Recording method and recording apparatus

Abstract

Provided are a recording method and a recording apparatus which are excellent in nozzle clogging recovery, image quality, and whitening reduction of printed matter. The recording method includes a processing liquid adhesion step and an ink adhesion step, the processing liquid adhesion step and the ink adhesion step are performed by scanning performed while moving a processing liquid inkjet head and an ink inkjet head relative to a recording medium, and the processing liquid and the ink composition are adhered to the same scanning region by the same scanning. The coagulant is a calcium salt in an amount of 0.35 mol / kg or less with respect to the total mass of the processing liquid, the maximum value range of the adhesion amount of the calcium salt in the region where the processing liquid and the ink composition are adhered to the recording medium in the processing liquid adhesion step is 0.6 [mu] mol / inch2 or less, and the processing liquid adhesion step and the ink adhesion step have an air blowing step for blowing air to the recording medium.

Description

Technical Field

[0001] The present invention relates to a recording method and a recording device. Background Art

[0002] The inkjet recording method can record high-definition images with a relatively simple device and has achieved rapid development in various aspects. Among them, research is being conducted on recording methods that use a treatment liquid to reduce the fluidity of the ink as soon as possible and fix it to obtain excellent image quality. In particular, for low-absorbency or non-absorbency recording media, since ink droplets are difficult to be absorbed by the recording medium, ink droplets sometimes mix with each other on the recording medium, resulting in uneven bleeding, and the use of a treatment liquid is being studied.

[0003] In addition, when a processing liquid is used for recording in a serial or horizontal printer, from the perspective of increasing the recording speed and miniaturizing the device, a recording method has been studied in which an inkjet head that ejects ink and an inkjet head that ejects the processing liquid are arranged horizontally in a scanning direction, and the ink and the processing liquid are simultaneously ejected in the same scanning area in the same scanning.

[0004] For example, Patent Document 1 discloses a recording method in which ink and a processing liquid are simultaneously ejected by the same scanning so that the ink and the processing liquid are attached to the same scanning area.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2020-32600 Summary of the invention

[0008] Technical problem to be solved by the invention

[0009] However, the recording method in which the ink and the processing liquid are attached to the same scan area by the same scan is not sufficient to achieve excellent nozzle clogging recovery, image quality, and whitening reduction of printed matter.

[0010] Technical solutions for solving technical problems

[0011] One embodiment of the recording method according to the present invention is a recording method comprising:

[0012] a treatment liquid attachment step of ejecting a treatment liquid containing a coagulant from an inkjet head for the treatment liquid so as to attach the treatment liquid to the recording medium; and

[0013] In the ink attaching step, an aqueous ink composition containing a coloring material is ejected from an inkjet head to attach the composition to a recording medium.

[0014] The process liquid attaching step and the ink attaching step are performed by scanning while the process liquid inkjet head and the ink inkjet head are moved relative to the recording medium.

[0015] By the same scanning, the treatment liquid and the ink composition are attached to the same scanning area,

[0016] The coagulant is a calcium salt,

[0017] The content of the calcium salt relative to the total mass of the treatment liquid is 0.35 mol / kg or less,

[0018] In the treatment liquid attachment step, the maximum value of the amount of the calcium salt attached in the region of the recording medium to which the treatment liquid and the ink composition are attached is in the range of 0.6 μmol / inch. 2 the following,

[0019] The processing liquid attaching step and the ink attaching step include an air supply step of supplying air to the recording medium.

[0020] One embodiment of the recording device according to the present invention is:

[0021] A recording device, which records on the recording medium using the recording method of one embodiment above,

[0022] The invention comprises the treatment liquid, the ink composition, an inkjet head for the treatment liquid, and an inkjet head for the ink. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a schematic cross-sectional view schematically showing a serial inkjet recording device.

[0024] Figure 2 This is a perspective view showing an example of the structure around the carriage of a serial inkjet recording device.

[0025] Figure 3 This is a schematic diagram showing an example of the arrangement of the inkjet heads.

[0026] Figure 4 This is a schematic diagram showing an example of the arrangement of the inkjet heads.

[0027] Figure 5 This is a schematic diagram showing an example of the arrangement of the inkjet heads.

[0028] Figure 6 It is a front view schematically showing an example of a landscape type recording device.

[0029] Figure 7 It is a bottom view partially showing the structure of a recording unit of a horizontal type recording device.

[0030] Figure 8 It is a figure which shows the composition example of a processing liquid (Table 1).

[0031] Fig. 9 It is a figure which shows the composition example of an ink composition (Table 2).

[0032] Fig.10 It is a figure which shows the example of a recording method and an evaluation result (Table 3).

[0033] Fig.11 It is a figure which shows the example of a recording method and an evaluation result (Table 4).

[0034] Description of Reference Numerals

[0035] 19: inkjet recording device; 29: inkjet head (29a: inkjet head for treatment liquid; 29b: inkjet head for ink); 391: IR heater; 49: platen heater; 59: heater; 69: cooling fan; 79: preheater; 89: ventilation fan; 99: carriage; 119: platen; 129: box; 139: carriage moving mechanism; 149: conveying unit; CONT: control unit; MS: main scanning direction; SS: sub-scanning direction; M: recording medium; 100: recording device; 200: host device; 210: printer driver; 230: communication control unit; 240: monitor; 300: Printer unit; 400: printer control unit; 1: main body shell; 2: delivery unit; 9: frame of slide; 12: main body of slide; 13: slide moving mechanism; 14: conveying unit; 21: delivery shaft; 3: printing chamber; 30, 11: platen; 31: recording unit; 32: slide; 33: support plate; 34: inkjet head for processing liquid; 35: inkjet head for ink; 37: X-axis guide; 38: suction unit; 39: heater; 4: drying unit; 5: winding unit; 51: winding shaft; 6: base; 71-77: rollers; 8: box mounting unit; 81: processing liquid box; 82: ink cartridge; R1, R2: rollers; S: sheet. DETAILED DESCRIPTION

[0036] The following describes the embodiments of the present invention. The embodiments described below illustrate examples of the present invention. The present invention is not limited to the following embodiments, but also includes various modifications implemented within the scope of the present invention. It should be noted that all the structures described below are not necessarily necessary structures of the present invention.

[0037] In the present specification, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0038] 1. Recording method

[0039] A recording method according to one embodiment of the present invention comprises: a treatment liquid attachment step of ejecting a treatment liquid containing a coagulant from an inkjet head for the treatment liquid so that the treatment liquid is attached to a recording medium; and an ink attachment step of ejecting an aqueous ink composition containing a coloring material from an inkjet head for the ink so that the treatment liquid is attached to a recording medium, wherein the treatment liquid attachment step and the ink attachment step are performed by scanning while the inkjet head for the treatment liquid and the inkjet head for the ink are moved relative to the recording medium, wherein the treatment liquid and the ink composition are attached to the same scanning area by the same scanning, wherein the coagulant is a calcium salt, wherein the content of the calcium salt relative to the total mass of the treatment liquid is 0.35 mol / kg or less, and wherein in the treatment liquid attachment step, the maximum amount of the calcium salt attached to the area of ​​the recording medium to which the treatment liquid and the ink composition are attached is in the range of 0.6 μmol / inch 2 Next, in the process liquid adhesion step and the ink adhesion step, there is an air supply step of supplying air to the recording medium.

[0040] Research is being conducted on a recording method that uses a treatment liquid to reduce the fluidity of the ink as soon as possible and fix it to obtain excellent image quality. In particular, for low-absorption or non-absorption recording media, since ink droplets are difficult to be absorbed by the recording medium, ink droplets sometimes mix with each other on the recording medium, causing uneven bleeding, and the use of a treatment liquid is being studied.

[0041] In addition, when the processing liquid is used in a serial or horizontal printer, if the processing liquid is first attached to the recording medium and then the ink is attached (the processing liquid is ejected first), there is a technical problem that the recording speed is slowed down. In addition, the above method can be realized by arranging an inkjet head that ejects the processing liquid on the upstream side of the direction (sub-scanning direction) intersecting the direction in which the inkjet head performs main scanning (main scanning direction) in the serial printer, and arranging an inkjet head that ejects ink on the downstream side, but in this case, the overall length of the inkjet head in the sub-scanning direction becomes longer, and the device becomes larger.

[0042] Therefore, from the perspective of improving the recording speed and miniaturizing the device, a recording method has been studied in which an inkjet head that ejects ink and an inkjet head that ejects a processing liquid are arranged horizontally in the scanning direction, and the ink and the processing liquid are simultaneously ejected in the same scanning area with the same scanning.

[0043] However, the image quality is more likely to deteriorate when the simultaneous jetting is compared with the treatment liquid jetting first. It is speculated that this is because there are ink droplets on the recording medium that cannot contact the treatment liquid droplets and do not undergo a coagulation reaction. As mentioned above, the deterioration of the image quality is caused by the aggregation and mixing of the ink droplets, which leads to disordered image quality. It is also called uneven bleeding. In order to obtain excellent image quality, it is necessary to suppress uneven bleeding.

[0044] Therefore, by using a polyvalent metal salt with excellent reactivity, especially a calcium salt with excellent reactivity as the coagulant contained in the treatment liquid, excellent image quality (suppressing uneven bleeding) can be obtained. It is speculated that this is because the fluidity of the ink droplets that can contact the treatment liquid droplets on the recording medium can be firmly blocked. However, when a polyvalent metal salt is used as a coagulant, depending on the concentration contained in it, it sometimes becomes a crystallized substance near the surface of the recorded object, causing a whitening phenomenon that appears as white spots on the printed surface.

