-acrylate copolymers, etc. For styrene-acrylic resins, commercially available products can 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, 7610 (trade name, manufactured by BASF), Mowinyl 966A, 975N (trade name, manufactured by Nippon Synthetic Chemicals Co., Ltd.), Vinyblan2586 (manufactured by Nissin Chemical Co., Ltd.), etc.

[0065] Polyolefin resins are resins that contain olefins such as ethylene, propylene, and butene in their structural backbone. Well-known resins can be selected appropriately. As olefin resins, commercially available products can be used, such as ArrowBase CB-1200 and CD-1200 (trade name, manufactured by Uniqlo Co., Ltd.).

[0066] In addition, resin particles can be supplied in the form of an emulsion. Examples of commercially available resin emulsions include: Microgel E-1002, E-5002 (trade name of PAINT Corporation, Japan, styrene-acrylic resin emulsion); Voncoat 4001 (trade name of DIC Corporation, acrylic resin emulsion); Voncoat 5454 (trade name of DIC Corporation, styrene-acrylic resin emulsion); Polysol AM-710, AM-920, AM-2300, AP-4735, AT-860, 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) (trade name manufactured by Showa Denko Corporation); Polysol SAE1014 (trade name, styrene-acrylic resin emulsion, manufactured by Zeon Corporation of Japan), Saivinol SK-200 (trade name, acrylic resin emulsion, manufactured by Saiden Chemical Co., Ltd.), AE-120A (trade name manufactured by JSR Corporation, acrylic resin emulsion), AE373D (trade name manufactured by E-TEC Corporation, carboxyl-modified styrene-acrylic resin emulsion), Seikadyne 1900W (trade name manufactured by Dainisei Chemical Industry Co., Ltd., ethylene-vinyl acetate resin emulsion), Vinyblan 2682 (acrylic resin emulsion), Vinyblan 2886 (vinyl acetate-acrylic resin emulsion), Vinyblan 5202 (acrylic acetate-acrylic resin emulsion) (trade name manufactured by Nissin Chemical Industry Co., Ltd.); Elitel KA-5071S, KT-8803, KT-9204, KT-8701, KT-8904, KT-0507 (trade names of Uniqlo Corporation, polyester resin emulsions); HYTEC SN-2002 (trade name of Toho Chemical Co., Ltd., polyester resin emulsion); Takelac W-6020, W-635, W-6061, W-605, W-635, W-6021 (trade names of Mitsui Chemicals Polyurethane Co., Ltd., urethane-based resin emulsions); Superflex 870, 800, 150, 420, 460, 470, 610, 700 (trade names of Daiichi Kogyo Pharmaceutical Co., Ltd., urethane-based resin emulsions); Permarin UA-150 (manufactured by Sanyo Chemical Co., Ltd., urethane-based resin emulsion); Sancure 2710 (trade name, manufactured by Lubrizol Co., Ltd., Japan, urethane-based resin emulsion);NeoRez R-9660, R-9637, R-940 (manufactured by Kusumoto Chemical Co., Ltd., urethane resin emulsion); Adeka BonTighter HUX-380, 290K (trade name, manufactured by ADEKA Co., Ltd., urethane resin emulsion); Movinyl 966A, Mowinyl 7320 (manufactured by Nippon Synthetic Chemical Co., Ltd.); Joncryl 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, 7610 (all manufactured by BASF); NK Binder R-5HN (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.); HydranWLS-210 (non-crosslinked polyurethane: manufactured by DIC Corporation); Joncryl 7610 (manufactured by BASF), etc.

[0067] The glass transition temperature (Tg) of the resin particles is preferably -50°C or higher and 200°C or lower, more preferably 0°C or higher and 150°C or lower, and even more preferably 50°C or higher and 100°C or lower. Furthermore, 50°C or higher and 80°C or lower is particularly preferred. By keeping the glass transition temperature (Tg) of the resin particles within the above range, there is a tendency for superior durability and clog resistance. The glass transition temperature is measured, for example, using a differential scanning calorimeter "DSC7000" manufactured by Hitachi High Technology Scientific Co., Ltd., according to JIS K7121 (Method for Determination of Transition Temperature of Plastics).

[0068] The volume average particle size of the resin particles is preferably 10 nm or more and 300 nm or less, more preferably 30 nm or more and 300 nm or less, even more preferably 30 nm or more and 250 nm or less, and particularly preferably 40 nm or more and 220 nm or less. The volume average particle size can be determined by the method described above.

[0069] The acid value of the resin particles is preferably 50 mg KOH / g or less, more preferably 30 mg KOH / g or less, even more preferably 20 mg KOH / g or less, and particularly preferably 10 mg KOH / g or less. Furthermore, the lower limit of the acid value is 0 mg KOH / g or more, preferably 5 mg KOH / g or more, and more preferably 10 mg KOH / g or more. In this case, image quality is excellent and preferred. The acid value can be determined using the method described above.

[0070] When the white ink composition contains resin particles, the content of these particles relative to the total mass of the white ink composition, calculated as solids, is 0.1% or more and 20% or less, preferably 1% or more and 15% or less, and more preferably 2% or more and 10% or less.

[0071] (Organic solvent)

[0072] The white ink composition used in the recording method according to this embodiment may contain an organic solvent. The organic solvent is preferably water-soluble. One function of the organic solvent is to improve the wettability of the white ink composition to the recording medium or to improve the moisture retention of the white ink composition. Additionally, the organic solvent may also function as a penetrant.

[0073] Examples of organic solvents include: esters, alkylene glycol ethers, cyclic esters, nitrogen-containing solvents, and polyhydroxy alcohols. Examples of nitrogen-containing solvents include: cyclic amides and non-cyclic amides. Examples of non-cyclic amides include alkoxyalkylamides.

[0074] Examples of esters include: ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, and other ethylene glycol monoacetates; and ethylene glycol diacetates, diethylene glycol diacetate, propylene glycol diacetate, and other diol diesters.

[0075] As alkylene glycol ethers, any mono- or di-ether of an alkylene glycol is acceptable, with alkyl ethers being preferred. Specific examples include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and other alkylene glycol monoalkyl ethers; and ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and other alkylene glycol dialkyl ethers.

[0076] Examples of cyclic esters include cyclic esters (lactones) such as β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, and β-butyrolactone, as well as compounds obtained by substituting the hydrogen atom of the methylene group adjacent to their carbonyl group with an alkyl group having 1 to 4 carbon atoms.

[0077] 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.

[0078] Examples of cyclic amides include lactams, such as 2-pyrrolidone, 1-methyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, and other pyrrolidone derivatives. These are preferred in terms of their solubility as coagulants and their ability to promote the film formation of resin particles (described later). 2-pyrrolidone is particularly preferred.

[0079] In addition, as an alkoxyalkylamide, a compound represented by the following general formula (1) is preferred.

[0080] R 1 -O-CH2CH2-(C=O)-NR 2 R 3 ...(1)

[0081] In the above formula (1), R 1 R represents an alkyl group having 1 or more but less than 4 carbon atoms. 2 and R 3 Each can be represented independently as methyl or ethyl. "Alkyl group having 1 or more carbon atoms and less than 4 carbon atoms" can be a straight-chain or branched alkyl group, for example, it can be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl. The compound represented by the above formula (1) can be used alone or in combination of two or more.

[0082] As a nitrogen-containing solvent, its function can be exemplified by improving the surface drying and fixing properties of white ink compositions adhered to low-absorbency recording media. In particular, the compound represented by formula (1) above exhibits excellent properties in moderately softening and dissolving vinyl chloride-based resins. Therefore, the compound represented by formula (1) above can soften and dissolve the recording surface containing vinyl chloride-based resins, thereby allowing the white ink composition to penetrate into the interior of the low-absorbency recording medium. Through this penetration of the white ink composition into the low-absorbency recording medium, the white ink composition is firmly fixed, and the surface of the white ink composition becomes easier to dry. Therefore, the resulting image is more likely to exhibit excellent surface drying and fixing properties.

[0083] The content of nitrogen-containing solvent is not particularly limited relative to the total mass of the white ink composition, but is approximately 5% by mass or more and 50% by mass or less, preferably 10% by mass or more and 30% by mass or less. By keeping the content within the above range, it is sometimes possible to further improve the fixing properties and surface drying properties of the image (especially the surface drying properties when recording is performed in a high-temperature and high-humidity environment).

[0084] Examples of polyhydroxy alcohols include: 1,2-alkanediols (e.g., ethylene glycol, propylene glycol (also known as propane-1,2-diol), 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, etc.), and polyhydroxy alcohols (polyols) other than 1,2-alkanediols (e.g., diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol (also known as 1,3-butylenediol)). (e.g., 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, glycerol, etc.)

[0085] Examples of polyhydroxy alcohols include alkyldiols and polyols. Alkalkyldiols are diols of alkanes having 5 or more carbon atoms. The number of carbon atoms in the alkanes is preferably 5 to 15, more preferably 6 to 10, and even more preferably 6 to 8. 1,2-Alkalkyldiols are preferred.

[0086] The polyols are intermolecular condensations between hydroxyl groups of alkane polyols having 4 or fewer carbon atoms, or alkane polyols having 4 or fewer carbon atoms. The alkane preferably has 2 to 3 carbon atoms. The polyol molecule has 2 or more hydroxyl groups, preferably 5 or less, more preferably 3 or less. When the polyol is an intermolecular condensation as described above, the intermolecular condensation number is 2 or more, preferably 4 or less, more preferably 3 or less. Polyhydroxy alcohols can be used alone or in mixtures of two or more.

[0087] Alkanediols and polyols can primarily function as penetrating solvents and / or moisturizing solvents. However, alkanediols tend to be stronger penetrating solvents, while polyols tend to be stronger moisturizing solvents.

[0088] When the white ink composition contains an organic solvent, one organic solvent can be used alone, or two or more can be used in combination. Furthermore, the content of the organic solvent relative to the total mass of the white 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 keeping the content of the organic solvent within the above range, a better balance between wetting and spreading properties and drying properties is achieved, making it easier to form high-quality images.

[0089] Furthermore, the white ink composition more preferably contains an organic solvent among the organic solvents exemplified above, with a standard boiling point of 150.0°C or higher and 280.0°C or lower. This allows for faster drying and fixing of the desired image.

[0090] Furthermore, the white ink composition more preferably does not contain more than 1.0% by mass of a polyol-based organic solvent with a standard boiling point exceeding 280.0°C. The content of polyol-based organic solvents with a standard boiling point exceeding 280°C in the white ink composition relative to the total mass of the white ink composition is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 1% by mass or less, particularly preferably 0.5% by mass or less, and even more particularly preferably 0.1% by mass or less. The lower limit of the content of polyol-based organic solvents with a standard boiling point exceeding 280°C can also be 0% by mass.

[0091] This results in better drying of the image, enabling faster recording and improved adhesion to the recording medium. Furthermore, the white ink composition preferably uses an organic solvent (not limited to polyols) with a standard boiling point exceeding 280.0°C within the aforementioned range. Examples of organic solvents with a standard boiling point exceeding 280°C include glycerol and polyethylene glycol monomethyl ether.

[0092] (surfactant)

[0093] White ink compositions may contain surfactants. Surfactants have functions such as adjusting the surface tension of the white ink composition and adjusting, for example, its wettability with recording media. Among surfactants, acetylenic diol surfactants, silicone surfactants, and fluorinated surfactants are preferred, for example.

[0094] As an alkynyl diol surfactant, there are no particular limitations; examples 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, DF110D (all trade names, manufactured by Air Products & Chemicals); Olfine 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 Industries, Ltd.); Acetylenol E00, E00P, E40, E100 (all trade names, manufactured by Kawaken Fine Chemicals Co., Ltd.).

[0095] There are no particular limitations on the silicone-based surfactant, but polysiloxane-based compounds are preferred. There are no particular limitations on the polysiloxane-based compound; for example, polyether-modified organosiloxanes can be cited. Commercially available examples of this polyether-modified organosiloxane include: BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-348 (trade names, manufactured by BYK Chemie 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 (trade names, manufactured by Shin-Etsu Chemical Industry Co., Ltd.); Silface SAG002, 005, 503A, 008 (the above are product names, manufactured by Nisshin Chemical Industry Co., Ltd.), etc.