[0045] On the other hand, there is a technical problem of poor nozzle blockage recovery during simultaneous jetting. During simultaneous jetting in the main scanning of the inkjet head, the mist of the treatment liquid easily flies to the nozzle that ejects the ink. If the ink and the mist of the treatment liquid react in the nozzle and become foreign matter, the blockage is difficult to recover even if it is cleaned. In addition, when calcium salt is used as a coagulant, the blockage recovery is significantly deteriorated.

[0046] Therefore, when the concentration of calcium salt in the treatment liquid is set below a certain level, excellent clogging recovery can be obtained. It is speculated that this is because by making the concentration of calcium salt in the treatment liquid relatively low, the reactivity can be suppressed, and the foreignization of ink and treatment liquid in the nozzle can be reduced. However, in this case, due to the low reactivity of the treatment liquid, the image quality of the recorded image (suppressing uneven bleeding) deteriorates.

[0047] As described above, it has been very difficult to achieve excellent nozzle clogging recovery, image quality (suppression of uneven bleeding), and whitening reduction of printed matter during simultaneous ejection.

[0048] Recently, it has been found that in the process of making ink adhere, by carrying out the air supply process of promoting drying by supplying air to the ink adhesion area of ​​the recording medium, the clogging recovery of the nozzle, the picture quality (suppressing uneven seepage) and the whitening reduction of the printed matter can be excellent when spraying at the same time. Through the air supply process, the evaporation of the water contained in the ink or the treatment liquid attached to the recording medium can be promoted, and the concentration of calcium ions can be increased. It is speculated that calcium ions have a tendency to be particularly reactive when the concentration increases, and even if the evaporation of water is promoted by the air supply process, excellent picture quality (reducing uneven seepage) can be obtained. In addition, since the coagulant concentration of the treatment liquid is low before being promoted to evaporate on the recording medium, it is also possible to reduce the situation of foreignization caused by the reaction of ink and the treatment liquid in the nozzle, and the clogging recovery is also excellent.

[0049] Hereinafter, each step of the recording method according to the present embodiment will be described.

[0050] 1.1 Treatment liquid attachment process

[0051] The recording method according to the present embodiment includes a processing liquid attaching step of ejecting a processing liquid containing an aggregating agent from an inkjet head for processing liquid and attaching the processing liquid to a recording medium.

[0052] 1.1.1 Attachment method

[0053] The recording method according to the present embodiment performs a process liquid attachment step and an ink attachment step described later by scanning while moving an inkjet head for a process liquid and an inkjet head for ink relative to a recording medium, and the process liquid and the ink composition described later are attached to the same scanning area by the same scanning. In the process liquid attachment step, the maximum amount of calcium salt attached to the area where the process liquid and the ink composition of the recording medium are attached is in the range of 0.6 μmol / inch. 2 the following.

[0054] The above-mentioned attachment method is, for example, when there are a plurality of nozzle arrays composed of a plurality of nozzles arranged along a direction intersecting the direction in which the inkjet head moves (hereinafter also referred to as the "head moving direction") on the nozzle surface of the inkjet head for processing liquid and the inkjet head for ink along the head moving direction, when the nozzle array for ejecting the processing liquid of the inkjet head for ejecting the processing liquid is projected along the head moving direction, it can be arranged in a manner that at least partially overlaps with the nozzle array of the inkjet head for ejecting the ink in the nozzle array direction (jetted in front), preferably arranged in a manner that completely overlaps (jetted at the same time). An example of the arrangement of such an inkjet head will be described later.

[0055] In the process liquid attachment step, the maximum amount of calcium salt attached to the region where the process liquid and the ink composition are attached to the recording medium is in the range of 0.6 μmol / inch. 2 Below, preferably 0.5 μmol / inch 2 Below, more preferably 0.4 μmol / inch 2 Below, more preferably 0.3 μmol / inch 2 Below, particularly preferably 0.2 μmol / inch 2 The lower limit is not particularly limited, but is preferably 0.05 μmol / inch 2 More preferably 0.1 μmol / inch 2 above.

[0056] On the other hand, the maximum value of the calcium salt adhesion amount is in the range of 0.6 μmol / inch 2 Below, preferably 0.55 μmol / inch 2 Below, more preferably 0.50 μmol / inch 2The lower limit is not particularly limited, but is preferably 0.1 μmol / inch 2 More preferably 0.2 μmol / inch 2 More preferably, 0.3 μmol / inch 2 Above, particularly preferably 0.4 μmol / inch 2 above.

[0057] If the maximum amount of calcium salt attached is in the range of 0.6 μmol / inch 2 The maximum amount of calcium salt adhesion is particularly in the range of 0.05 μmol / inch. 2 When the above values ​​are used, there is a tendency to obtain excellent image quality (uneven bleeding). It should be noted that the above-mentioned adhesion amount range is the maximum adhesion amount, and there may be an adhesion amount area less than the maximum adhesion amount on the recording medium. On the recording medium, the light-colored part of the image can reduce the adhesion amount of calcium salt according to the ink adhesion amount, or the adhesion amount can be made constant.

[0058] It should be noted that the amount of calcium salt attached [μmol / inch 2 ]Can pass the amount of treatment liquid attached [mg / inch 2 ] and the calcium salt concentration [mol / kg]. 2 ]Preferably, the amount of calcium ions attached is [μmol / inch 2 ]. That is, the number of moles of the calcium salt is preferably the number of moles of calcium contained in the calcium salt.

[0059] The amount of the treatment liquid applied is preferably 0.1 to 5 mg / inch per unit area of ​​the recording medium. 2 , more preferably 0.1 to 4 mg / inch 2 , more preferably 0.1 to 3 mg / inch 2 , particularly preferably 0.3 to 2.5 mg / inch 2 , more preferably 0.3 to 2 mg / inch 2 .

[0060] On the other hand, the amount of the treatment liquid deposited is preferably 1 to 10 mg / inch per unit area of ​​the recording medium. 2 , more preferably 1 to 7 mg / inch 2 , more preferably 1 to 5 mg / inch 2 , particularly preferably 1.5 to 4 mg / inch 2 , more preferably 1.5 to 3.5 mg / inch2 .

[0061] When the amount of treatment liquid attached is large, the number of treatment liquid droplets sprayed in one pass also increases, so mist is more likely to be generated, and there is a tendency for clogging recovery to be slightly poor. In addition, it has recently been found that the amount of calcium salt attached [μmol / inch] has a particular influence on clogging recovery. 2 ] rather than the amount of treatment fluid attached [mg / inch 2 If the range of the treatment liquid adhesion amount is within the above range, there is a tendency for the nozzle clogging recovery, image quality (uneven bleeding) and whitening reduction of the printed matter to be better. It should be noted that it is also preferred to set the range of the maximum adhesion amount of the treatment liquid to the above adhesion amount range.

[0062] The maximum weight of each drop of the treatment liquid is preferably in the range of 0.1 to 30 ng, more preferably 0.5 to 5 ng, more preferably 1 to 5 ng, further preferably 2 to 4 ng, and particularly preferably 2.5 to 3.5 ng.

[0063] On the other hand, the maximum weight range of each drop of the treatment liquid is preferably 5 to 30 ng, more preferably 5 to 25 ng, further preferably 7 to 20 ng, and particularly preferably 9 to 15 ng.

[0064] This can further increase the contact opportunities between the treatment liquid and the ink on the recording medium, thereby achieving better image quality (bleeding unevenness) and tending to achieve better nozzle clogging recovery properties.

[0065] 1.1.2 Recording Media

[0066] In the recording method according to the present embodiment, in the treatment liquid attaching step and the ink attaching step described later, the surface temperature of the recording medium to be attached is preferably 45° C. or lower. Further, it is preferably 40° C. or lower, preferably 35° C. or lower, more preferably 30° C. or lower, and further preferably 25° C. or lower. In addition, room temperature without heating is particularly preferred.

[0067] The lower limit of the surface temperature is not particularly limited, but is preferably 10° C. or higher, more preferably 15° C. or higher, further preferably 20° C. or higher, further preferably 30° C. or higher, more preferably 35° C. or higher, and further preferably 38° C. or higher.

[0068] As a method for promoting the evaporation of water from the ink or reaction liquid attached to the recording medium, a method of heating the recording medium using hot air or a platen heater is also considered. However, with such a heating method, the ink near the nozzle is also promoted to dry due to the heat, and the clogging recovery is particularly prone to deterioration. In addition, if the foreign matter generated near the nozzle is solidified due to heating, the clogging recovery is particularly poor. Therefore, in the case of the surface temperature below the range, there is a tendency for the clogging recovery to be more excellent, so it is preferred. On the other hand, in the case of the surface temperature above the range, there is a tendency for the image quality to be more excellent, so it is preferred.

[0069] The recording medium for forming an image using the recording method of the present embodiment may have a recording surface that absorbs liquids such as an ink composition, or may not have a recording surface that absorbs liquids. Therefore, there are no particular restrictions on the recording medium, and for example, liquid-absorbing recording media such as paper and cloth, liquid-low-absorbing recording media such as printing paper, and liquid-non-absorbing recording media such as metal, glass, film, and polymers can be cited. However, the excellent effect of the recording method of the present embodiment is more significant when recording images on low-absorbing or non-absorbing recording media. That is, according to the recording method of the present embodiment, even a low-absorbing recording medium or a non-absorbing recording medium that is more prone to uneven seepage can obtain excellent image quality.