[0096] As a fluorinated surfactant, fluorinated modified polymers are preferred. Specific examples include: BYK-3440 (manufactured by BYK Chemie Japan), Surflon S-241, S-242, S-243 (trade names, manufactured by AGC SeimiChemical), Ftergent 215M (manufactured by neos), etc.

[0097] When a white ink composition contains a surfactant, it may contain a variety of surfactants. The content of surfactant in the white ink composition relative to the total mass of the white ink composition can be set to 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.

[0098] (wax)

[0099] White ink compositions may contain wax. Wax provides lubrication to images formed from white ink compositions, thus reducing issues such as peeling.

[0100] As components of wax, various types of waxes can be used alone or in combination, such as plant and animal waxes like carnauba wax, candelilla wax, beeswax, rice bran wax, and lanolin; petroleum-based waxes like paraffin wax, microcrystalline wax, polyethylene wax, oxidized polyethylene wax, and petrolatum; mineral-based waxes like lignite wax and ceresin wax; synthetic waxes like carbon wax, Hoechst wax, polyolefin wax, and stearamide; and natural and synthetic wax emulsions or composite waxes like α-olefin-maleic anhydride copolymers. From the viewpoint of improving the fixing properties of the flexible packaging film described later, polyolefin waxes (especially polyethylene wax and polypropylene wax) and paraffin wax are preferred.

[0101] As a wax, commercially available products can also be used directly, such as: NopcotePEM-17 (trade name, manufactured by SanNopco Co., Ltd.), ChemipearlW4005 (trade name, manufactured by Mitsui Chemicals Co., Ltd.), AQUACER515, 539, 593 (the above are trade names, manufactured by BYK Chemie Japan Co., Ltd.), etc.

[0102] Furthermore, when the recording method includes a heating process, from the viewpoint of preventing the wax from melting excessively and reducing its performance, it is preferable to use a wax with a melting point of 50°C or higher and 200°C or lower, more preferably a melting point of 70°C or higher and 180°C or lower, and even more preferably a melting point of 90°C or higher and 150°C or lower.

[0103] The wax can be supplied in the form of an emulsion or a suspension. The wax content, calculated as solids relative to the total mass of the white ink composition, is 0.1% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 5% by mass or less, and even more preferably 0.5% by mass or more and 2% by mass or less. If the wax content is within the above range, the functions of the wax can be effectively performed. It should be noted that if one or both of the white ink composition and the non-white ink composition described later contain wax, sufficient lubrication of the image can be achieved.

[0104] (additive)

[0105] White ink compositions may contain ureas, amines, sugars, etc., as additives. Examples of ureas include: urea, ethylidene urea, tetramethylurea, thiourea, 1,3-dimethyl-2-imidazolinone, etc., and betaine derivatives (trimethylglycine, triethylglycine, tripropylglycine, triisopropylglycine, N,N,N-trimethylalanine, N,N,N-triethylalanine, N,N,N-triisopropylalanine, N,N,N-trimethylmethylalanine, carnitine, acetylcarnitine, etc.).

[0106] Examples of amines include diethanolamine, triethanolamine, and triisopropanolamine. Ureas or amines can function as pH adjusters.

[0107] Examples of sugars include: glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol (sorbitol), maltose, cellobiose, lactose, sucrose, trehalose, and maltotriose.

[0108] (other)

[0109] The white ink composition used in the recording method according to this embodiment may also contain, as needed, preservatives, mildew inhibitors, rust inhibitors, chelating agents, viscosity modifiers, antioxidants, mildew inhibitors, and other components.

[0110] 1.1.3. Physical properties of the white ink composition

[0111] When the white ink composition is applied to the recording medium by inkjet printing, the viscosity of the white ink composition at 20°C is preferably 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. When the white ink composition is applied to the recording medium by inkjet printing, a predetermined image can be easily and efficiently formed on the recording medium.

[0112] From the viewpoint of achieving appropriate wetting and spreading properties on the recording medium, the surface tension of the white ink composition at 25°C is 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. Furthermore, the surface tension is preferably 20 mN / m or more, more preferably 25 mN / m or more.

[0113] It should be noted that the surface tension can be determined by confirming the surface tension when the composition wets a platinum plate at 25°C using an automatic surface tension meter CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.).

[0114] 1.1.4. Thickening rate of the white ink composition

[0115] The viscosity of the white ink composition increases more than fivefold when mixed with a 7% (w / w) aqueous solution of calcium formate at a mass ratio of 10:1. This thickening property allows for sufficient cohesion of the white ink composition components upon contact with the processing liquid, resulting in excellent image quality for both images formed from the white ink composition and those formed with non-white ink compositions used in conjunction. In particular, it reduces the thinning of fine lines used for text, etc.

[0116] Here, the increase in ink viscosity when mixed with a 7% by mass aqueous solution of calcium formate (test solution) is defined as "thickness increase rate" as follows. That is, the viscosity increase rate is the ratio (multiple) of the viscosity of the mixture after mixing with the ink used in the recording method at a mass ratio of 10:1 to the viscosity of the ink before mixing. Viscosity is measured at 20°C. Therefore, the viscosity increase rate is a multiple of the viscosity after mixing based on the viscosity before mixing. The viscosity increase rate is, for example, approximately 0.5 times or more and 10.0 times or less. It should be noted that, depending on the composition of the ink, sometimes the viscosity increase rate is less than 1.0 times, and the viscosity decreases, but this is still referred to as the viscosity increase rate. Viscosity can be measured using a rheometer.

[0117] The lower limit of the thickening rate of the white ink composition is 5 times or more, but more preferably more than 5 times, more preferably 5.5 times or more, even more preferably 6 times or more, particularly preferably 7 times or more. Even more preferably 10 times or more.

[0118] On the other hand, the upper limit of the viscosity increase rate of the white ink composition is not limited, but it is preferably 20 times or less, more preferably 10 times or less, more preferably 9 times or less, more preferably 8.5 times or less, and even more preferably 8 times or less. When the viscosity increase rate of the white ink composition is within the above range, the image quality, crack resistance, abrasion resistance, and ejection stability are superior, which is preferred. In addition, the image quality of the non-white ink composition used together is also excellent, especially in reducing the thinning of fine lines used for text, etc. Furthermore, even when the ink adhesion is high, the image quality is excellent, thus enabling an increase in ink adhesion and excellent background concealment of white images.

[0119] The viscosity increase of the white ink composition can be adjusted primarily by modifying the type and content of the white pigment (including the resin dispersant) or resin particles. In particular, adjustments made by modifying the type and content of the white pigment (including the resin dispersant) are easy to make and preferred.

[0120] 1.1.5. Method for adhering a white ink composition to a recording medium

[0121] The white ink application process can be performed in any manner, as long as the inkjet head scans the recording medium while the white ink composition is applied. For example, it is preferable to use an inkjet head as the inkjet head and eject the white ink composition from the inkjet head. This allows for efficient, low-volume, multi-variety printing with a small device.

[0122] The preferred amount of white ink composition applied in the white ink application process is 5.0 mg / 645.16 mm. 2 The above. Further, preferably 7.0 mg / 645.16 mm. 2 The preferred value is 9.0 mg / 645.16 mm. 2 The above, more preferably 10.0 mg / 645.16 mm 2 The above is further preferred to be 12.0 mg / 645.16 mm. 2 The above is further preferred to be 15.0 mg / 645.16 mm. 2 That's it. This way, we can obtain a white image with better embedding properties and better background concealment.

[0123] Furthermore, the preferred upper limit is 25.0 mg / 645.16 mm. 2 The following is more preferred: 20.0 mg / 645.16 mm 2 The following is a further preferred value: 15.0 mg / 645.16 mm. 2 the following.

[0124] In the recording method of this embodiment, the amount of white ink composition adhered is the amount of white ink composition and non-white ink composition adhered in overlapping areas. Alternatively, it is preferable to set the maximum amount of white ink composition adhered in this area to the range described above.

[0125] 1.2. Non-white ink adhesion process

[0126] The non-white ink adhesion process is the process of adhering a non-white ink composition to a recording medium. Methods for adhering to the recording medium will be described later.

[0127] The following is a description of the non-white ink composition.

[0128] 1.2.1. Non-white color materials

[0129] Non-white ink compositions are so-called colored inks that contain non-white colorants. The non-white colorants contained in a non-white ink composition refer to colorants other than the white colorants mentioned above. Examples of non-white colorants include dyes and pigments. Preferred non-white colorants are, for example, colored colorants such as cyan, yellow, magenta, and black.

[0130] The non-white colorant can be any of dyes and pigments, or a mixture thereof. However, among dyes and pigments, pigments are more preferably included. Pigments exhibit excellent storage stability in terms of lightfastness, weather resistance, and gas resistance; from this perspective, organic pigments are further preferred.

[0131] Specifically, the pigments used include insoluble azo pigments, condensed azo pigments, azo lakes, chelated azo pigments, phthalocyanine pigments, perylene and pyrene pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindolinone pigments, isoindolinone pigments, quinophthalone pigments, and other polycyclic pigments, dye chelates, dyeing lakes, nitro pigments, nitroso pigments, aniline black, daylight fluorescent pigments, carbon black, etc. One of these pigments can be used alone, or two or more can be used in combination. Furthermore, glossy pigments can also be used as non-white colorants.

[0132] There are no particular limitations on the specific examples of pigments; for example, the following pigments can be cited.

[0133] Examples of black pigments include: No. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, No. 2200B, etc. (manufactured by Mitsubishi Chemical Corporation); Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, etc. (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, etc. (cabot Corporation, Japan). (Made by KK); Pigment Black FW1, Pigment Black FW2, Pigment Black FW2V, Pigment Black FW18, Pigment Black FW200, Pigment Black S150, Pigment Black S160, Pigment Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, Special Black 5, Special Black 4A, Special Black 4 (all made by Degussa).

[0134] 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, 180.

[0135] 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, or CI Pigment Violet 19, 23, 32, 33, 36, 38, 43, 50.

[0136] Examples of cyan pigments include: CI Pigment Blue 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:34, 15:4, 16, 18, 22, 25, 60, 65, 66; CI Vat Blue 4, 60.

[0137] In addition, there are no special restrictions on pigments other than magenta, cyan, and yellow. For example, CI pigments green 7 and 10, CI pigment brown 3, 5, 25, 26, CI pigment orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63 can be listed.

[0138] As for pearlescent pigments, there are no particular limitations. Examples include titanium dioxide coated with mica, fish scale foil, bismuth oxychloride, and other pigments that have a pearly or interference luster.

[0139] As a metallic pigment, there are no particular limitations. Examples include particles composed of elements or alloys such as aluminum, silver, gold, platinum, nickel, chromium, tin, zinc, indium, titanium, and copper.

[0140] In addition, as dyes, various dyes commonly used in inkjet recording can be used, such as direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, disperse dyes, vat dyes, soluble vat dyes, and reactive disperse dyes.

[0141] Non-white pigments are preferably stable and dissolve in the dispersion medium, and may also be dispersed using a dispersant as needed. Examples of dispersants include those used to improve the dispersibility of the white pigment in the aforementioned white ink composition.

[0142] Non-white pigments can also be dispersed using a dispersant. A dispersant resin is preferred as the dispersant. The acid value of the dispersant resin for non-white pigments can be the same as that of the dispersant resin for white pigments, and is particularly preferably 30 mg KOH / g or higher. The acid value of the dispersant resin for non-white pigments is preferably higher than that of the dispersant resin for white pigments, more preferably 5 mg KOH / g or higher, and even more preferably 10 to 30 mg KOH / g higher. In this case, image quality is superior, and therefore preferred.

[0143] The content of non-white pigment relative to the total mass of the non-white ink composition is preferably 0.3% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 15% by mass or less. Further, it is preferably 1% by mass or more and 10% by mass or less, more preferably 2% by mass or more and 7% by mass or less.

[0144] When using pigments in non-white pigments, the volume average particle size of the pigment particles is preferably 10 nm or more and 300 nm or less, more preferably 30 nm or more and 250 nm or less, even more preferably 50 nm or more and 250 nm or less, and particularly preferably 70 nm or more and 200 nm or less. Further, it is preferably 80 nm or more and 150 nm or less. The volume average particle size of the non-white pigment is determined as an initial state using the aforementioned method for confirming the volume average particle size. When the volume average particle size is within the above range, it is preferable in that it is easy to obtain the desired pigment and to easily improve the properties of the pigment.

[0145] 1.2.2. Other ingredients

[0146] Non-white ink compositions may contain, in addition to non-white colorants, water, resin particles, organic solvents, surfactants, waxes, additives, resin dispersants, preservatives, mildew inhibitors, rust inhibitors, chelating agents, viscosity modifiers, antioxidants, and mildew inhibitors.

[0147] The components of the non-white ink composition, excluding the colorant, are the same as those in the white ink composition and can be selected independently of the white ink composition. These components can all be the same as those in the white ink composition described above; detailed explanation is omitted by replacing "white ink composition" with "non-white ink composition".

[0148] The non-white ink composition is more preferably a water-based ink, and even more preferably a water-based resin ink, just like the white ink composition. This allows for recording with reduced environmental impact and less odor.

[0149] Furthermore, the non-white ink composition, like the white ink composition, preferably contains an organic solvent with a standard boiling point of 150.0°C or higher and 280.0°C or lower. This allows for faster image fixing and recording.

[0150] Furthermore, the non-white ink composition, like the white ink composition, preferably does not contain more than 1.0% by mass of an organic solvent with a standard boiling point exceeding 280.0°C. This allows for faster image drying and recording, and also promises improved image adhesion.

[0151] 1.2.3. Tickling rate of non-white ink compositions

[0152] More preferably, the viscosity of the non-white ink composition increases by more than five times when mixed with a 7% (w / w) aqueous solution of calcium formate at a mass ratio of 10:1. This thickening property allows for sufficient cohesion of the components of the non-white ink composition upon contact with the processing liquid, thereby improving the image quality of images formed from the non-white ink composition, particularly reducing the thinning of fine lines used for text, etc. The thickening rate is defined in the same way as for the white ink composition described above.

[0153] The thickening rate of the non-white ink composition is preferably 5 times or more, more preferably over 5 times, more preferably 5.5 times or more, even more preferably 6 times or more, particularly preferably 7 times or more. Further, it is preferably 10 times or more.

[0154] On the other hand, the upper limit of the viscosity increase rate of the non-white ink composition is not limited, but it is preferably 20 times or less, further preferably 10 times or less, more preferably 9 times or less, even more preferably 8.5 times or less, and even more preferably 8 times or less. When the viscosity increase rate of the non-white ink composition is within the above range, the image quality, crack resistance, abrasion resistance, and spraying stability are superior, which is preferred.

[0155] The viscosity increase of non-white ink compositions can be mainly adjusted by modifying the type and content of pigments (including resin dispersants) and resin particles. The viscosity and surface tension of non-white ink compositions are the same as those of white ink compositions, therefore descriptions are omitted.

[0156] 1.2.4. Method for adhering a non-white ink composition to a recording medium

[0157] The non-white ink adhesion process can be performed in any manner, as long as the inkjet head scans the recording medium while the non-white ink composition is adhered. However, it is more preferable to use an inkjet head as the inkjet head and eject the non-white ink composition from the inkjet head. This allows for efficient, low-volume, multi-variety printing with a small device.

[0158] The preferred adhesion amount of the non-white ink composition in the non-white ink adhesion process is 3.0 mg / 645.16 mm. 2 The above, more preferably 5.0 mg / 645.16 mm 2 The above is further preferred to be 6.0 mg / 645.16 mm. 2 That's all. This allows for the production of non-white images with better color rendering. Furthermore, the upper limit is preferably 15.0 mg / 645.16 mm. 2 The following is more preferably 10.0 mg / 645.16 mm 2 The following is a further preferred value: 7.0 mg / 645.16 mm. 2 the following.

[0159] In the recording method of this embodiment, the amount of non-white ink composition adhered is the amount of adhesion in the recording area where the white ink composition and the non-white ink composition are adhered in an overlapping manner. Alternatively, it is preferable to set the maximum amount of non-white ink composition adhered in this area to the range described above.

[0160] Furthermore, more preferably, the maximum amount of white ink composition adhered in the white ink adhesion process is greater than the maximum amount of non-white ink composition adhered in the non-white ink adhesion process. This allows for recording with better background concealment.

[0161] 1.3. First treatment liquid adhesion process

[0162] The first processing liquid adhesion step is a step that follows the white ink adhesion step, in which a processing liquid containing a coagulant is adhered to the recording medium. The processing liquid will be explained below. The method of adhesion to the recording medium will be described later.

[0163] 1.3.1. Treatment fluid

[0164] The treatment fluid contains a coagulant.

[0165] 1.3.1.1. Coagulants

[0166] The processing solution contains a coagulant that causes the components of inks (white ink compositions and non-white ink compositions) to agglomerate. The coagulant has the function of causing pigments or resin particles contained in the ink to agglomerate by reacting with them. However, the degree of agglomeration of pigments or resin particles caused by the coagulant varies depending on the type of coagulant, pigment, and resin particles, and can be adjusted. Furthermore, the coagulant can cause pigments and resin particles to agglomerate by reacting with them. Through such agglomeration, for example, the color development of pigments can be improved, the fixing properties of resin particles can be improved, and / or the viscosity of the ink can be increased.

[0167] The coagulant is not particularly limited and can include metal salts, inorganic acids, organic acids, cationic compounds, etc. As a cationic compound, cationic resins (cationic polymers), cationic surfactants, etc., can be used. Among these, polyvalent metal salts are preferred as metal salts, and cationic resins are preferred as cationic compounds. Therefore, as a coagulant, cationic resins, organic acids, and polyvalent metal salts are preferred in terms of particularly superior image quality, abrasion resistance, and gloss.

[0168] As a metal salt, a polyvalent metal salt is preferred, but metal salts other than polyvalent metal salts can also be used. Among these coagulants, at least one selected from metal salts and organic acids is preferred due to its excellent reactivity with the components contained in the ink. Furthermore, among cationic compounds, cationic resins are preferred due to their easy solubility in the processing liquid. In addition, multiple coagulants can be used in combination.

[0169] Polyvalent metal salts are compounds composed of divalent or higher metal ions and anions. Examples of divalent or higher metal ions include ions of calcium, magnesium, copper, nickel, zinc, barium, aluminum, titanium, strontium, chromium, cobalt, and iron. Among these metal ions constituting polyvalent metal salts, calcium ions and magnesium ions are preferred from the perspective of excellent cohesiveness of ink components.

[0170] The anions constituting polyvalent metal salts are either inorganic or organic ions. That is, the polyvalent metal salts in this invention refer to salts composed of inorganic or organic ions and polyvalent metals. Examples of such inorganic ions include chloride ions, bromide ions, iodide ions, nitrate ions, sulfate ions, and hydroxide ions. Examples of such organic ions include organic acid ions, such as carboxylic acid ions.

[0171] It should be noted that the polyvalent metal compound is preferably an ionic polyvalent metal salt, especially when the polyvalent metal salt is a magnesium salt or a calcium salt, the stability of the treatment solution is further improved. Furthermore, the counter ion of the polyvalent metal can be any of inorganic acid ions or organic acid ions.

[0172] Specific examples of the aforementioned polyvalent metal salts 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, aluminum acetate, etc. These polyvalent metal salts can be used alone or in combination of two or more. Among them, calcium formate, magnesium sulfate, calcium nitrate, and calcium chloride are preferred because they ensure sufficient solubility in water and reduce the residue of the treatment solution (the residue is not obvious), and calcium formate and calcium nitrate are more preferred. It should be noted that these metal salts can also have hydrated water in their raw material form.

[0173] As metal salts other than polyvalent metal salts, monovalent metal salts such as sodium salts and potassium salts can be listed, for example, sodium sulfate and potassium sulfate.

[0174] Examples of preferred 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, phosphoric acid, pyrrolidone carboxylic acid, pyranone carboxylic acid, pyrrolic carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, or derivatives of these compounds, or their salts. An organic acid may be used alone or in combination with two or more. Salts of organic acids that are metal salts are included in the aforementioned metal salts.

[0175] Examples of inorganic acids include sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid. Inorganic acids can be used alone or in combination with two or more.

[0176] Examples of cationic resins (cationic polymers) include: cationic urethane resins, cationic olefin resins, cationic amine resins, and cationic surfactants. Water-soluble cationic polymers are preferred.

[0177] As cationic urethane resins, commercially available products can be used, such as Hydron CP-7010, CP-7020, CP-7030, CP-7040, CP-7050, CP-7060, CP-7610 (trade name, manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.), Superflex 600, 610, 620, 630, 640, 650 (trade name, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.), and polyurethane emulsions WBR-2120C and WBR-2122C (trade name, manufactured by Taisei Fine Chemical Co., Ltd.).

[0178] Cationic olefin resins are resins containing olefins such as ethylene and propylene in their structural backbone, and known resins can be appropriately selected and used. Furthermore, cationic olefin resins can also be in an emulsion state dispersed in a solvent containing water and / or organic solvents. Commercially available products can be used as cationic olefin resins, such as ArrowBaseCB-1200 and CD-1200 (trade name, manufactured by Uniqlo Co., Ltd.).

[0179] As cationic amine resins (cationic polymers), any resin containing amino groups in its structure is acceptable, and well-known resins can be appropriately selected. Examples include polyamine resins, polyamide resins, and polyallylamine resins. Polyamine resins are resins containing amino groups in their main structure. Polyamide resins are resins containing amide groups in their main structure. Polyallylamine resins are resins with a structure derived from allyl groups in their main structure.

[0180] In addition, examples of cationic polyamine resins include: Unisense KHE103L (hexamethylenediamine / epimyl chloride resin, 1% aqueous solution with pH approximately 5.0, viscosity 20–50 mPa·s, and solids concentration of 50% by mass) and Unisense KHE 104L (dimethylamine / epimyl chloride resin, 1% aqueous solution with pH approximately 7.0, viscosity 1–10 mPa·s, and solids concentration of 20% by mass) manufactured by Senka Co., Ltd. Furthermore, specific examples of commercially available cationic polyamine resins include: FL-14 (trade name, manufactured by SNF Corporation), Arafix 100, 251S, 255, 255LOX (manufactured by Arakawa Chemical Co., Ltd.), DK-6810, 6853, 6885; WS-4010, 4011, 4020, 4024, 4027, 4030 (manufactured by Starlight PMC Co., Ltd.), Papyogen P-105 (trade name, 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 Company).

[0181] As a polyamine resin, polyallylamine resin can also be cited. Examples of polyallylamine resins 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, diallyl methyl ethyl ammonium ethyl sulfate-sulfur dioxide copolymer, methyl diallylamine hydrochloride-sulfur dioxide copolymer, diallyldimethylammonium chloride-sulfur dioxide copolymer, diallyldimethylammonium chloride-acrylamide copolymer, etc.

[0182] Examples of cationic surfactants include: primary amine, secondary amine and tertiary amine salts, alkylamine salts, dialkylamine salts, aliphatic amine salts, benzyl alkylammonium salts, quaternary ammonium salts, alkyl quaternary ammonium salts, alkylpyridinium salts, sulfonium salts, onium salts, imidazoline onium salts, etc.

[0183] A variety of these coagulants can be used. In addition, if at least one of polyvalent metal salts, organic acids, and cationic resins is selected among these coagulants, the coagulation effect is better, thus enabling the formation of images with higher image quality (especially good color reproduction).

[0184] The total content of the coagulant in the treatment solution is, for example, 0.1% by mass or more and 20% by mass or less relative to the total mass of the treatment solution, preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less. It should be noted that when the coagulant is shared by both the solution and the dispersion, the content as a solid component is also preferably within the above range. If the coagulant content is 1% by mass or more, the ability of the coagulant to coagulate the components contained in the ink can be sufficiently obtained. Furthermore, by keeping the coagulant content at 30% by mass or less, the solubility and dispersibility of the coagulant in the treatment solution are better, and the storage stability of the treatment solution can be improved.

[0185] Based on the fact that the coagulant has good solubility in the treatment solution even when the organic solvent contained in the treatment solution is highly hydrophobic, it is preferable to use a coagulant with a solubility of 1g or more relative to 100g of water at 25°C, and more preferably a coagulant with a solubility of 3g or more and 80g or less.