[0070] The recording medium with low liquid absorption or non-liquid absorption refers to a recording medium having the property of not absorbing liquid at all or hardly absorbing liquid. Quantitatively speaking, the recording medium with low liquid absorption or non-liquid absorption refers to a recording medium with a low liquid absorption from the start of contact to 30 msec in the Bristow method. 1 / 2 The water absorption is 10mL / m 2 The Bristow method is the most popular method for measuring the amount of liquid absorbed in a short period of time, and is also 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 - Bristow Method" of "JAPAN TAPPI Pulp Test Method 2000 Edition". In contrast, a recording medium having liquid absorption refers to a recording medium that does not have liquid non-absorption and liquid low absorption. It should be noted that in this specification, low liquid absorption and liquid non-absorption are sometimes referred to as low absorption and non-absorption.

[0071] As liquid non-absorbent recording media, for example, films or plates of plastics such as polyvinyl chloride, polyethylene, polypropylene, polyethylene terephthalate (PET), plates of metals such as iron, silver, copper, aluminum, or metal plates or plastic films made by evaporating these various metals, plates of alloys such as stainless steel or true casting, etc. can be listed. In addition, recording media coated with plastics on substrates such as paper, recording media bonded with plastic films on substrates such as paper, plastic films without an absorption layer (receiving layer), etc. can also be illustrated. As the plastics mentioned here, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polystyrene, polyurethane, polyethylene, polypropylene, etc. can be listed.

[0072] In addition, as recording media with low liquid absorption, for example, there can be listed recording media having a low absorption coating layer provided on the surface. For example, as recording media whose substrate is paper, there can be listed printing papers such as coated paper, coated paper, and cast paper. As recording media whose substrate is a plastic film, there can be listed recording media whose surfaces are coated with hydrophilic polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, polystyrene, polyurethane, polyethylene, polypropylene, etc., and recording media coated with particles of silica, titanium, etc. together with an adhesive.

[0073] The liquid-absorbing recording medium is not particularly limited, and examples thereof include ordinary paper such as electrophotographic paper having high liquid permeability, and inkjet paper (inkjet paper having an ink-absorbing layer composed of silica particles or alumina particles, or an ink-absorbing layer composed of a hydrophilic polymer such as polyvinyl alcohol (PVA) or polyvinyl pyrrolidone (PVP). In addition, examples of the liquid-absorbing recording medium include cloth, nonwoven fabric, and the like.

[0074] It should be noted that the recording medium may be colorless and transparent, semi-transparent, colored and transparent, colored and opaque, colorless and opaque, etc. In addition, the recording medium itself may be colored, semi-transparent or transparent.

[0075] In the above examples, the recording medium is preferably a low-absorption recording medium or a non-absorption recording medium. Thus, the effect of the present invention can be further enjoyed. That is, such a recording medium is more prone to uneven bleeding because the ink composition is more difficult to wet and spread, but according to the recording method involved in this embodiment, even such a recording medium can achieve excellent reduction in uneven bleeding.

[0076] 1.1.3 Treatment fluid

[0077] Hereinafter, the components contained in the treatment liquid used in the treatment liquid attachment process are described. It should be noted that the treatment liquid is not an ink composition for coloring the recording medium, but an auxiliary liquid used together with the ink composition for coloring. In addition, the treatment liquid may contain a coloring material such as a pigment, preferably 0.2% by mass or less, more preferably 0.1% by mass or less, and further preferably 0.05% by mass or less, with a lower limit of 0% by mass, relative to the total mass of the treatment liquid. The treatment liquid preferably does not contain a coloring material.

[0078] 〔Coagulant〕

[0079] The processing liquid used in the recording method according to the present embodiment contains a coagulant which is a calcium salt, and the content of the calcium salt relative to the total mass of the processing liquid is 0.35 mol / kg or less.

[0080] Calcium salt has the effect of agglomerating the coloring material or the resin particles by reacting with the coloring material contained in the ink, the resin particles that may be contained in the ink, etc. Such agglomeration can, for example, improve the color development of the coloring material, improve the fixability of the resin particles and / or increase the viscosity of the ink.

[0081] It should be noted that coagulants other than calcium salts have lower reactivity than calcium salts, and therefore cannot obtain sufficient image quality. In addition, when cationic polymers are used as coagulants, the clogging recovery during simultaneous injection is particularly poor, which is presumably because particularly large foreign matter is generated in the reaction with the ink. In addition, when coagulants other than calcium salts are used, even if the concentration increases due to evaporation of water caused by air supply, the reactivity is difficult to improve.

[0082] Calcium salt is a compound composed of calcium ion and anion. The anion constituting the calcium salt is an inorganic ion or an organic ion. As such inorganic ions, chloride ion, bromide ion, iodide ion, nitrate ion, sulfate ion, hydroxide ion, etc. can be listed. As organic ions, organic acid ions can be listed, for example, carboxylic acid ion, formate ion, etc. can be listed.

[0083] Among them, the calcium salt is preferably a calcium salt of an organic acid. Calcium salts of organic acids tend to have better abrasion resistance than calcium salts composed of inorganic ions.

[0084] As specific examples of calcium salts, calcium carbonates such as heavy calcium carbonate and light calcium carbonate, calcium nitrate, calcium chloride, calcium sulfate, calcium hydroxide, calcium formate (molecular weight 130.1), calcium propionate (molecular weight 186.2), calcium acetate, calcium lactate, etc. can be listed. These calcium salts can be used alone or in combination of two or more. It should be noted that these calcium salts can also have hydration water in the raw material form, for example, calcium nitrate tetrahydrate (molecular weight 236.2), calcium chloride dihydrate (molecular weight 236.2), calcium acetate monohydrate (molecular weight 176.2), calcium lactate pentahydrate (molecular weight 308.3), etc. can be listed.

[0085] The content of calcium salt relative to the total mass of the treatment liquid is 0.35 mol / kg or less, preferably 0.32 mol / kg or less, more preferably 0.30 mol / kg or less. The lower limit is not particularly limited, but is preferably 0.01 mol / kg or more, more preferably 0.05 mol / kg or more, further preferably 0.10 mol / kg or more, and particularly preferably 0.20 mol / kg or more.

[0086] The content of the calcium salt is preferably 10.0% by mass or less, more preferably 0.1 to 6% by mass, further preferably 1.0 to 5% by mass, and particularly preferably 1.5 to 4% by mass, relative to the total mass of the treatment liquid.

[0087] 〔Water-soluble low molecular weight organic compounds〕

[0088] The processing liquid used in the recording method of this embodiment may contain a water-soluble low-molecular organic compound. The water-soluble low-molecular organic compound may be an organic solvent whose monomer is liquid at room temperature or a compound whose monomer is solid at room temperature. An organic solvent is preferred.

[0089] Here, in a water-soluble low-molecular organic compound, "water-soluble" means that the solubility in 100g of water at 20°C exceeds 10g. The method for determining the solubility of a water-soluble low-molecular organic compound is as follows. First, a specified amount of compound is mixed in 100g of water at 20°C and stirred for 30 minutes. After stirring, for a compound that is liquid at room temperature, if no phase separation or sea island structure is formed, it is judged to be dissolved. In addition, for a compound that is solid at room temperature, if no dissolved residue is left, it is judged to be dissolved.

[0090] Thus, when a predetermined amount of the compound is mixed in 100 g of water, the largest predetermined amount among the predetermined amounts judged to be dissolved is taken as the solubility. A low molecular weight organic compound having a solubility exceeding 10 g is taken as a water-soluble low molecular weight organic compound.

[0091] It should be noted that the water-soluble low-molecular organic compound may be a compound that is completely miscible with water or a compound that is miscible with water.

[0092] In this specification, "completely miscible with water" means that water and the organic compound are mutually soluble, that is, the solubility of the organic compound in 100 g of water at 20°C is infinite. In addition, "miscible with water" means that water and the organic compound have limited solubility, that is, the solubility of the organic compound in at least 100 g of water at 20°C exceeds 10 g.

[0093] The solubility of the water-soluble low-molecular organic compound exceeds 10 g, but the upper limit is not limited and may be infinite. The solubility is preferably 11 g or more, and more preferably 50 g or more.

[0094] In the water-soluble low-molecular organic compound, "low molecular weight" means a molecular weight of 500 or less. The molecular weight is preferably 400 or less, more preferably 300 or less, and further preferably 50-200.

[0095] As the water-soluble low-molecular organic compound, it is preferred to contain a compound having a normal boiling point of 150 to 350°C. The normal boiling point is more preferably 150 to 300°C. In addition, the water-soluble low-molecular organic compound preferably contains a compound having a melting point of 90°C or less. Furthermore, it is preferred to contain a compound having a melting point of 80°C or less. In addition, the melting point is preferably -70°C or more.

[0096] Examples of the water-soluble low-molecular organic compound include resin-dissolving substances, polyols, glycol ethers, alkanolamines, etc. The resin-dissolving substance is preferably selected from amides, sulfur-containing solvents, and cyclic ethers.

[0097] Among them, resin-soluble substances, polyols, and glycol ethers are preferred.

[0098] More preferably, there can be mentioned any resin dissolving substance of amides, sulfur-containing solvents, and cyclic ethers having a normal boiling point of 150 to 300° C., and any compound of polyols and glycol ethers having a normal boiling point of 150 to 250° C. Other water-soluble low molecular weight organic compounds may be contained as required.

[0099] The water-soluble low molecular weight organic compound preferably contains 50% by mass or less relative to the total mass of the treatment liquid. In addition, it is preferably contained at least 1% by mass relative to the total mass of the treatment liquid. Furthermore, it is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, and particularly preferably 20 to 30% by mass.