[0186] 1.3.1. 2. Other ingredients

[0187] Provided it does not impair functionality, the treatment fluid may contain resin particles, water-soluble organic solvents, surfactants, water, waxes, additives, resin dispersants, and preservatives in addition to coagulants. The ingredients include mildew inhibitors, rust inhibitors, chelating agents, viscosity modifiers, antioxidants, and so on. These ingredients are the same as those in the white ink composition described above, therefore detailed descriptions are omitted.

[0188] 1.3.2. Physical properties of the treatment solution

[0189] From the viewpoint of ensuring appropriate wetting and spreading properties to the recording medium, the surface tension of the processing liquid used in the recording method of this embodiment is 40 mN / m or less at 25°C, preferably 38 mN / m or less, more preferably 35 mN / m or less, and even more preferably 30 mN / m or less. It should be noted that the surface tension can be measured using an automatic surface tension meter CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) and by confirming the surface tension when the composition wets a platinum plate at 25°C.

[0190] The processing fluid is more preferably adhered to the recording medium by inkjet printing. In this case, the viscosity at 20°C is preferably 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. When the processing fluid is adhered to the recording medium by inkjet printing, the predetermined processing fluid adhesion area can be easily and efficiently formed on the recording medium.

[0191] 1.3.3. Method for adhering the processing fluid to the recording medium

[0192] As a method for attaching the processing liquid to the recording medium, any of the following non-contact and contact methods, or combinations thereof, can be used: inkjet printing, coating with rollers or rods, applying the processing liquid to the recording medium using various sprayers, immersing the recording medium in the processing liquid for coating, or applying the processing liquid to the recording medium using a brush. Among these, inkjet printing is preferred.

[0193] The mechanism used to adhere processing liquid or ink to the recording medium is called an adhesion mechanism. This mechanism performs the adhesion methods described above. Such mechanisms include rollers, inkjet heads, sprayers, brushes, etc.

[0194] The first processing liquid adhesion step is performed concurrently with the white ink adhesion step. Here, "concurrently performed" means that the adhesion of the processing liquid from the first processing liquid adhesion step to the recording medium occurs before or simultaneously with the application of the white ink composition to the recording medium by the white ink adhesion step. That is, the application of white ink to the recording medium based on the white ink adhesion step occurs either after the processing liquid is applied to the recording medium or simultaneously with the application of the processing liquid to the recording medium. Furthermore, as a method for applying white ink to the recording medium based on the white ink adhesion step simultaneously with the application of the processing liquid to the recording medium, an example is the method of applying the processing liquid to the same scan area as the scan (process) in which the white ink composition is applied to the recording medium. This also includes the concept of applying the processing liquid and the white ink composition to the recording medium in a "single-pass" manner in the recording apparatus described later.

[0195] For example, in the case of a processing liquid adhesion process performed by inkjet printing, the first processing liquid adhesion process can be performed in the same scan as the white ink adhesion process, and the second processing liquid adhesion process can be performed in the same scan as the non-white ink adhesion process.

[0196] In addition, "accompanying execution" also means that the white ink composition that is attached to the recording medium by the white ink attachment process and the processing liquid that is attached to the recording medium by the first processing liquid attachment process can come into contact and react on the recording medium.

[0197] 1.4. Second treatment liquid adhesion process

[0198] The second processing liquid adhesion step is a process that follows the non-white ink adhesion step to adhere a processing liquid containing a coagulant to the recording medium. Regarding the processing liquid, since it is the same as the processing liquid used in the first processing liquid adhesion step described above, its description is omitted. It should be noted that the processing liquid used in the second processing liquid adhesion step may be the same as or different from the processing liquid used in the first processing liquid adhesion step.

[0199] The attachment mechanism used in the second treatment liquid attachment process can be the same mechanism used in the first treatment liquid attachment process, or it can be a different mechanism. That is to say, the same attachment mechanism can be used for both the first and second treatment liquid attachment processes.

[0200] The properties of the treatment liquid used in the second treatment liquid adhesion step and the method for adhering it to the recording medium are the same as those of the treatment liquid used in the first treatment liquid adhesion step. It should be noted that the second treatment liquid adhesion step is performed following the non-white ink adhesion step. Regarding this following execution, it is the same as the first treatment liquid adhesion step described above. It should be noted that the second treatment liquid adhesion step is performed after the white ink adhesion step.

[0201] Alternatively, the surface tension of the treatment liquid used in each treatment liquid adhesion process can be made lower than that of the non-white ink composition, and the surface tension of the non-white ink composition can be made lower than that of the white ink composition. This facilitates the wetting and spreading of the treatment liquid on the substrate, and also facilitates the wetting and spreading of the white ink on it, thus improving filling and pinholes. Furthermore, since the non-white ink composition weeps and spreads more easily than the white ink composition, it is easier to form a non-white image on a white image.

[0202] 1.5. Adhesion amount in each process

[0203] In the recording method of this embodiment, the amount of processing liquid applied in the second processing liquid application step is less than the amount of processing liquid applied in the first processing liquid application step. If the amount of processing liquid applied in the second processing liquid application step is too large, excessive aggregation of the components of the non-white ink composition occurs, sometimes resulting in thinning of lines in the image. Furthermore, some processing liquid remains after the application of the white ink composition in the second processing liquid application step. Therefore, by reducing the amount of processing liquid applied in the second processing liquid application step, excessive aggregation of the components of the non-white ink composition is suppressed, thus reducing line thinning in the image and suppressing uneven ink bleeding.

[0204] It should be noted that the amount of treatment liquid adhered in the first treatment liquid adhesion process and the amount of treatment liquid adhered in the second treatment liquid adhesion process are the amounts of treatment liquid adhered in the same recording area where the first treatment liquid adhesion process and the second treatment liquid adhesion process are performed.

[0205] The preferred amount of treatment liquid in the first treatment liquid adhesion step is 0.1 mg / 645.16 mm. 2 Above 4.0mg / 645.16mm 2 The following is a further preferred formulation: 0.5 mg / 645.16 mm. 2 Above 3.0mg / 645.16mm 2 The following is more preferred: 0.4 mg / 645.16 mm 2 Above 2.5mg / 645.16mm 2 The following is a further preferred value: 0.5 mg / 645.16 mm. 2 Above and 2.0mg / 645.16mm 2 The following is a further preferred value: 0.8 mg / 645.16 mm. 2 Above and 1.5mg / 645.16mm 2It should be noted that the maximum amount of processing liquid applied in the first processing liquid application step can also be set within the range described above. This allows for maintaining a very high image quality for images formed from white ink compositions and further reduces uneven color bleeding and thinning of fine lines in images formed from non-white ink compositions.

[0206] Furthermore, the preferred amount of treatment liquid in the second treatment liquid adhesion step is 2.5 mg / 645.16 mm. 2 The following is more preferably 0.05 mg / 645.16 mm 2 Above and 2.3mg / 645.16mm 2 The following is more preferably 0.1 mg / 645.16 mm. 2 Above and 2.2mg / 645.16mm 2 The following is a further, more preferably, formulation 0.2 mg / 645.16 mm. 2 Above and 2.0mg / 645.16mm 2 The following is a further preferred value: 0.4 mg / 645.16 mm. 2 Above and 1.5mg / 645.16mm 2 The following is a further preferred value: 0.5 mg / 645.16 mm. 2 Above and 1.0mg / 645.16mm 2 It should be noted that the maximum amount of processing liquid applied in the second processing liquid application step can also be set within the range described above. This further reduces uneven bleeding and thinning of fine lines in images formed from non-white ink compositions.

[0207] Furthermore, the total amount of treatment liquid adhered in the first treatment liquid adhesion step and the treatment liquid adhered in the second treatment liquid adhesion step is preferably 4.0 mg / 645.16 mm. 2 The following is more preferably 0.1 mg / 645.16 mm. 2 Above 3.8mg / 645.16mm 2 The following is a further, more preferably, formulation 0.5 mg / 645.16 mm. 2 Above 3.5mg / 645.16mm 2 The following is a further preferred value: 0.8 mg / 645.16 mm. 2 Above 2.5mg / 645.16mm 2 The following is a further preferred value: 1.0 mg / 645.16 mm. 2 Above and 2.0mg / 645.16mm 2The following is an explanation. In this way, the inadequacy of the filling properties of images formed by white ink compositions can be further suppressed, and the image quality of images formed by non-white ink compositions can be improved.

[0208] It should be noted that in the areas where white and non-white pigments are adhered, the amount of processing liquid adhering to the recording medium can be constant or vary depending on the location. In particular, the amount of processing liquid adhering can vary depending on the location based on the amount of non-white ink composition adhering. However, in the recording method of this embodiment, at any location (recording area) where recording is performed, the amount of processing liquid adhering in the second processing liquid adhering step in the same recording area is less than the amount of processing liquid adhering in the first processing liquid adhering step.

[0209] For example, even in the recording area where the amount of processing liquid adhered in the second processing liquid adhesion step is the maximum amount, it is recorded that the amount of processing liquid adhered in the second processing liquid adhesion step is smaller than the amount of processing liquid adhered in the first processing liquid adhesion step. Furthermore, even in the recording area where the amount of processing liquid adhered in the second processing liquid adhesion step is the maximum amount and the amount of processing liquid adhered in the first processing liquid adhesion step is the minimum amount, it is recorded that in the same recording area, the amount of processing liquid adhered in the second processing liquid adhesion step is smaller than the amount of processing liquid adhered in the first processing liquid adhesion step.

[0210] The ratio (by mass) of the amount of treatment liquid adhered in the second treatment liquid adhesion step to the amount of treatment liquid adhered in the first treatment liquid adhesion step is less than 1, preferably 0.1 or more and 0.9 or less, more preferably 0.2 or more and 0.5 or less, even more preferably 0.3 or more and 0.49 or less, and particularly preferably 0.4 or more and 0.47 or less. In this case, the image quality is superior, which is preferred.

[0211] 1.6. Mass of droplets in each process

[0212] When the first and second processing liquid adhesion steps are performed using an inkjet method, the mass of the multiple droplets of processing liquid in both steps is preferably 10 ng or less. More preferably, it is 7 ng or less. This allows for greater contact between the processing liquid and the ink on the recording medium.

[0213] From this perspective, the mass of the multiple droplets of the treatment liquid in the first treatment liquid attachment step and the second treatment liquid attachment step is more preferably 5 ng or less, further preferably 4 ng or less, and even more preferably 3 ng or less. Additionally, it is preferable to have 1 ng or more.

[0214] Here, the mass of the droplet refers to the mass of a single droplet ejected from the inkjet head. The mass of the droplet is also called the point mass of the droplet.

[0215] When the white ink adhesion process and the non-white ink adhesion process are performed together with the first treatment liquid adhesion process and the second treatment liquid adhesion process in a single scan, the timing at which the white ink composition, the non-white ink composition, and the treatment liquid land at the same location in the same area during a single scan may sometimes differ, but the time difference is very small. However, the order in which the white ink composition, the non-white ink composition, and the treatment liquid land at the same location in the same area during a single scan is not particularly limited.

[0216] When performing the recording method of this embodiment, recording can also be performed, as with the inkjet recording apparatus described later, by repeatedly performing a main scan of the inkjet head and a sub-scan that changes the relative position of the inkjet head and the recording medium in a direction intersecting the scanning direction. Recording can also be performed by alternately and repeatedly performing the main scan and the sub-scan. Furthermore, in the sub-scan following the main scan, the relative position between the inkjet head and the recording medium can be moved in the sub-scanning direction by a length shorter than the length of the inkjet head's nozzle array, and the area scanned in the previous main scan can be scanned in the subsequent main scan. In this case, the area where ink or processing liquid was adhered by the inkjet head's nozzle array in one scan is re-adhered to by the inkjet head's nozzle array in another scan. That is, the inkjet head's nozzle array can be aligned again with the area of ​​the recording medium that was aligned with the inkjet head's nozzle array in one scan in another scan.

[0217] Sub-scanning can be performed by moving the recording medium relative to the inkjet head, or by moving the inkjet head relative to the recording medium.

[0218] Thus, in the recording, there can be areas on the recording medium where an area coated with ink or processing liquid by a single scan of the inkjet head is then coated with the same ink or processing liquid again by a subsequent scan. In other words, there can also be areas where the same area is scanned more than once. It should be noted that the number of times the same area is scanned is called the number of scans (scan count, pass count). The number of scans is the amount of ink per scan.