[0100] <Resin dissolved substances>

[0101] Examples of the resin dissolving substance include amides, sulfur-containing solvents, and cyclic ethers. Among them, any one of amides, sulfur-containing solvents, and cyclic ethers having a normal boiling point of 150 to 300° C. is preferred. It should be noted that the resin dissolving substance refers to an organic compound that has the function of dissolving the resin and improving the abrasion resistance, but is not limited to this function.

[0102] Examples of the amides include cyclic amides (lactams) such as 2-pyrrolidone (2P), 2-piperidone, ε-caprolactam (CPL), N-methyl-ε-caprolactam, N-cyclohexyl-2-pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, N-butylpyrrolidone, 5-methyl-2-pyrrolidone, β-propiolactam, and ω-enantholactam, and N,N-dimethylacetoacetamide, N,N-diethylacetoacetamide, N-methylacetoacetamide, and N,N-dimethyl Chain amides such as isobutyric acid amide, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylpropionamide, 3-methoxy-N,N-dimethylpropionamide (DMPA), 3-n-butoxy-N,N-dimethylpropionamide, 3-methoxy-N,N-diethylpropionamide, 3-methoxy-N,N-methylethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, and 3-ethoxy-N,N-diethylpropionamide. Among them, any one of 2-pyrrolidone (2P), ε-caprolactam (CPL), and 3-methoxy-N,N-dimethylpropionamide (DMPA) is more preferred, and there is a tendency that the storage stability of the treatment liquid can be further improved.

[0103] Examples of the sulfur-containing solvent include 3-methylsulfolane, sulfolane, ethyl isopropyl sulfone, ethyl methyl sulfone, dimethyl sulfone, dimethyl sulfoxide (DMSO), diethyl sulfoxide, tetramethylene sulfoxide, and methyl phenyl sulfoxide. Among them, dimethyl sulfoxide (DMSO) is more preferred because it tends to provide a more excellent storage stability of the treatment solution.

[0104] Examples of the cyclic ethers include dimethyl isosorbide, 3-methyl-3-oxetanemethanol, 3-ethyl-3-oxetanemethanol (DMHD), 2-hydroxymethyloxetane, tetrahydrofurfuryl alcohol, sorbitol, glycerol formal, 1,4-dioxane-2,3-diol, and dihydro-levulinic acid ketone. Among them, 3-ethyl-3-oxetanemethanol (DMHD) is more preferred because it tends to provide a more excellent storage stability of the treatment solution.

[0105] <Polyols, glycol ethers>

[0106] Examples of the water-soluble low-molecular organic compound other than the resin-dissolving substance include polyols and glycol ethers, among which polyols and glycol ethers having a normal boiling point of 150 to 250°C are preferred.

[0107] (Polyols)

[0108] The polyol is preferably a diol or a compound in which diol molecules are condensed between hydroxyl groups. In this case, it is a compound having two hydroxyl groups.

[0109] In addition, examples of polyols include compounds in which hydrogen atoms possessed by diols or compounds obtained by intermolecular condensation of diols with hydroxyl groups are replaced by hydroxyl groups. In this case, the compounds have three or more hydroxyl groups.

[0110] The diol unit in the diol constituting the polyol or the compound formed by intermolecular condensation of diols between hydroxyl groups preferably has 2 to 10 carbon atoms, more preferably 3 to 8. The number of carbon atoms in the molecule of the polyol is preferably 2 to 15, more preferably 3 to 10. The normal boiling point of the polyol is preferably 150 to 250°C.

[0111] Examples of the polyols having a normal boiling point of 150 to 250° C. include ethylene glycol (normal boiling point of 198° C., miscible with water), diethylene glycol (normal boiling point of 244° C., completely miscible with water), 1,2-propylene glycol (propylene glycol: PG) (normal boiling point of 188° C., completely miscible with water), dipropylene glycol (normal boiling point of 227° C., completely miscible with water), 1,2-butylene glycol (normal boiling point of 193° C., miscible with water), 1,2-pentanediol (normal boiling point of 210° C., miscible with water), 1,2-hexanediol (1,2HD) (normal boiling point of 223° C., completely miscible with water), 1,3-propylene glycol (normal boiling point of 214° C., completely miscible with water), 1,4-butylene glycol (normal boiling point of 228° C., completely miscible with water), and 2,3-butylene glycol (normal boiling point of 177° C., miscible with water). , 1,3-butanediol (standard boiling point is 207°C, completely miscible with water), 3-methyl-1,3-butanediol (standard boiling point is 203°C, completely miscible with water), 2-methyl-1,3-propanediol (standard boiling point is 214°C, completely miscible with water), 2,2-dimethyl-1,3-propanediol (standard boiling point is 208°C, solubility is 83 [g / 100g water]), 2-methylpentane-2,4- diol (normal boiling point 197°C, completely miscible with water), 2,5-dimethyl-2,5-hexanediol (normal boiling point 218°C, solubility 14 [g / 100g water]), 1,5-pentanediol (normal boiling point 242°C, miscible with water), 3-methyl-1,5-pentanediol (normal boiling point 250°C, completely miscible with water), 1,6-hexanediol (normal boiling point 250°C, miscible with water), etc. As the polyols, polyols having 10 or less carbon atoms are more preferred.

[0112] Among the polyols, alkanediols having a normal boiling point of 150 to 250° C. and a carbon number of 10 or less are more preferred, and alkanediols having a normal boiling point of 150 to 250° C. and a carbon number of 6 or less are further preferred. Examples of the alkanediols include ethylene glycol, propylene glycol, 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, and the like as 1,2-alkanediols, and 1,3-propanediol, 1,3-butanediol, and the like.

[0113] (Diol ethers)

[0114] Glycol ethers are compounds formed by etherifying one or more hydroxyl groups of a diol. Here, the diol also includes a diol formed by condensation of two or more molecules of a diol between the hydroxyl groups of the molecules.

[0115] As the above-mentioned glycol ethers, monoethers or diethers of alkylene glycols are preferred. As the above-mentioned ethers obtained by etherification, alkyl ethers are preferred. The alkylene group of the alkylene glycol constituting the glycol ethers and the alkyl group of the alkyl ethers independently preferably have 1 to 5 carbon atoms, more preferably 2 to 4 carbon atoms. Glycol ethers having a normal boiling point of 150 to 250°C are preferred.

[0116] Examples of glycol ethers include ethylene glycol monomethyl ether (completely miscible with water), ethylene glycol monoethyl ether (miscible with water), ethylene glycol monoisopropyl ether (solubility: 100 [g / 100 g water]), ethylene glycol monopropyl ether (miscible with water), ethylene glycol monoisobutyl ether (solubility: 75.5 [g / 100 g water]), ethylene glycol mono-tert-butyl ether (miscible with water), ethylene glycol monobutyl ether (solubility: 100 [g / 100 g water]), Alkylene glycol dialkyl ethers (glyme dimethyl ethers) such as diethylene glycol monomethyl ether (completely miscible with water), diethylene glycol monoethyl ether (completely miscible with water), diethylene glycol monoisopropyl ether (miscible with water), diethylene glycol monoisobutyl ether (completely miscible with water), diethylene glycol monobutyl ether (completely miscible with water), triethylene glycol monomethyl ether (completely miscible with water), triethylene glycol monoethyl ether (completely miscible with water), triethylene glycol diol monobutyl ether (miscible with water).

[0117] In addition, among the above-mentioned glycol ethers, diethers are more preferred because they tend to dissolve or swell the resin in the ink more easily than monoethers, and tend to improve the abrasion resistance of the formed image. On the other hand, monoethers are preferred from the viewpoint of excellent storage stability of the treatment liquid.

[0118] In the treatment liquid used in the recording method according to the present embodiment, it is preferred that 40% by mass or less, more preferably 30% by mass or less of any one of polyols and glycol ethers be contained as a water-soluble low-molecular organic compound relative to the total mass of the treatment liquid. In addition, as a lower limit, it is 0% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more relative to the total mass of the ink composition.

[0119] In addition, it is more preferred that the above content range is set to contain any one of polyols and glycol ethers with a normal boiling point of 150 to 250°C, further preferably contain alkanediols with a normal boiling point of 150 to 250°C and a carbon number of 10 or less, and particularly preferably contain alkanediols with a normal boiling point of 150 to 250°C and a carbon number of 6 or less.

[0120] <Other compounds>

[0121] The processing liquid used in the recording method according to the present embodiment may contain other water-soluble low-molecular organic compounds as necessary.

[0122] (Alkanolamines)

[0123] The treatment liquid may contain alkanolamines as water-soluble low molecular organic compounds. Alkanolamines refer to compounds having hydroxyl groups and amino groups on an alkane skeleton. The number of hydroxyl groups in the molecule of the alkanolamines is 1 or more, preferably 1 to 5, and more preferably 2 to 3. The number of carbon atoms in the molecule of the alkanolamines is preferably 1 to 20, more preferably 2 to 10, and further preferably 6 to 9. The number of carbon atoms per alkane skeleton of the alkane skeleton is preferably 1 to 6, and more preferably 2 to 4. The number of amino groups in the molecule of the alkanolamines is 1 or more, preferably 1 to 5, and more preferably 1 to 2.

[0124] The alkanolamines are not particularly limited, and examples thereof include ethanolamine (miscible with water), N-methylethanolamine (solubility: 100 [g / 100 g water]), N,N-dimethylethanolamine (completely miscible with water), N-ethylethanolamine (miscible with water), N-butylethanolamine (miscible with water), N,N-diethylethanolamine (miscible with water), diethanolamine (solubility: 100 [g / 100 g water]), N-methyldiethanolamine (solubility: 100 [g / 100 g water]), N-ethyldiethanolamine (miscible with water), N-butyldiethanolamine (miscible with water), N-tert-butyldiethanolamine (completely miscible with water), triethanolamine (completely miscible with water), isopropanolamine (miscible with water), N,N-dimethylisopropanolamine (completely miscible with water), N,N -diethylisopropanolamine (mixed with water), diisopropanolamine (solubility is 87 [g / 100g water]), triisopropanolamine (solubility is 83 [g / 100g water]), diethanolisopropanolamine (mixed with water), ethanoldiisopropanolamine (mixed with water), N,N-dimethylpropanolamine (mixed with water), 2-amino-1-propanol (completely mixed with water), 2-amino-2-methyl-1-propanol (completely mixed with water), 5-amino-1-pentanol (mixed with water), 2-amino-2-methyl-1,3-propanediol (mixed with water), 2-amino-2-hydroxymethyl-1,3-propanediol (mixed with water), 3-amino-1,2-propanediol (mixed with water), 3-methylamino-1,2-propanediol (completely mixed with water), tripropanolamine, and tributanolamine. Among them, triethanolamine and triisopropanolamine are preferred, and triisopropanolamine is more preferred. The alkanolamines may be used alone or in combination of two or more.

[0125] When the alkanolamines are contained, the content is preferably 1% by mass or less, more preferably 0.05 to 0.5% by mass, based on the total mass of the treatment liquid.

[0126] (Polyols with a normal boiling point exceeding 280°C)

[0127] The treatment liquid preferably does not contain more than 3% by mass of a polyol having a normal boiling point of more than 280° C. as a water-soluble low molecular weight organic compound relative to the total mass of the treatment liquid. More preferably, it does not contain more than 1% by mass, and even more preferably, it does not contain more than 0.5% by mass. Even more preferably, it does not contain more than 0.1% by mass.

[0128] In this case, the processing liquid may or may not contain a polyol having a standard boiling point exceeding 280°C, and even if contained, the content is below the above-mentioned content. If the content of the polyol having a standard boiling point exceeding 280°C is within the above-mentioned range, it is possible to prevent the drying property of the processing liquid from being greatly reduced, and as a result, even when recording is performed on a low-absorbent or non-absorbent recording medium, there is a tendency to prevent the fixability of the image from being reduced. In addition, even when the temperature of the recording medium during heat drying is relatively low, there is a tendency to be able to perform sufficient drying. Examples of such polyols having a standard boiling point exceeding 280°C include glycerin (standard boiling point is 290°C), and alkanolamines such as triisopropanolamine are not contained.

[0129] 〔water〕

[0130] The processing liquid used in the recording method according to the present embodiment may contain water, and is preferably an aqueous processing liquid. A composition containing at least water as a main solvent component (liquid medium component) of the composition is referred to as an aqueous composition.

[0131] Examples of water include pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water, and water with reduced ionic impurities such as ultrapure water. In addition, if water is sterilized by ultraviolet irradiation or addition of hydrogen peroxide, the generation of bacteria or fungi can be suppressed when the treatment solution is stored for a long time.

[0132] The content of water in the liquid medium component is preferably 30% by mass or more, more preferably 30 to 99% by mass. Further, it is preferably 30 to 95% by mass, more preferably 40 to 90% by mass, and even more preferably 50 to 80% by mass. It should be noted that the liquid medium refers to a solvent component such as water or an organic solvent.

[0133] In addition, the water content is preferably 30% by mass or more, more preferably 40% by mass or more, more preferably 45% by mass or more, and particularly preferably 50% by mass or more relative to the total mass of the treatment liquid. The upper limit of the water content is not particularly limited, for example, preferably 99% by mass or less, further preferably 90% by mass or less, and more preferably 80% by mass or less relative to the total mass of the treatment liquid.

[0134] 〔Surfactant〕

[0135] The processing liquid used in the recording method of this embodiment may also contain a surfactant. The surfactant has the function of adjusting the surface tension of the processing liquid, for example, adjusting the wettability with the recording medium. Among the surfactants, for example, acetylene glycol-based surfactants, silicone-based surfactants, and fluorine-based surfactants can be preferably used, and silicone-based surfactants are more preferred.

[0136] The acetylene glycol-based surfactant is not particularly limited, and examples thereof include SURFYNOL 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, and DF110D (all of the above are trade names, Air Products & Chemicals Co., Ltd.), 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 of the above are trade names, manufactured by Nissin Chemical Industry Co., Ltd.), ACETYLENOLE 00, E00P, E40, E100 (all of the above are trade names, manufactured by Kawaken Fine Chemicals Co., Ltd.).

[0137] The silicone surfactant is not particularly limited, but preferably a polysiloxane compound is used. The polysiloxane compound is not particularly limited, but examples thereof include polyether-modified organosiloxanes. Examples of commercially available products of the polyether-modified organosiloxane include BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, and BYK-348 (these are trade names, manufactured by BYK-Chemie JAPAN Co., Ltd.), 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, and KF-6017 (these are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), SILFACE SAG002, 005, 503A, 008 (these are trade names, manufactured by Nissin Chemical Industry Co., Ltd.) and the like.

[0138] As the fluorine-based surfactant, a fluorine-modified polymer is preferably used. Specific examples thereof include BYK-3440 (manufactured by BYK-Chemie JAPAN Co., Ltd.), SURFLON S-241, S-242, S-243 (these are trade names, manufactured by AGC Seimi Chemical Co., Ltd.), and FTERGENT 215M (manufactured by NEOS Co., Ltd.).

[0139] When the treatment liquid contains a surfactant, it may contain multiple surfactants. The content of the surfactant in the treatment liquid can be 0.1% by mass or more and 2% by mass or less relative to the total mass of the treatment liquid, preferably 0.2% by mass or more and 1.5% by mass or less, and more preferably 0.3% by mass or more and 1.0% by mass or less.

[0140] [Other ingredients]

[0141] The processing liquid used in the recording method involved in this embodiment may contain additives, resin dispersants, preservatives / mildewproof agents, rust inhibitors, chelating agents, viscosity modifiers, antioxidants and other components in addition to the above-mentioned components as long as the function is not impaired.

[0142] Examples of the additive include ureas, amines, sugars, and the like.

[0143] Examples of ureas include urea, ethylene urea, tetramethyl urea, thiourea, 1,3-dimethyl-2-imidazolidinone, and betaines (trimethylglycine, triethylglycine, tripropylglycine, triisopropylglycine, N,N,N-trimethylalanine, N,N,N-triethylalanine, N,N,N-triisopropylalanine, N,N,N-trimethylmethylalanine, carnitine, acetylcarnitine, and the like).

[0144] Examples of the amines include diethanolamine, triethanolamine, triisopropanolamine, etc. Ureas and amines can also function as pH adjusters.

[0145] Examples of the sugars include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol (sorbitol), maltose, cellobiose, lactose, sucrose, trehalose, and maltotriose.

[0146] 1.2 Ink Adhesion Process

[0147] The method includes an ink attaching step of causing a water-based ink composition containing a coloring material to be ejected from an inkjet head and attached to a recording medium.

[0148] 1.2.1 Attachment method

[0149] The recording method according to the present embodiment performs the above-mentioned treatment liquid attachment step and ink attachment step by scanning while moving the treatment liquid inkjet head and the ink inkjet head relative to the recording medium, and is performed in a manner that the above-mentioned treatment liquid and ink composition are attached to the same scanning area by the same scanning. Such an attachment method can be realized by the above-mentioned or later-mentioned inkjet head configuration.

[0150] Thus, the processing liquid and the ink composition are overlapped and deposited in the same scan area by the same scan.

[0151] The amount of ink composition deposited per unit area of ​​the recording medium is preferably 0.5 to 40 mg / inch. 2 .

[0152] Furthermore, 0.5 to 20 mg / inch is preferred. 2 , more preferably 1 to 17 mg / inch 2 , more preferably 2 to 15 mg / inch 2 , particularly preferably 3 to 12 mg / inch 2 , more preferably 4 to 10 mg / inch 2 .

[0153] On the other hand, the amount of the ink composition deposited per unit area of ​​the recording medium is preferably 1 to 40 mg / inch. 2 , more preferably 2 to 34 mg / inch 2 , more preferably 4 to 30 mg / inch 2 , particularly preferably 6 to 24 mg / inch 2 , more preferably 8 to 20 mg / inch 2 .

[0154] The above-mentioned adhesion amount of the ink composition may be within the range of the maximum adhesion amount of the ink composition per unit area of ​​the recording medium.

[0155] In the recording method according to the present embodiment, the number of scans to make the ink composition adhere to the same scan area is preferably 10 times or less, more preferably 8 times or less. The lower limit is preferably 2 times or more, more preferably 4 times or more, and even more preferably 6 times or more.

[0156] On the other hand, the number of scans to make the ink composition adhere to the same scan area is preferably 10 times or less, more preferably 5 times or less, further preferably 3 times or less, and particularly preferably 2 times or less. It is further preferably 1 time or less. It should be noted that the number of scans is 1 time or more.

[0157] The fewer the number of the above-mentioned scans, the faster the recording speed, so it is preferred. However, since the number of processed droplets increases each time, the clogging recovery is likely to deteriorate. In addition, since the number of ink drops each time also increases, the ink drops are likely to ooze out, and the image quality is likely to deteriorate. In addition, the ink drops gather, and the filling of the ink covering the recording medium is also likely to deteriorate. If it is within the range of the above-mentioned number of scans, there is a tendency to achieve good recording speed while making the clogging recovery and image quality (uneven oozing) excellent.