[0219] The number of scans is 1 or more, preferably 2 or more, and more preferably 4 or more. While not limited, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. Further, it is preferably 4 or less, and more preferably 2 or less.

[0220] When the number of scans exceeds the above-mentioned range, the reduction in uneven density and the decrease in image quality are superior and preferred. When the number of scans is below the above-mentioned range, the printing speed is superior and preferred.

[0221] The number of scans depends on the configuration of the recording device, but it can be calculated as follows: The number of scans is obtained by dividing the length of the sub-scanning direction of the inkjet head by the distance of one sub-scan in the sub-scanning direction of the recording medium.

[0222] In this embodiment, when scanning as described above, the recording method appropriately configures the nozzles of the inkjet head that eject the white ink composition, the nozzles that eject the non-white ink composition, and the nozzles that eject the processing liquid to control the ejection, thereby enabling the formation of an area in the recording area of ​​the recording medium in a single main scan where the white ink composition lands before the non-white ink composition.

[0223] 1.7. Other processes

[0224] The recording method of this embodiment includes a step of adhering a processing liquid, a white ink composition, and a non-white ink composition to a recording medium, respectively. However, it may also include a step of further adhering one or more of the processing liquid, white ink composition, and non-white ink composition to the recording medium, as needed. Moreover, there is no limitation on the order or number of these steps, and they can be performed as appropriate as needed. In addition, the processing liquid and ink are preferably adhered to the same area on the recording medium.

[0225] The recording method of this embodiment may include a drying step (primary heating step) to dry the liquid adhering to the recording medium and / or a heating step (post-heating step), etc.

[0226] 1.7.1. Drying process

[0227] The recording method of this embodiment may include a drying step (a single heating step). The recording method of this embodiment may include a step of drying the recording medium before or during the application of the processing liquid or ink composition. The drying step can be performed not only by stopping recording and placing the medium, but also by using a drying mechanism. Examples of using a drying mechanism include methods that supply air at room temperature or warm air to the recording medium (air-supply type), methods that irradiate the recording medium with radiation (infrared rays, etc.) to generate heat (radiation type), components that contact the recording medium and transfer heat to it (conductive type), and combinations of two or more of these methods. In the case of a drying step, an air-supply type is more preferred.

[0228] The use of a drying mechanism that heats the recording medium in a drying process (primary drying process) is specifically referred to as a heating process (primary heating process). For example, a drying process using room temperature air supply in the aforementioned drying mechanism does not constitute a heating process.

[0229] The surface temperature of the recording medium when the processing liquid or ink composition is applied is preferably 45°C or lower, more preferably 20°C or higher and 45°C or lower. Furthermore, it is preferably 27.0°C or higher and 40°C or lower, more preferably 28°C or higher and 30°C or lower. This temperature is the surface temperature of the portion of the recording surface of the recording medium to which the liquid is applied during the application process, and is the highest temperature of the application process in the recording area. When the surface temperature is within the above-mentioned range, it is more preferable in terms of image quality, abrasion resistance, and reduced clogging.

[0230] The drying process can be performed simultaneously with one or more of the aforementioned processing liquid adhesion process and ink adhesion process. When the drying process and ink adhesion process are performed simultaneously, the surface temperature of the recording medium is preferably set to 30°C or below, more preferably to 28°C or below.

[0231] When the drying process of the recording medium is performed before or during the processing liquid application process, the surface temperature of the recording medium at the moment the processing liquid is applied to the recording medium is 30.0°C or higher, preferably 35.0°C or higher, and more preferably 40.0°C or higher. This makes it easier to form a film of the processing liquid, especially when the processing liquid contains resin particles, thus potentially further improving the adhesion and abrasion resistance of the resulting image.

[0232] Furthermore, each adhesion process can be completed without a heating step. This allows for better spraying stability of the inks and other materials. Also, each adhesion process can be completed without a drying step.

[0233] 1.7.2. Post-heating process

[0234] The recording method according to this embodiment may include a post-heating step after each of the above-described attachment steps, wherein the recording medium is heated. The post-heating step may be performed using a suitable heating means, for example. The post-heating step may be performed using a post-heater (equivalent to heater 5 in the example of the inkjet recording apparatus described later). Furthermore, the heating means are not limited to those found in inkjet recording apparatuses; other drying means may also be used. This allows the obtained image to dry more thoroughly and be more fully fixed, thus enabling the recorded material to be used at an earlier stage.

[0235] In this case, the temperature of the recording medium is not particularly limited, and can be set based on factors such as the Tg of the resin component constituting the resin particles contained in the recording. Taking into account the Tg of the resin component constituting the resin particles or wax, it can be set to be 5.0°C or more higher than the Tg of the resin component constituting the resin particles, preferably 10.0°C or more.

[0236] The surface temperature of the recording medium reached by the post-heating process is 30.0°C or higher and 120.0°C or lower, preferably 40.0°C or higher and 100.0°C or lower, more preferably 50.0°C or higher and 95°C or lower, and even more preferably 70°C or higher and 90°C or lower. The surface temperature of the recording medium reached by the post-heating process is particularly preferably 80°C or higher. If the temperature of the recording medium is within this range, it is possible to form a film or planarize the resin particles or wax contained in the recording, and to dry and fix the resulting image more thoroughly.

[0237] 1.8. Effects

[0238] According to the recording method of this embodiment, the processing liquid is applied not only in the first processing liquid application step accompanying the application of the white ink composition, but also in the second processing liquid application step accompanying the application of the non-white ink composition. Therefore, the image quality of the image formed by the white ink composition can be improved, and uneven color bleeding of the image formed by the non-white ink composition can be suppressed.

[0239] Furthermore, since the amount of processing liquid applied in the second processing liquid application step is smaller than that in the first processing liquid application step, the amount of processing liquid applied in the second processing liquid application step will not be excessive relative to the amount used to coagulate the components of the non-white ink composition. Therefore, the coagulation of the components of the non-white ink composition will not be excessive, thus suppressing the thinning of lines in the image formed by the non-white ink composition.

[0240] 1.9. Recording Media

[0241] The recording medium used to form an image using the recording method according to this embodiment may or may not have an ink-absorbing recording surface. Therefore, there are no particular limitations on the recording medium, and examples include liquid-absorbing recording media such as paper, film, and cloth; liquid-low-absorbent recording media such as printing paper; and liquid-non-absorbent recording media such as metal, glass, and polymer.

[0242] Recording media with low or no liquid absorption are those that have the property of being completely non-absorbent or almost non-absorbent of ink. Quantitatively, recording media with low or no liquid absorption are defined as those that, in the Bristol process, from the start of contact to 30 msec… 1 / 2 The water absorption rate up to this point is 10 mL / m 2 The following is a description of the recording medium. The Bristol method is the most widely used method for determining liquid absorption over a short period of time and is being adopted by the Japan Pulp and Paper Technology Association (JAPAN TAPPI). Details of the test method are described in Standard No. 51 "Paper and Board - Liquid Absorption Test Method - Bristol Method" of "JAPAN TAPPI Pulp and Paper Test Methods 2000 Edition". In contrast, liquid-absorbent recording media refers to recording media that do not conform to liquid-non-absorbent or low-absorbent recording media. It should be noted that in this specification, low-absorbent and liquid-non-absorbent are sometimes simply referred to as low-absorbent and non-absorbent.

[0243] Examples of non-absorbent liquid recording media include recording media coated with plastic on a paper substrate, recording media with a plastic film bonded to a paper substrate, and plastic films without an absorbent layer (acceptor layer). Examples of plastics mentioned here include polyvinyl chloride, polyethylene terephthalate, polycarbonate, polystyrene, polyurethane, polyethylene, and polypropylene.

[0244] Furthermore, recording media with low liquid absorption can be exemplified by having a coating layer with low liquid absorption on its surface. For example, a recording medium known as coated paper. Examples of printing papers such as art paper, coated paper, and matte paper can be used as recording media with a paper substrate. In the case of a plastic film substrate, examples include recording media made by coating polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, polystyrene, polyurethane, polyethylene, and polypropylene onto their surfaces, and recording media made by coating particles such as silica and titanium together with an adhesive.

[0245] Liquid-absorbing recording media can also be used as recording media. Liquid-absorbing recording media refers to the aforementioned medium described as being suitable for use in the Bristol method from the start of contact to 30 msec. 1 / 2 The water absorption rate up to 10 mL / m 2 "Recording medium".

[0246] As a liquid-absorbing recording medium, examples include recording media that become liquid-absorbing recording media by providing a liquid-absorbing receiving layer on the surface of the recording medium. For example, inkjet paper (inkjet-specific paper) can be cited. As the liquid-absorbing receiving layer, examples include layers composed of liquid-absorbing resins, liquid-absorbing inorganic particles, etc.

[0247] As a liquid-absorbing recording medium, another example is a recording medium whose substrate itself is liquid-absorbing. Examples include fabrics made of fibers and paper made of pulp. Examples of paper include ordinary paper, thick paper, and coated paper. Coated paper can be made from kraft pulp, waste paper, etc.

[0248] 2. Inkjet recording device

[0249] The recording apparatus according to this embodiment includes: an attachment mechanism for performing the above-described white ink attachment process, an attachment mechanism for performing the above-described non-white ink attachment process, an attachment mechanism for performing the above-described first processing liquid attachment process, and an attachment mechanism for performing the above-described second processing liquid attachment process, wherein the recording apparatus performs any one of the above-described recording methods.

[0250] Hereinafter, an example of an inkjet recording apparatus capable of implementing the recording method according to this embodiment will be described with reference to the accompanying drawings.

[0251] Figure 1 This is a schematic cross-sectional view of an inkjet recording device. Figure 2 It is shown Figure 1 A perspective view of an example of the configuration of the carriage periphery of an inkjet recording device 1. Figure 1 , 2 As shown, the inkjet recording device 1 includes an inkjet head 2, an IR heater 3, a pressure plate heater 4, a heater 5, a cooling fan 6, a preheater 7, an air supply fan 8, a carriage 9, a pressure plate 11, a carriage moving mechanism 13, a transport device 14, and a control unit CONT. The inkjet recording device 1... Figure 2 The control unit CONT shown controls the overall operation of the inkjet recording device 1.

[0252] Figure 1 The inkjet recording device 1 is a serial recording device that records by performing multiple main scans and sub-scans separately. It should be noted that scanning is also referred to as main scanning. In the case of a serial recording device, compared to a line recording device described later, it is preferable that the recording device can be miniaturized.

[0253] The inkjet head 2 is configured to eject ink and processing liquid from its nozzles, thereby adhering them to the recording medium M and recording data. In this embodiment, the inkjet head 2 is a serial inkjet head that performs multiple scans relative to the recording medium M in the main scanning direction to adhere ink or processing liquid to the recording medium M. The inkjet head 2 is mounted on... Figure 2 The carriage 9 is shown. The inkjet head 2 performs multiple scans relative to the recording medium M in the main scanning direction by the action of the carriage moving mechanism 13, which moves the carriage 9 in the media width direction. The media width direction refers to the main scanning direction of the inkjet head 2. Scanning along the main scanning direction is also called main scanning.

[0254] Furthermore, here, the main scanning direction is the direction of movement of the carriage 9, which carries the inkjet head 2. Figure 1 In this context, the main scanning direction intersects with the secondary scanning direction, which is the transport direction of the recording medium M, indicated by arrow SS. Figure 2 In this diagram, the width direction of the recording medium M, that is, the direction represented by S1-S2, is the main scanning direction MS, and the direction represented by T1→T2 is the sub-scanning direction SS. It should be noted that in a single scan, scanning is performed in the main scanning direction, i.e., in either direction of arrow S1 or arrow S2. Furthermore, recording is achieved by repeatedly performing the main scan of the inkjet head 2 and the sub-scans that transport the recording medium M.

[0255] The ink cartridge 12, which supplies ink or processing fluid to the inkjet head 2, comprises multiple independent ink cartridges. The ink cartridge 12 is detachably mounted on the carriage 9 on which the inkjet head 2 is mounted. Each of the multiple ink cartridges is filled with ink or processing fluid, and a predetermined amount of ink or processing fluid is supplied from the ink cartridge 12 to each nozzle. It should be noted that in this embodiment, an example of the ink cartridge 12 being mounted on the carriage 9 is shown, but this is not a limitation; it could also be located in a location other than the carriage 9 and supplied to each nozzle via a supply pipe (not shown). Furthermore, the nozzles that eject ink and the nozzles that eject processing fluid can be appropriately designed in conjunction with the configuration of the ink cartridge 12. Moreover, multiple inkjet heads 2 can be mounted on the ink cartridge 12.