[0158] It should be noted that the number of scans mentioned above refers to the number of scans performed on a certain ink composition even when multiple ink compositions are used. In addition, in the case of completely simultaneous jetting, the number of scans to attach the ink composition to the same scan area is the same as the number of scans to attach the treatment liquid to the same scan area.

[0159] When recording an arbitrary area, the number of times the inkjet head passes over the area is also referred to as a “pass.” For example, when four main scans are performed to deposit ink on the same area, the number of passes is referred to as four passes.

[0160] For example, in Figure 3 In the case where the length of one sub-scan in the sub-scanning direction (SS direction) is one quarter of the length of the nozzle array in the sub-scanning direction (SS direction), a rectangular scanning area having a length of one sub-scan in the sub-scanning direction (SS direction) and extending in the main scanning direction (MS direction) is scanned four times. This is the number of scans when observed in this way.

[0161] When the main scanning and the sub scanning are performed alternately, the scanning area is a rectangular area having a length of one sub scanning in the sub scanning direction and extending in the main scanning direction.

[0162] Or, for example, in Figure 3 In the embodiment, the sub-scanning is not performed, and the main scanning for attaching ink is performed 4 times on the same area of ​​the stopped recording medium, so that the number of scans can be 4. In this case, the sub-scanning can be performed after performing the 4 scans.

[0163] When main scanning is performed once or more without performing sub scanning on a recording medium at a fixed position, the scanning area is a rectangular area that is the length of the inkjet head in the sub scanning direction and extends in the main scanning direction.

[0164] The number of scans is also called the number of scans or the number of passes, etc.

[0165] 1.2.2 Ink composition

[0166] Hereinafter, components contained in the ink composition used in the ink adhesion step will be described. The ink composition is an aqueous composition containing a coloring material.

[0167] The composition may be the same as that of the treatment liquid except that the calcium salt or a coagulant other than the calcium salt is not contained and a coloring material is contained as an essential component.

[0168] 〔Coloring materials〕

[0169] The ink composition used in the recording method according to the present embodiment contains a coloring material. Examples of the coloring material include pigments and dyes.

[0170] (pigment)

[0171] As the pigment, for example, carbon black, inorganic pigments including titanium white, organic pigments, etc. can be used.

[0172] As the inorganic pigment, carbon black (CI Pigment Black 7) such as furnace black, lamp black, acetylene black, and channel black, iron oxide, titanium oxide, zinc oxide, and silica can be used.

[0173] Examples of carbon black include No. 2300, 900, MCF88, No. 20B, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, No. 2200B, etc. manufactured by Mitsubishi Chemical Corporation. Examples include Color Black FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Pretex 35, U, V, 140U, Special Black 6, 5, 4A, 4, 250, etc. manufactured by Degussa. Examples include Conductex SC, Raben 1255, 5750, 5250, 5000, 3500, 1255, 700, etc. manufactured by Columbia Carbon Company. Examples include Regal 400R, 330R, 660R, Mogul L, Monarch 700, 800, 880, 900, 1000, 1100, 1300, 1400, and Elftex 12 manufactured by Cabot Corporation.

[0174] Examples of organic pigments include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthraquinone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perindone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, isoindolinone pigments, azomethine pigments, and azo pigments.

[0175] Specific examples of the organic pigment used in the ink composition include the following pigments.

[0176] Examples of cyan pigments include CI Pigment Blue 1, 2, 3, 15:3, 15:4, 15:34, 16, 22, 60, etc.; CI Vat Blue 4, 60, etc. Preferably, one or a mixture of two or more selected from the group consisting of CI Pigment Blue 15:3, 15:4 and 60 can be used.

[0177] Examples of magenta pigments include CI Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57:1, 112, 122, 123, 168, 184, 202, and CI Pigment Violet 19. Preferably, one or a mixture of two or more selected from the group consisting of CI Pigment Red 122, 202 and 209, and CI Pigment Violet 19 can be used. Solid solutions of the above pigments may also be used.

[0178] Examples of the yellow pigment include CI Pigment Yellow, 1, 2, 3, 12, 13, 14C, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 119, 110, 114, 128, 129, 138, 150, 151, 154, 155, 180, and 185. Preferably, one or a mixture of two or more selected from the group consisting of CI Pigment Yellow 74, 109, 110, 128, 138, 155, and 180 can be used.

[0179] Examples of orange pigments include CI Pigment Orange 36 or 43, or a mixture thereof. Examples of green pigments include CI Pigment Green 7 or 36, or a mixture thereof.

[0180] In addition, bright pigments can also be used, as long as they can show bright pigments when attached to a medium, there is no particular limitation, for example, metal particles of one or more alloys (also called metal pigments) selected from the group consisting of aluminum, silver, gold, platinum, nickel, chromium, tin, zinc, indium, titanium and copper, and pearlescent pigments with pearlescent luster. As representative examples of pearlescent pigments, titanium dioxide-covered mica, fish scale foil, bismuth oxychloride and other pigments with pearlescent luster or interference luster can be listed. In addition, bright pigments can also be subjected to surface treatment for inhibiting reaction with water.

[0181] In addition, white pigments may also be used, for example, metal compounds such as metal oxides, barium sulfate, and calcium carbonate may be listed. As metal oxides, for example, titanium dioxide, zinc oxide, silicon dioxide, aluminum oxide, and magnesium oxide may be listed. In addition, white pigments may also be used as particles having a hollow structure.

[0182] The above-mentioned pigments may be used alone or in combination of two or more. From the viewpoint of storage stability such as light resistance, weather resistance, and gas resistance, the pigment is preferably an organic pigment.

[0183] Regarding the volume average particle size (D50) of the pigment, the volume average particle size (D50) when measured by a dynamic light scattering method is 20 nm or more and 300 nm or less, more preferably the volume average particle size (D50) is 30 nm or more and 200 nm or less, and further preferably the volume average particle size (D50) is 40 nm or more and 100 nm or less.

[0184] The volume average particle size can be measured, for example, by a Nanotrac series particle distribution measuring device manufactured by Microtrac Bell Co., Ltd. In addition, as a method for adjusting the volume average particle size, for example, a method for adjusting the degree of pulverization of the pigment before dispersion, a method for adjusting the stirring conditions (such as stirring speed, stirring temperature, etc.) during dispersion, a method for adjusting the filtration using a filter after dispersion, etc. can be cited.

[0185] The pigment may be dispersed using a pigment dispersant. Alternatively, the pigment may be dispersed as a self-dispersible pigment by oxidizing or sulfonating the pigment surface with ozone, hypochlorous acid, fuming sulfuric acid, or the like.

[0186] The pigment dispersant has the function of dispersing the pigment in the ink composition. The pigment dispersant may be water-soluble, but preferably is not completely water-soluble. It is believed that the pigment is dispersed by partially or completely combining with or adsorbing the pigment to increase the hydrophilicity of the pigment surface. The pigment dispersant is preferably a polymer compound, more preferably a resin. It should be noted that the pigment dispersed by the pigment dispersant as a resin is also particularly referred to as a resin-dispersed pigment.

[0187] As the resin of the pigment dispersant, for example, acrylic resins and their salts such as 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, styrene-(meth)acrylic acid copolymer, 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 can be listed. It should be noted that in this specification, a polymer having a skeleton derived from (meth)acrylic acid and not having a skeleton derived from maleic acid or its analogous compounds is referred to as an acrylic resin. It should be noted that in this specification, "(meth)acrylic acid" refers to acrylic acid or methacrylic acid.

[0188] In addition, resins used as pigment dispersants include maleic acid resins and their salts such as styrene-maleic acid copolymers, styrene-maleic anhydride copolymers, vinyl naphthalene-maleic acid copolymers, and vinyl acetate-maleate copolymers; carbamate resins and their salts, whether or not they have a cross-linked structure; polyvinyl alcohols; and resins such as vinyl acetate-crotonic acid copolymers and their salts.

[0189] It should be noted that, in addition to the polymer of the acrylic monomer (acrylic monomer) as described above, the acrylic resin may also be a copolymer of an acrylic monomer and other monomers. For example, an acrylic vinyl resin which is a copolymer of other monomers and a vinyl monomer is also referred to as an acrylic resin. In addition, for example, in the above-mentioned styrene resin, a resin which is a copolymer of a styrene monomer and an acrylic monomer is also included in the acrylic resin. In addition, when referred to as an acrylic resin, its salt or its esterification product is also included.

[0190] Commercially available products of pigment dispersants include, for example, X-200, X-1, X-205, X-220, and X-228 (manufactured by Starlight PMC Co., Ltd.), Nopcos Perth (registered trademark) 6100 and 6110 (manufactured by SAN NOPCO Co., Ltd.), Joncryl 67, 586, 611, 678, 680, 682, and 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, and E-EN10 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).

[0191] Commercially available products of acrylic pigment dispersants include BYK-187, BYK-190, BYK-191, BYK-194N, BYK-199 (manufactured by BYK-Chemie Co., Ltd.), Aron A-210, A6114, AS-1100, AS-1800, A-30SL, A-7250, CL-2 (manufactured by Toagosei Co., Ltd.), and the like.

[0192] Examples of commercially available urethane pigment dispersants include BYK-182, BYK-183, BYK-184, and BYK-185 (manufactured by BYK Chemie Co., Ltd.), TEGO Disperse 710 (manufactured by Evonic Tego Chemi Co., Ltd.), and Borchi (registered trademark) Gen 1350 (manufactured by OMG Borschers Co., Ltd.).