[0256] The ejection from the inkjet head 2 can be performed using conventionally known methods. In this embodiment, a method of ejecting droplets by utilizing the vibration of a piezoelectric element, that is, an ejection method that forms ink droplets by the mechanical deformation of an electrostrictive element, is used.

[0257] When the inkjet head 2 ejects the aforementioned white ink composition, non-white ink composition, and processing liquid, the inkjet head 2 constitutes part of the attachment mechanism for performing the white ink attachment process, the attachment mechanism for performing the non-white ink attachment process, the attachment mechanism for performing the first processing liquid attachment process, and the attachment mechanism for performing the second processing liquid attachment process.

[0258] The inkjet recording apparatus 1 includes an IR heater 3 and a pressure plate heater 4 for heating the recording medium M when ink or processing liquid is ejected from the inkjet head 2. In this embodiment, when drying the recording medium M through a drying process, drying mechanisms such as the IR heater 3, the air blower 8, the pressure plate heater 4, and the preheater 7 can be used. The drying process performed on the ink adhering to the recording medium during ink adhesion is also referred to as a primary drying process.

[0259] It should be noted that if an IR heater 3 is used, the recording medium M can be radially heated from the inkjet head 2 side by infrared radiation. Therefore, although the inkjet head 2 can also be easily heated simultaneously, the temperature rise is unaffected by the thickness of the recording medium M, compared to heating from the back of the recording medium M, such as from the pressure plate heater 4. Additionally, various fans (e.g., blower fan 8) can be provided to blow warm air or air at the same temperature as the ambient environment onto the recording medium M to dry the ink and non-white inks on the recording medium M.

[0260] The platen heater 4 heats the recording medium M across the platen 11 at a position opposite to the inkjet head 2, allowing it to dry earlier from the moment the ink or processing liquid ejected from the inkjet head 2 adheres to the recording medium M. The platen heater 4 is a heater capable of conductively heating the recording medium M, and as described above, it is used as needed in the recording method of this embodiment. When used, it is preferable to control the surface temperature of the recording medium M to be below 40.0°C.

[0261] In the ink adhesion process, a drying process that dries the ink adhered to the recording medium using a drying unit may be omitted, or the drying process may be performed at a relatively low temperature. In this case, the speed of drying of the ink adhered to the recording medium is suppressed, which is superior for applications such as landfilling and is therefore preferred.

[0262] During the ink adhesion process, whether the recording medium M is dried using a drying mechanism or not, the upper limit of the surface temperature of the recording medium M is preferably 45.0°C or less, more preferably 40.0°C or less, further preferably 38.0°C or less, and particularly preferably 35.0°C or less. Further, it is preferably 30°C or less, more preferably 28°C or less, and more preferably 25°C or less. Additionally, the lower limit of the surface temperature of the recording medium M is preferably 20°C or more, more preferably 25.0°C or more, more preferably 28.0°C or more, further preferably 30.0°C or more, and particularly more preferably 32.0°C or more. Alternatively, it is preferable to heat the recording medium without using a drying mechanism as described above.

[0263] When the temperature is below the aforementioned range, the drying and compositional changes of the ink or processing liquid within the inkjet head 2 can be suppressed, and the deposition of resin particles, etc., onto the inner wall of the inkjet head 2 is suppressed. Furthermore, it is preferable to have better filling, color development, and reduced image quality. Conversely, when the temperature is above the aforementioned range, the ink or processing liquid can be fixed onto the recording medium M at an earlier stage, thereby improving image quality. It should be noted that the aforementioned temperature is the highest temperature at the position on the surface of the recording medium opposite the inkjet head during the ink or processing liquid adhesion process.

[0264] Heater 5 is used for drying and curing the ink adhered to the recording medium M, i.e., for secondary heating or secondary drying. Heater 5 can be used in post-heating processes. By heating the recording medium M on which the image is recorded by heater 5, the water and other substances contained in the liquid evaporate and disperse more rapidly, thereby forming an ink film from the resin contained in the liquid. In this way, the ink film is firmly fixed or adhered to the recording medium M, exhibiting excellent film-forming properties, and excellent high-quality images can be obtained in a short time. The upper limit of the surface temperature of the recording medium M heated by heater 5 is preferably 120.0°C or less, more preferably 100.0°C or less, and even more preferably 90.0°C or less. In addition, the lower limit of the surface temperature of the recording medium M is preferably 60.0°C or more, more preferably 70.0°C or more, and even more preferably 80.0°C or more. By keeping the temperature within the above range, high-quality images can be obtained in a short time. It should be noted that the above temperatures are the highest temperatures of the portion of the recording medium receiving secondary heating during recording.

[0265] The inkjet recording device 1 may include a cooling fan 6. After the ink recorded on the recording medium M is dried, the ink on the recording medium M is cooled by the cooling fan 6, thereby enabling the formation of an ink coating film with good adhesion on the recording medium M.

[0266] Alternatively, the inkjet recording apparatus 1 may also include a preheater 7, which preheats the recording medium M before the ink adheres to it.

[0267] Below the carriage 9 are: a pressure plate 11 supporting the recording medium M; a carriage moving mechanism 13 for moving the carriage 9 relative to the recording medium M; and a conveying device 14, which is a roller for conveying the recording medium M in the sub-scanning direction. The operation of the carriage moving mechanism 13 and the conveying device 14 is controlled by the control unit CONT.

[0268] Figure 3This is a functional block diagram of the inkjet recording device 1. The control unit CONT is a control unit for controlling the inkjet recording device 1. The interface unit 101 (I / F) is used for sending and receiving data between the computer 130 (COMP) and the inkjet recording device 1. The CPU 102 is an arithmetic processing unit for controlling the inkjet recording device 1 as a whole. The memory 103 (MEM) is used to store the program area, working area, etc., of the CPU 102. The CPU 102 controls each unit through the unit control circuit 104 (UCTRL). It should be noted that the detector group 121 (DS) monitors the condition inside the inkjet recording device 1, and based on the detection results, the control unit CONT controls each unit.

[0269] The transport unit 111 (CONVU) controls the sub-scan (transport device) of the inkjet recording, specifically, it controls the transport direction and speed of the recording medium M. Specifically, it controls the transport direction and speed of the recording medium M by controlling the rotation direction and speed of the transport roller driven by the electric motor.

[0270] The carriage unit 112 (CARU) controls the main scan (process) of inkjet recording (scanning device), specifically, it causes the inkjet head 2 to reciprocate in the main scan direction. The carriage unit 112 includes a carriage 9 that carries the inkjet head 2 and a carriage moving mechanism 13 for reciprocating the carriage 9.

[0271] The printhead unit 113 (HU) controls the amount of ink or processing liquid ejected from the nozzles of the inkjet head 2. For example, when the nozzles of the inkjet head 2 are driven by piezoelectric elements, the operation of the piezoelectric elements in each nozzle is controlled. The printhead unit 113 controls the timing of liquid adhesion, dot size, quality, etc. of the ink and processing liquid. In addition, the amount of ink and processing liquid adhered in each scan is controlled by the combination of the control of the carriage unit 112 and the printhead unit 113.

[0272] The drying unit 114 (DU) controls the temperature of various heaters, including IR heater 3, preheater 7, pressure plate heater 4, and heater 5.

[0273] The inkjet recording apparatus 1 described above alternately performs two actions: moving the carriage 9 carrying the inkjet head 2 in the main scanning direction (main scanning) and transporting the inkjet head 2 (sub-scanning). During each operation, the control unit CONT controls the carriage unit 112, causing the inkjet head 2 to move in the main scanning direction, and simultaneously controls the printhead unit 113, causing ink or processing fluid droplets to be ejected from predetermined nozzles of the inkjet head 2, adhering to the recording medium M. Furthermore, the control unit CONT controls the transport unit 111, thereby transporting the recording medium M in the transport direction at a predetermined feed rate during the transport operation.

[0274] In the inkjet recording apparatus 1, the nozzles of the inkjet heads 2 are arranged in rows, and a predetermined amount of ink or processing liquid can be dispensed to each row. Furthermore, the presence and timing of inkjet ejection can be controlled within the rows of nozzles. Moreover, multiple inkjet heads 2 can be mounted on the carriage 9; in this case, the presence and timing of inkjet ejection from each inkjet head 2 can also be controlled.

[0275] Figure 4 This is an example illustrating the configuration of the inkjet head of a recording apparatus that performs the recording method of this embodiment. Figure 4 (1) is one example, which is observed from below. Figure 1 A diagram of the overall inkjet head. On the overall inkjet head (quadrilateral frame), the inkjet head R for processing liquid, the inkjet head W for white ink composition, and the inkjet head C for non-white ink composition are arranged side-by-side in the main scanning direction (horizontal direction in the diagram). Each inkjet head has a nozzle array with multiple nozzles arranged in the sub-scanning direction SS. The number of nozzle arrays for each inkjet head is not limited to two arrays as shown in the diagram; one or more arrays are acceptable. The recording portion of the nozzle array of each inkjet head is shown enclosed by dashed lines. By performing main and sub-scans sequentially, as recording proceeds, the processing liquid and ink composition are attached to the same scanning area of ​​the recording medium in the following order: the portion enclosed by dashed lines upstream of the sub-scanning direction of the processing liquid inkjet head R, the portion enclosed by dashed lines of the white ink composition inkjet head W, the portion enclosed by dashed lines downstream of the sub-scanning direction of the processing liquid inkjet head R, and the portion enclosed by dashed lines of the non-white ink composition inkjet head C. The first processing liquid adhesion process is performed on the portion enclosed by the dashed line on the upstream side of the sub-scanning direction of the processing liquid inkjet head R, and the second processing liquid adhesion process is performed on the portion enclosed by the dashed line on the downstream side of the sub-scanning direction of the processing liquid inkjet head R.

[0276] Figure 4 (2) indicates that it is related to Figure 4 (1) An example of the configuration of different inkjet heads. (and) Figure 4(1) Similarly, the white ink adhesion process is performed through the portion of the white ink composition inkjet head W surrounded by the dashed line. Additionally, a first processing liquid adhesion process is performed through the portion of the processing liquid inkjet head R that overlaps with the portion of the white ink composition inkjet head W surrounded by the dashed line in the sub-scanning direction when projected in the main scanning direction, using the same main scan as the white ink adhesion process. By sequentially performing the main scan and sub-scan, a non-white ink adhesion process is performed through the portion of the non-white ink composition inkjet head C surrounded by the dashed line as recording progresses. Furthermore, a second processing liquid adhesion process is performed through the portion of the processing liquid inkjet head R that overlaps with the portion of the non-white ink composition inkjet head C surrounded by the dashed line in the sub-scanning direction when projected in the main scanning direction, using the same main scan as the non-white ink adhesion process.

[0277] Figure 4 (3) is an example of the configuration of another inkjet head. A white ink application process is performed using the entire inkjet head with a white ink composition. Additionally, a first processing liquid application process is performed using the entire processing liquid inkjet head R with the same main scan as the white ink application process. Then, a non-white ink application process is performed using the entire non-white ink composition inkjet head C. Additionally, a second processing liquid application process is performed using the entire processing liquid inkjet head R with the same main scan as the non-white ink application process. Between the white ink application process and the non-white ink application process, a sub-scan may not be performed, or a sub-scan may be performed for image alignment. A sub-scan may also be performed after the non-white ink application process.

[0278] exist Figure 4 In the example, recording was performed by defining the portion of each inkjet head used for recording, but inkjet heads could also exist only in... Figure 4 The part enclosed by the dotted line. In other words, the part of each inkjet head used for recording can also be considered as the inkjet head itself.

[0279] In addition to the recording method using a serial recording device as described in the above example, the recording method of this embodiment can also be a recording method using a line recording device.

[0280] Figure 5 This is an example of a line recording device. Figure 5In the inkjet recording apparatus 1 shown, the recording medium 10 is conveyed along the conveying direction by the recording medium support device 15, the transport roller 16, and the transport roller 17. As recording proceeds, the conveyed recording medium is attached in the following sequence: a first processing liquid attachment step performed by the inkjet head 2a, a white ink attachment step performed by the inkjet head 2b, a second processing liquid attachment step performed by the inkjet head 2c, and a non-white ink attachment step performed by the inkjet head 2d. In the case of a line-type recording apparatus, compared to the serial recording apparatus described above, a higher recording speed is possible, which is preferable.