[0193] The pigment dispersant may be used alone or in combination of two or more. The total content of the pigment dispersant is 0.1% by mass or more and 30% by mass or less relative to 100% by mass of the ink, preferably 5% by mass or more and 25% by mass or less, and more preferably 10% by mass or more and 20% by mass or less. By making the content of the pigment dispersant 0.1% by mass or more, the dispersion stability of the pigment can be ensured. In addition, if the content of the pigment dispersant is 30% by mass or less, the viscosity of the ink composition can be suppressed to be relatively small.

[0194] Furthermore, the weight average molecular weight of the pigment dispersant is more preferably not less than 500. By using such a pigment dispersant, odor can be reduced and the dispersion stability of the pigment can be further improved.

[0195] When the pigment is dispersed by a pigment dispersant, the ratio of the pigment to the pigment dispersant is preferably 10:1 to 1:10, and more preferably 4:1 to 1:3.

[0196] The self-dispersible pigment is a pigment whose surface is modified by directly or indirectly bonding one or more functional groups selected from the group consisting of carbonyl group, carboxyl group, aldehyde group, hydroxyl group, sulfone group, ammonium group and salts thereof to the surface.

[0197] Examples of the self-dispersible pigment include organic pigments such as carbon black, azo lakes, insoluble azo pigments, condensed azo pigments, chelated azo pigments, phthalocyanine pigments, perylene pigments, perinone pigments, quinacridone pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, nitro pigments, nitroso pigments, and aniline black; and inorganic pigments such as titanium white, zinc white, lead white, carbon black, red iron oxide, cinnabar, cadmium red, chrome yellow, ultramarine, cobalt blue, cobalt violet, and zinc chromate.

[0198] Among them, the self-dispersible pigment is preferably carbon black, since black can be printed at a high concentration and the ejection reliability is more excellent.

[0199] As the self-dispersible pigment, a preparation prepared by a known method or a commercial product can be used. Examples of commercial products include "Microjet CW1", "Microjet CW2" manufactured by Orient Chemical Industry Co., Ltd., "CAB-O-JET 200", "CAB-O-JET 300" manufactured by Cabot Corporation, and the like.

[0200] (dye)

[0201] A dye can be used as a coloring material in the ink composition. The dye is not particularly limited, and an acid dye, a direct dye, a reactive dye, a basic dye, and a disperse dye can be used.

[0202] The above dyes may be used alone or in combination of two or more.

[0203] Among them, the coloring material is preferably any one of a resin-dispersible pigment, a self-dispersible pigment, and a dye. Such a coloring material can be well dispersed in an aqueous ink, and thus has a tendency to further improve color development and ejection stability.

[0204] The lower limit of the content of the coloring material is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1.0% by mass or more, and further preferably 1.5% by mass or more relative to the total amount of the ink composition. If the content of the coloring material is within the above range, the color development property tends to be more excellent.

[0205] The upper limit of the content of the coloring material is not particularly limited, but is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 7% by mass or less, and particularly preferably 5% by mass or less, relative to the total amount of the ink composition. If the content of the coloring material is within the above range, there is a tendency for the ejection stability to be more excellent.

[0206] 〔water〕

[0207] The ink composition used in the recording method of this embodiment is an aqueous ink composition. "Aqueous" means containing at least water as a solvent component, and may also contain water as a main solvent component. The type or content of water is the same as that of the above-mentioned treatment liquid, and the description is made by replacing "treatment liquid" with "ink composition".

[0208] 〔Water-soluble low molecular weight organic compounds〕

[0209] The ink composition used in the recording method according to the present embodiment may contain a water-soluble low molecular weight organic compound. The type and content of the water-soluble low molecular weight organic compound are the same as those of the above-mentioned treatment liquid, and the description will be made by replacing "treatment liquid" with "ink composition".

[0210] The water-soluble low molecular weight organic compound preferably contains 40% by mass or less of the ink composition of the treatment liquid. In addition, it is preferably contained at least 1% by mass relative to the total mass of the treatment liquid. Furthermore, it is preferably 5 to 30% by mass, more preferably 5 to 25% by mass, and particularly preferably 10 to 25% by mass.

[0211] 〔Surfactant〕

[0212] The ink composition used in the recording method according to the present embodiment may contain a surfactant. The type and content of the surfactant are the same as those of the above-mentioned treatment liquid, and the description will be given by replacing "treatment liquid" with "ink composition".

[0213] 〔Resin particles〕

[0214] The ink composition used in the recording method involved in the present embodiment may also contain resin particles. The resin particles can further improve the adhesion of the image formed by the ink composition attached to the recording medium. As resin particles, for example, resin particles composed of carbamate resins, acrylic resins (including styrene acrylic resins), fluorene resins, polyolefin resins, rosin-modified resins, terpene resins, polyester resins, polyamide resins, epoxy resins, vinyl chloride resins, vinyl chloride-vinyl acetate copolymers, ethylene vinyl acetate resins, etc. can be listed. Among them, carbamate resins, acrylic resins, polyolefin resins, and polyester resins are preferred. These resin particles are mostly processed in the form of emulsions, but they can also be the properties of powders. In addition, the resin particles can be used alone or in combination of two or more.

[0215] Urethane resin is a general term for resins having urethane bonds. Urethane resins include polyether urethane resins having ether bonds in the main chain, polyester urethane resins having ester bonds in the main chain, and polycarbonate urethane resins having carbonate bonds in the main chain. In addition, as the urethane resin, commercially available products can also be used, for example, SUPER FLEX 460, 460s, 840, E-4000 (trade names, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), REZAMINE D-1060, D-2020, D-4080, D-4200, D-6300, D-6455 (trade names, manufactured by Dainichi Seika Industries, Ltd.), TAKELAC WS-6021, W-512-A-6 (trade names, manufactured by Mitsui Chemicals Polyurethanes, Ltd.), SANCURE 2710 (trade name, manufactured by LUBRIZOL), PERMARIN UA-150 (trade name, manufactured by Sanyo Chemical Industries, Ltd.) and the like can be used.

[0216] Acrylic resin is a general term for polymers obtained by polymerizing at least one acrylic monomer such as (meth)acrylic acid or (meth)acrylate as one component, and examples thereof include resins obtained from acrylic monomers, copolymers of acrylic monomers and other monomers, etc. For example, acrylic-vinyl resins, which are copolymers of acrylic monomers and vinyl monomers, etc., can be cited. In addition, for example, styrene and the like can be cited as vinyl monomers.

[0217] As acrylic monomers, acrylamide, acrylonitrile, etc. can also be used. In the resin emulsion using acrylic resin as raw material, commercial products can be used, for example, FK-854 (trade name, manufactured by Chuo Rika Industry Co., Ltd.), MOWINYL952B, 718A (trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), NipolLX852, LX874 (trade name, manufactured by Japan ZEON Co., Ltd.), etc. can be selected for use.

[0218] It should be noted that, in the present specification, the acrylic resin may also be a styrene-acrylic resin described below. In addition, in the present specification, the term (meth)acrylic acid means acrylic acid or methacrylic acid.

[0219] Styrene-acrylic resins are copolymers obtained from styrene monomers and (meth)acrylic monomers, and examples thereof include styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-methacrylic acid-acrylate copolymers, styrene-α-methylstyrene-acrylic acid copolymers, and styrene-α-methylstyrene-acrylic acid-acrylate copolymers. As the styrene-acrylic resin, commercially available products can be used. For example, Joncryl 62J, 7100, 390, 711, 511, 7001, 631, 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 names, manufactured by BASF), MOWINYL 966A, 975N (trade names, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), VINYBLAN 2586 (manufactured by Nissin Chemical Industry Co., Ltd.), etc. can be used.

[0220] The polyolefin resin has olefins such as ethylene, propylene, and butene in the structural skeleton, and known olefins can be appropriately selected and used. As the olefin resin, commercially available products can also be used, for example, Arrow Base CB-1200, CD-1200 (trade name, manufactured by Unitika Co., Ltd.) and the like can be used.

[0221] The glass transition temperature (Tg) of the resin particles is preferably above -50°C and below 200°C, more preferably above 0°C and below 150°C, and further preferably above 50°C and below 100°C. In addition, it is particularly preferably above 50°C and below 80°C. By making the glass transition temperature (Tg) of the resin particles within the above range, there is a tendency for better durability and clogging resistance. The glass transition temperature is measured, for example, using a differential scanning calorimeter "DSC7000" manufactured by HITACHI HI-TECH SCIENCE Co., Ltd. in accordance with JIS K7121 (Method for Determination of Transition Temperature of Plastics).

[0222] The volume average particle size of the resin particles is preferably 10 nm to 300 nm, more preferably 30 nm to 300 nm, further preferably 30 nm to 250 nm, particularly preferably 40 nm to 220 nm. The volume average particle size can be measured by the above method.

[0223] The acid value of the resin of the resin particles is preferably 50 mgKOH / g or less, more preferably 30 mgKOH / g or less, further preferably 20 mgKOH / g or less, and particularly preferably 10 mgKOH / g or less. In addition, the lower limit of the acid value is 0 mgKOH / g or more, preferably 5 mgKOH / g or more, and more preferably 10 mgKOH / g or more. In this case, the image quality is excellent, so it is preferred. The acid value can be measured by the above method.

[0224] When the ink composition contains the resin particles, the content thereof is 0.1% by mass to 10% by mass, preferably 0.5% by mass to 5% by mass, and more preferably 1% by mass to 5% by mass, in terms of solid content, relative to the total mass of the ink composition.