[0281] Regarding the configuration and settings of the inkjet head used to perform the recording method of this embodiment, an example will be given in the following embodiments. For example, in the above recording method, it can be set so that the white ink adhesion process is performed in one scan in areas where ink can be adhered in one scan, and the non-white ink adhesion process is performed in one scan in areas where ink can be adhered in one scan. In this way, recording can be performed at a better recording speed.

[0282] Furthermore, the above recording method can be configured to perform the first processing liquid adhesion process in the same scan as the white ink adhesion process, and the second processing liquid adhesion process in the same scan as the non-white ink adhesion process, thereby enabling recording at a better recording speed.

[0283] According to the recording apparatus of this embodiment, the processing liquid is applied not only in the first processing liquid application step accompanying the application of the white ink composition, but also in the second processing liquid application step accompanying the application of the non-white ink composition. Therefore, the image quality of the image formed from the white ink composition can be improved, and uneven color bleeding in the image formed from the non-white ink composition can be suppressed.

[0284] Furthermore, since the amount of processing liquid applied in the second processing liquid application step is smaller than that in the first processing liquid application step, the amount of processing liquid applied in the second processing liquid application step will not be excessive relative to the amount used to coagulate the components of the non-white ink composition. Therefore, the coagulation of the components of the non-white ink composition will not be excessive, thus suppressing the thinning of lines in the image formed by the non-white ink composition.

[0285] 3. Examples and Comparative Examples

[0286] The present invention will now be specifically described through examples, but the invention is not limited to these examples. Hereinafter, "parts" and "%" are used as quality standards unless otherwise specified. It should be noted that, unless otherwise stated, evaluations were conducted at a temperature of 25.0°C and a relative humidity of 40.0%.

[0287] 3.1. Preparation of ink and treatment solution

[0288] According to the composition in Table 1, the components were placed in a container and mixed and stirred with a magnetic stirrer for 2 hours. Then, the mixture was further dispersed using a bead mill filled with 0.3 mm diameter zirconia beads to ensure thorough mixing. After stirring for 1 hour, the mixture was filtered using a 5.0 μm PTFE membrane filter to obtain white ink compositions (W1–W4), non-white ink compositions (C1, C2), and treatment solutions (R1–R3). The values ​​in Table 1 represent mass percent. Pure water was used and added at 100% by mass for each ink. The pigments, dispersant resins, and other components were used to prepare the dispersions described later.

[0289]

[0290] The components shown in Table 1, excluding the compound names, are as follows:

[0291] Cationic polymer: "CatioMaster PD-7, polyamine resin (epoxychloropropane-amine derivative resin)", manufactured by Yokkaichi Synthetic Co., Ltd.

[0292] Dispersant resin, Resin A (anionic): Acrylic acid-acrylate copolymer (weight average molecular weight: 25,000, acid value: 25)

[0293] Dispersant resin, Resin B (nonionic): Acrylic acid-acrylate copolymer (weight average molecular weight: 25,000, acid value: 0)

[0294] Dispersant resin, resin C (anionic): acrylic acid-acrylate copolymer (weight average molecular weight: 25,000, acid value: 35)

[0295] Carbon black: No. 33 (manufactured by Mitsubishi Chemical Corporation)

[0296] • Resin particles, styrene-acrylic A: See below (high cohesiveness)

[0297] • Resin particles, styrene-acrylic B: See below (low cohesion)

[0298] Wax and polyethylene: "NopcotePEM-17" (trade name, manufactured by SanNopco Co., Ltd.)

[0299] Surfactant: Silicone-based surfactant "BYK348", manufactured by BYK Corporation.

[0300] (Preparation of resin particles: styrene-acrylic B)

[0301] Resin emulsion B (acid value 7 mg KOH / g) was obtained by emulsifying and copolymerizing 75 parts by weight of styrene, 0.8 parts by weight of acrylic acid, 14.2 parts by weight of methyl methacrylate, and 10 parts by weight of cyclohexyl methacrylate. It should be noted that Newcol NT-30 (manufactured by Nippon Emulsifier Co., Ltd.) was used as the surfactant for emulsification polymerization, with an amount of 2 parts by weight per 100 parts by weight of monomers.

[0302] (Preparation of resin particles: styrene-acrylic A)

[0303] Except for changing the monomer composition, the same procedure as described above was followed to obtain resin emulsion A (acid value 30 mg KOH / g). The surfactant used for emulsification polymerization was 1 part by mass relative to 100 parts by mass of the total monomer.

[0304] (Preparation of pigment dispersion)

[0305]

[0306] First, 12 parts by mass of anionic acrylic-acrylate copolymer (weight average molecular weight: 25,000, acid value: 25) were added to 155 parts by mass of ion-exchanged water containing 0.1 parts by mass of 30% ammonia solution (neutralizing agent) as a resin dispersant to dissolve it. Then, 40 parts by mass of titanium dioxide (CI Pigment White 6) as a white pigment were added, and the mixture was dispersed using a zirconia ball mill for 10 hours. Next, the mixture was centrifuged and filtered to remove coarse particles and impurities, adjusting the concentration of the white pigment to 20% by mass to obtain a white pigment dispersion. The average particle size of the white pigment was 350 nm.

[0307]

[0308] Except for the use of acrylic-acrylate copolymer (weight average molecular weight: 25,000, acid value: 0) as the resin dispersant, the same procedure was followed to obtain a white pigment dispersion. The particle size of the white pigment was 350 nm on average.

[0309] <Utilizing a non-white pigment dispersion made from resin C>

[0310] Acrylic acid-acrylate copolymer (weight average molecular weight: 25,000, acid value: 35) was used as the resin dispersant, and carbon black was used as the pigment. The amount of resin dispersant added was such that the mass ratio of resin dispersant to pigment was as shown in Table 1. Otherwise, the same procedure was followed to obtain a non-white pigment dispersion (black). The pigment particle size was 60 nm on average.

[0311] 3.2. Evaluation Methods

[0312] 3.2.1. Viscosity Increasing Rate

[0313] Table 1 lists the "Reactivity with Test Solution (Tickling Rate)" as follows: Each ink was mixed with a 7% (w / w) calcium formate aqueous solution at a mass ratio of 10:1 and stirred for 1 minute. The mixture was then tested using a rheometer (MCR302 / Anton-Paar) at 25°C and a shear rate of 200 s⁻¹. -1 The viscosity ratio of the mixed liquid to the original ink viscosity was determined under the specified conditions.

[0314] 3.2.2. Record the experiment

[0315] The modified SC-R5050 inkjet printer (manufactured by Seiko Epson Corporation) is filled with various ink compositions and processing liquids. The printheads are configured such that a printhead ejecting the white ink composition and processing liquid is positioned upstream in the recording media transport direction, and a printhead ejecting the non-white ink composition and processing liquid is positioned downstream. In each example, the same processing liquid is used for both the first and second processing liquids.

[0316] The inkjet head on the upstream side of the transport direction that ejects the processing liquid is the same inkjet head that performs the first processing liquid adhesion process. It is arranged laterally with the inkjet head that ejects the white ink composition, and both the white ink composition and the first processing liquid are adhered to it simultaneously. The same applies to the inkjet head on the downstream side of the transport direction that ejects the non-white ink composition and processing liquid.

[0317] Each experiment was conducted under the conditions shown in Tables 2-1 to 2-8. For example, in Example 1, an example was conducted by simultaneously spraying the processing liquid and white ink composition in a single pass, followed by simultaneously spraying the processing liquid and non-white ink composition in the same order. In Example 1, the pressure plate heater was turned off. Other examples were also recorded under the conditions shown in Tables 2-1 to 2-8. Examples 9 and 18 involved a single heating process using the pressure plate heater. Example 16 had a pass count of 4. In Example 17, the inkjet heads were arranged from upstream to downstream in the recording medium transport direction in the order of inkjet head performing the first processing liquid adhesion process, inkjet head ejecting the white ink composition, inkjet head performing the second processing liquid adhesion process, and inkjet head ejecting the non-white ink composition, and adhesion was performed in this order.

[0318] The recording resolution was based on 1200×1200 dpi, and the number of droplets per pixel was adjusted to achieve the adhesion amounts shown in Tables 2-1 to 2-8. Furthermore, secondary heating was performed using a secondary heater downstream of the recording medium in the transport direction to heat the medium to 70°C. The recording medium used was PET 50A (manufactured by Lintec).

[0319] 3.2.3. Evaluation of landfill pinholes

[0320] The full-page image area of ​​the recorded material is visually observed under fluorescent light and evaluated according to the following criteria. It should be noted that the evaluation of white ink is performed on the portion of the recorded pattern where the white ink composition and the first processing liquid are adhered, but the non-white ink composition and the second processing liquid are not adhered. The evaluation of non-white ink is performed on the portion of the recorded pattern where the white ink composition and the first processing liquid are adhered, and the non-white ink composition and the second processing liquid are further adhered, overlapping each other.

[0321] A: There are no unfilled areas or pinholes.

[0322] B: Some unfilled areas or pinholes are visible.

[0323] C: Unfilled areas or pinholes are clearly visible.

[0324] 3.2.4. Evaluation of uneven concentration

[0325] Visually observe the full-page image area of ​​the recorded material under fluorescent light and evaluate it according to the following criteria.

[0326] The recording pattern used for evaluating white ink, the recording pattern used for evaluating non-white ink, and the recording pattern used for evaluating landfill and pinholes are the same.

[0327] A: No bleeding (uneven color intensity).

[0328] B: Some bleeding is visible (uneven color intensity).

[0329] C: Visible bleeding (uneven color intensity).

[0330] 3.2.5. Evaluation of 3pt text

[0331] (blank text)

[0332] Create a non-white full-page image on top of a white full-page image. In the non-white full-page image, create white text (3pt) in the areas without non-white ink. Then, observe the bleeding at the boundary between the white and non-white ink. Evaluate according to the following criteria. Record the results in the white areas of the table.

[0333] A: There is no color bleeding at the boundaries of blank text.

[0334] B: There is some color bleeding at the boundaries of the blank text.

[0335] C: Color seepage exists at the boundaries of blank text.

[0336] (Non-white text)

[0337] Text (3pt) is recorded on a white full-page image using non-white ink. Then, the thinning breaks in the lines of the non-white text are evaluated.

[0338] Evaluate the non-white text according to the following evaluation criteria. Record the results in the non-white section of the table.

[0339] A: I can clearly read the non-white text on a full-page white background.

[0340] B: There are some interruptions in the non-white text on the full white page.

[0341] C: There are breaks in the non-white text on the white full-page layout.

[0342] 3.2.6. Evaluation of abrasion resistance

[0343] Abrasion resistance was evaluated using the recorded test patterns as described below. The recording medium used was GIY43R5 (transparent PVC manufactured by Lintec Sign Systems). Secondary heating was set to dry at 70°C for 10 minutes. Recorded patterns for evaluating white inks, recorded patterns for evaluating non-white inks, and landfill were also included. The evaluation records for pinholes are identical.

[0344] A: No peeling occurred after wiping with a 500g load 10 times in the vibration and abrasion resistance test.

[0345] B: Peeling occurred after 10 rubs with a 500g load in the vibration abrasion resistance test, but it was within 10% of the evaluation area.

[0346] C: In the vibration and abrasion resistance test, more than 10% peeling occurred after 10 rubs with a load of 500g.

[0347] 3.2.7. Evaluation of Ejection Stability

[0348] Under image formation conditions, continuous image recording was performed for 1 hour, and the nozzles of the ejector nozzle group were inspected after recording. The total number of non-ejecting nozzles was divided by the total number of nozzles, and the results were evaluated according to the following criteria and recorded in the table.

[0349] A: The percentage of nozzles that do not spray is less than 1.0%.

[0350] B: No more than 1.0% of the nozzle does not spray and is below 2.0%.

[0351] C: No more than 2.0% of the nozzle does not spray out and is below 5.0%.

[0352]

[0353]

[0354]

[0355]

[0356] 3.3. Evaluation Results

[0357] According to the recording method of each embodiment where the viscosity of the white ink composition increases by more than 5 times when mixed with a 7% (w / w) aqueous solution of calcium formate at a mass ratio of 10:1, and the amount of treatment liquid adhering in the second treatment liquid adhering step is less than the amount of treatment liquid adhering in the first treatment liquid adhering step, it was determined that the image quality of the image formed by the white ink composition can be improved, and the uneven bleeding of the image formed by the non-white ink composition can be suppressed. Furthermore, it was determined that the thinning of lines in the image formed by the non-white ink composition can be suppressed.

[0358] This invention includes configurations that are substantially the same as those described in the embodiments, such as configurations with the same function, method, and result, or configurations with the same purpose and effect. Additionally, this invention includes configurations that replace non-essential parts of the configurations described in the embodiments. Furthermore, this invention includes configurations that achieve the same effect as those described in the embodiments or that can achieve the same purpose. Additionally, this invention includes configurations incorporating known technology into the configurations described in the embodiments.

[0359] The following content is derived from the above implementation methods and variations.

[0360] The recording methods include:

[0361] The white ink adhesion process involves adhering a white ink composition containing white pigment to a recording medium.

[0362] The non-white ink adhesion process involves adhering a non-white ink composition containing a non-white pigment to the already adhered white ink composition in an overlapping manner.

[0363] The first processing liquid adhesion step, which follows the white ink adhesion step, causes the processing liquid containing a coagulant to adhere to the recording medium; and

[0364] The second processing liquid adhesion step, which follows the non-white ink adhesion step, causes the processing liquid containing a coagulant to adhere to the recording medium.

[0365] The viscosity of the white ink composition increases more than fivefold when mixed with a 7% (w / w) aqueous solution of calcium formate at a mass ratio of 10:1.

[0366] The amount of treatment liquid adhering in the second treatment liquid adhesion step is smaller than the amount of treatment liquid adhering in the first treatment liquid adhesion step.

[0367] According to this recording method, the processing liquid is applied not only in the first processing liquid application step accompanying the application of the white ink composition, but also in the second processing liquid application step accompanying the application of the non-white ink composition. Therefore, the image quality of the image formed from the white ink composition can be improved, and uneven color bleeding in the image formed from the non-white ink composition can be suppressed.

[0368] Furthermore, since the amount of processing liquid applied in the second processing liquid application step is smaller than that in the first processing liquid application step, the amount of processing liquid applied in the second processing liquid application step will not be excessive relative to the amount used to coagulate the components of the non-white ink composition. Therefore, the coagulation of the components of the non-white ink composition will not be excessive, thus suppressing the thinning of lines in the image formed by the non-white ink composition.

[0369] In the above recording method,

[0370] The amount of treatment liquid adsorbed in the first treatment liquid adhesion step can be 0.4 mg / 645.16 mm. 2 Above 2.5mg / 645.16mm 2 the following.

[0371] According to this recording method, the image quality of images formed by white ink compositions can be maintained at a very high level, and the uneven bleeding and thinning of fine lines in images formed by non-white ink compositions can be further reduced.

[0372] In the above recording method,

[0373] The amount of treatment liquid adsorbed in the second treatment liquid adhesion step can be 2.5 mg / 645.16 mm. 2 the following.

[0374] According to this recording method, it is possible to further reduce the uneven bleeding and thinning of fine lines in images formed by non-white ink compositions.

[0375] In the above recording method,

[0376] The white ink composition may contain a white pigment as a white colorant and an anionic dispersant resin.

[0377] According to this recording method, the dispersion and aggregation of white pigment are improved, resulting in images with better dispersion stability and image quality.

[0378] In the above recording method,

[0379] The amount of white ink composition applied in the white ink adhesion process can be 9.0 mg / 645.16 mm. 2 above.

[0380] This recording method can produce a better white image.

[0381] In the above recording method, it is also possible to:

[0382] The white ink adhesion process is performed in a single scan in areas where ink can be adhered in a single scan, and the non-white ink adhesion process is performed in a single scan in areas where ink can be adhered in a single scan.

[0383] This recording method allows for recording at a better speed.

[0384] In the above recording method, it is also possible to:

[0385] The first treatment liquid adhesion process is performed using the same scanning method as the white ink adhesion process.

[0386] The second treatment liquid adhesion process is performed using the same scanning as the non-white ink adhesion process.

[0387] This recording method allows for recording at a better speed.

[0388] In the above recording method,

[0389] The total amount of treatment liquid adhered in the first treatment liquid adhesion step and the treatment liquid adhered in the second treatment liquid adhesion step can be 4.0 mg / 645.16 mm. 2 the following.

[0390] According to this recording method, it is possible to further suppress the inadequacy of the embedding properties of images formed by white ink compositions.

[0391] In the above recording method,

[0392] The white ink adhesion process, the first treatment liquid adhesion process, the non-white ink adhesion process, and the second treatment liquid adhesion process can be performed by inkjet printing.

[0393] In the above recording method, it is also possible to:

[0394] The first and second processing liquid adhesion processes are performed using inkjet printing.

[0395] In the first and second processing liquid attachment steps, the mass of the multiple droplets of the processing liquid is less than 7 ng.

[0396] This recording method allows for greater contact between the processing liquid and the ink on the recording medium.

[0397] In the above recording method, it is also possible to:

[0398] The viscosity of the non-white ink composition increases by more than 5 times when it is mixed with a 7% (w / w) aqueous solution of calcium formate at a mass ratio of 10:1.

[0399] This recording method can produce white images with better image quality.

[0400] In the above recording method, it is also possible to:

[0401] The surface tension of the treatment liquid in the first treatment liquid adhesion step and the surface tension of the treatment liquid in the second treatment liquid adhesion step are both less than the surface tension of the non-white ink composition.

[0402] The surface tension of the non-white ink composition is less than that of the white ink composition.

[0403] Alternatively, the surface tension of the treatment liquid used in each treatment liquid adhesion process can be made lower than that of the non-white ink composition, and the surface tension of the non-white ink composition can be made lower than that of the white ink composition. This facilitates the wetting and spreading of the treatment liquid on the substrate, and also facilitates the wetting and spreading of the white ink on it, thus improving filling and pinholes. Furthermore, since the non-white ink composition weeps and spreads more easily than the white ink composition, it is easier to form a non-white image on a white image.

[0404] In the above recording method, it is also possible to:

[0405] The maximum amount of white ink composition adhered in the white ink adhesion process is greater than the maximum amount of non-white ink composition adhered in the non-white ink adhesion process.

[0406] This recording method enables recording with better background concealment.

[0407] In the above recording method, it is also possible to:

[0408] The surface temperature of the recording medium during the white ink adhesion process is below 30°C when the white ink composition is adhered.

[0409] The surface temperature of the recording medium during the non-white ink adhesion process is below 30°C when the non-white ink composition is adhered.

[0410] According to this recording method, the cohesiveness of the white ink composition can be further improved.

[0411] In the above recording method, it is also possible to:

[0412] The white ink adhesion process does not involve a heating step, and the non-white ink adhesion process does not involve a heating step.

[0413] This recording method can improve ejection stability.

[0414] The recording apparatus includes: an attachment mechanism for performing the white ink attachment process described above, an attachment mechanism for performing the non-white ink attachment process described above, an attachment mechanism for performing the first processing liquid attachment process described above, and an attachment mechanism for performing the second processing liquid attachment process described above, wherein the recording apparatus performs any one of the above recording methods.

[0415] According to this recording apparatus, the processing liquid is applied not only in the first processing liquid application step accompanying the application of the white ink composition, but also in the second processing liquid application step accompanying the application of the non-white ink composition. Therefore, the image quality of the image formed from the white ink composition can be improved, and uneven color bleeding in the image formed from the non-white ink composition can be suppressed.

[0416] Furthermore, since the amount of processing liquid adhered in the second processing liquid adhesion step is smaller than that in the first processing liquid adhesion step, the amount of processing liquid adhered in the second processing liquid adhesion step will not be excessive relative to the amount used to coagulate the components of the non-white ink composition. Therefore, the coagulation of the components of the non-white ink composition will not be excessive, thus suppressing the thinning of lines in the image formed by the non-white ink composition. It should be noted that the same adhesion mechanism can be both the adhesion mechanism performing the first processing liquid adhesion step and the adhesion mechanism performing the second processing liquid adhesion step.

Claims

1. A recording method, characterized in that, have: The white ink adhesion process involves adhering a white ink composition containing white pigment to a recording medium. The non-white ink adhesion process involves adhering a non-white ink composition containing a non-white pigment to the already adhered white ink composition in an overlapping manner. The first processing liquid adhesion step, which follows the white ink adhesion step, causes the processing liquid containing the coagulant to adhere to the recording medium. as well as The second processing liquid adhesion step, which follows the non-white ink adhesion step, causes the processing liquid containing a coagulant to adhere to the recording medium. The viscosity of the white ink composition increases more than fivefold when mixed with a 7% (w / w) aqueous solution of calcium formate at a mass ratio of 10:

1. The amount of treatment liquid adhering in the second treatment liquid adhesion step is smaller than the amount of treatment liquid adhering in the first treatment liquid adhesion step.

2. The recording method according to claim 1, characterized in that, The amount of treatment liquid adsorbed in the first treatment liquid adhesion step is 0.4 mg / 645.16 mm. 2 Above and 2.5mg / 645.16mm 2 the following.

3. The recording method according to claim 1, characterized in that, The amount of treatment liquid adsorbed in the second treatment liquid adhesion process is 2.5 mg / 645.16 mm. 2 the following.

4. The recording method according to claim 1, characterized in that, The white ink composition contains a white pigment as a white colorant and an anionic dispersant resin.

5. The recording method according to claim 1, characterized in that, The amount of white ink composition adhered in the white ink adhesion process is 9.0 mg / 645.16 mm. 2 above.

6. The recording method according to claim 1, characterized in that, The white ink adhesion process is performed in a single scan in areas where ink can be adhered in a single scan, and the non-white ink adhesion process is performed in a single scan in areas where ink can be adhered in a single scan.

7. The recording method according to claim 1, characterized in that, The first treatment liquid adhesion process is performed using the same scan as the white ink adhesion process. The second treatment liquid adhesion process is performed using the same scan as the non-white ink adhesion process.

8. The recording method according to claim 1, characterized in that, The total amount of treatment liquid adhered in the first treatment liquid adhesion step and the treatment liquid adhered in the second treatment liquid adhesion step is 4.0 mg / 645.16 mm. 2 the following.

9. The recording method according to claim 1, characterized in that, The white ink adhesion process, the first treatment liquid adhesion process, the non-white ink adhesion process, and the second treatment liquid adhesion process are performed by inkjet printing.

10. The recording method according to claim 1, characterized in that, The first and second processing liquid adhesion processes are performed using inkjet printing. In the first and second processing liquid attachment steps, the mass of the multiple droplets of the processing liquid is less than 7 ng.

11. The recording method according to claim 1, characterized in that, The viscosity of the non-white ink composition increases by more than 5 times when it is mixed with a 7% (w / w) aqueous solution of calcium formate at a mass ratio of 10:

1.

12. The recording method according to claim 1, characterized in that, The surface tension of the treatment liquid in the first treatment liquid adhesion step and the surface tension of the treatment liquid in the second treatment liquid adhesion step are both less than the surface tension of the non-white ink composition. The surface tension of the non-white ink composition is less than that of the white ink composition.

13. The recording method according to claim 1, characterized in that, The maximum amount of white ink composition adhered in the white ink adhesion process is greater than the maximum amount of non-white ink composition adhered in the non-white ink adhesion process.

14. The recording method according to claim 1, characterized in that, The surface temperature of the recording medium during the white ink adhesion process is below 30°C when the white ink composition is adhered. The surface temperature of the recording medium during the non-white ink adhesion process is below 30°C.

15. The recording method according to claim 1, characterized in that, The white ink adhesion process does not involve a heating step, and the non-white ink adhesion process does not involve a heating step. A heating process is a process of heating the recording medium before or during the ink adhesion process.

16. A recording device, characterized in that, It comprises: an attachment mechanism for performing the white ink attachment process, an attachment mechanism for performing the non-white ink attachment process, an attachment mechanism for performing the first treatment liquid attachment process, and an attachment mechanism for performing the second treatment liquid attachment process. The recording device performs the recording method according to claim 1.

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