[0225] [Other ingredients]

[0226] The ink composition used in the recording method according to the present embodiment may contain other components. The other components are the same as those of the above-mentioned treatment liquid, and the description will be given by replacing "treatment liquid" with "ink composition".

[0227] 1.3 Air supply process

[0228] The recording method according to the present embodiment includes an air supply step of supplying air to the recording medium in the above-mentioned processing liquid attaching step and ink attaching step.

[0229] In the processing liquid attachment process and the ink attachment process, the so-called air supply process for supplying air to the recording medium is that the air supply process is performed simultaneously with the processing liquid attachment process and the ink attachment process for the portion of the recording medium supported by the recording medium support portion such as the platen, and the conveying process is performed near the portion of the recording medium supported by the recording medium support portion.

[0230] The air supply process is performed on the recording medium on the platen at a position opposite to the inkjet head. The air supply process is performed by supplying air to the recording medium at a position where the process liquid attachment process and the ink attachment process are performed, so as to promote the drying of the process liquid and the ink attached to the recording medium. More specifically, the air supply is performed so that the solvent component of the process liquid or the ink evaporated from the recording medium is removed by the air supply, thereby promoting evaporation.

[0231] For example, the air is not limited to be sent near the surface of the recording medium, and the air may be sent to a position away from the surface of the recording medium.

[0232] The air blowing step may be performed simultaneously with, before, or after the time when the treatment liquid and the ink composition adhere to the recording medium, but is preferably performed after the time when the treatment liquid and the ink composition adhere to the recording medium.

[0233] The preferred wind speed for air supply in the air supply process is 0.5 m / s or more. Furthermore, the preferred wind speed is 1.0 m / s or more, preferably 1.5 m / s or more, more preferably 2.0 m / s or more, and further preferably 2.5 m / s or more. If the wind speed of the air supply is within the above range, there is a tendency that the dryness is further improved and the image quality (uneven seepage) is better. In addition, the vapor of the ink components can sometimes be diffused to reduce condensation on the nozzle surface. It should be noted that the upper limit of the wind speed is not particularly limited, and is preferably 20 m / s or less, more preferably 15 m / s or less, further preferably 10 m / s or less, and particularly preferably 5 m / s or less.

[0234] The wind speed is the maximum wind speed measured within the range of the recording medium at a position supported by the platen, and within the range from the surface of the recording medium to the height of the carriage on which the inkjet head is mounted.

[0235] The air temperature of the air supplied in the air supply process is preferably 80°C or less. Furthermore, it is preferably 45°C or less, preferably 40°C or less, preferably 35°C or less, more preferably 30°C or less, and further preferably 25°C or less. Unheated air is preferred, and air at room temperature is particularly preferred. The lower limit of the air temperature is not particularly limited, but is preferably 10°C or more, more preferably 15°C or more. In addition, it is preferably 20°C or more.

[0236] It should be noted that the air in the air supply process is preferably air at room temperature, but may also be hot air. The air temperature of the hot air is, for example, preferably 80° C. or less, more preferably 80 to 35° C., and further preferably 60 to 35° C. The air temperature is measured at the position where the wind speed is measured in a state where it is not affected by heat other than the temperature of the wind itself.

[0237] The air supply step may be performed using an air supply mechanism capable of supplying air toward the vicinity of the recording surface side of the recording medium supported by the platen, such as a fan.

[0238] 1.4 Secondary drying process

[0239] The recording method involved in this embodiment may further include a secondary drying process of heating the recording medium after the above-mentioned treatment liquid attachment process and ink attachment process. The secondary drying process can be performed using, for example, an appropriate heating mechanism. The secondary drying process is performed by, for example, a post-heater (equivalent to heater 59 in the example of a serial inkjet recording device described later), preferably after passing through the platen. In addition, the heating mechanism is not limited to the heating mechanism of the inkjet recording device, and other drying mechanisms may also be used. Since the image thus obtained can be dried and fixed more fully, for example, the recorded object can be made ready for use as soon as possible.

[0240] The surface temperature of the recording medium reached by heating in the secondary drying process is preferably 50°C or higher. It is preferably 60.0°C or higher and 120.0°C or lower, preferably 70.0°C or higher and 100.0°C or lower, more preferably 70.0°C or higher and 90°C or lower, and further preferably 70°C or higher and 80°C or lower. The surface temperature of the recording medium reached by heating in the secondary drying process is particularly preferably 70°C or higher. If the temperature of the recording medium is within this range, the resin particles can be coated and flattened, and the obtained image can be dried and fixed more fully.

[0241] 1.5 Other processes

[0242] The recording method of this embodiment may include a primary drying step. The primary drying step includes the above-mentioned air supply step, but may include a primary drying step other than the above-mentioned air supply step.

[0243] The primary drying step is a step of drying the recording medium in the above-mentioned treatment liquid adhesion step and ink adhesion step.

[0244] The primary drying process other than the air supply process can be performed by stopping recording and leaving it alone, or by using a drying mechanism to dry it. Examples of the drying method using a drying mechanism include a method of irradiating the recording medium with radiation (infrared rays, etc.) that generates heat (radiation method), a component that contacts the recording medium and transfers heat to the recording medium (conduction method), and a combination of two or more of these methods.

[0245] In the primary drying process, the case where a drying mechanism that heats the recording medium is used as the drying mechanism is particularly referred to as a primary heating process. For example, the above-mentioned drying mechanism corresponds to a conduction type or a radiation type.

[0246] Even when the drying step is performed once, as described above, the surface temperature of the recording medium to which the adhesive is applied is preferably 35° C. or lower.

[0247] In addition, the above-mentioned treatment liquid attachment process and ink attachment process may not be accompanied by a primary heating process. That is, the recording method of this embodiment preferably heats the recording medium at the place where the ink composition and the treatment liquid are attached, without using a heating mechanism for heating the recording medium provided by a member supporting the recording medium, and without using a heating mechanism for heating the recording medium from above. In such a case, the surface temperature of the recording medium in the treatment liquid attachment process and the ink attachment process is likely to be a low temperature below the specified temperature, and there is a tendency for better clogging recovery.

[0248] 1.6 Continuous printing time

[0249] The recording method involved in this embodiment preferably performs continuous recording for more than 0.5 hours, more preferably performs continuous recording for more than 1 hour, more preferably performs continuous recording for more than 1.5 hours, and further preferably performs continuous recording for more than 2 hours. The upper limit is not particularly limited, but preferably performs continuous recording for less than 10 hours, more preferably performs continuous recording for less than 7 hours, and particularly preferably performs continuous recording for less than 5 hours.

[0250] When the continuous recording time is long, the clogging recovery property tends to deteriorate. However, the recording method according to the present embodiment is preferred because it tends to be able to obtain good clogging recovery property even with the above-mentioned continuous recording time.

[0251] The continuous printing time is the time to repeatedly scan and transport the recording medium (sub-scanning, etc.) to continuously record multiple images. In continuous printing, maintenance that takes a long time, such as sucking ink from the inkjet head, is not performed. Maintenance that can be completed in a short time, such as flushing, can also be performed.

[0252] 2. Recording device

[0253] A recording device according to one embodiment of the present invention is a recording device that performs recording on a recording medium using the above-mentioned recording method, and includes the above-mentioned treatment liquid, ink composition, an inkjet head for the treatment liquid, and an inkjet head for the ink.

[0254] According to the recording apparatus of the present embodiment, by performing recording using the above-mentioned recording method, the nozzle clogging recovery property, image quality (blurring unevenness), and whitening reduction property of printed matter are excellent.

[0255] The processing liquid and the ink composition included in the recording device according to the present embodiment are as described above, and thus description thereof will be omitted. Hereinafter, an example of the recording device according to the present embodiment will be described with reference to the drawings.

[0256] 2.1 Serial Recording Device

[0257] Figure 1 It is a schematic cross-sectional view schematically showing a serial-type inkjet recording device 19 . Figure 2 Yes means Figure 1 A perspective view of an example of the structure of the carriage surrounding the inkjet recording device 19. Figure 1 , 2 As shown, the inkjet recording device 19 includes an inkjet head 29, an IR heater 391, a platen heater 49, a heater 59, a cooling fan 69, a preheater 79, a ventilation fan 89, a carriage 99, a platen 119, a carriage moving mechanism 139, a conveying unit 149, and a control unit CONT. The inkjet recording device 19 is Figure 2The control unit CONT shown controls the overall operation of the inkjet recording device 19 .

[0258] The inkjet head 29 includes a treatment liquid inkjet head 29a for discharging a treatment liquid and an ink inkjet head 29b for discharging an ink composition. Recording can be performed on the recording medium M by discharging the treatment liquid and the ink composition from the nozzles of the respective inkjet heads and causing them to adhere.

[0259] In this embodiment, the inkjet head 29 is a serial inkjet head, which performs multiple scans in the main scanning direction relative to the recording medium M to make the ink composition and the processing liquid (hereinafter also referred to as "ink, etc.") adhere to the recording medium M. The inkjet head 29 is installed Figure 2 The inkjet head 29 performs a plurality of scans in the main scanning direction relative to the recording medium M by the operation of the carriage moving mechanism 139 that moves the carriage 99 in the medium width direction of the recording medium M. The medium width direction refers to the main scanning direction of the inkjet head 29. Scanning in the main scanning direction is also referred to as main scanning.

[0260] Figure 3 The inkjet head 29a for ejecting the processing liquid is arranged transversely at the same position as the inkjet head 29b for ejecting the ink composition relative to the conveying direction (T2 direction) of the recording medium M. In this case, when the nozzle row of the inkjet head 29a for ejecting the processing liquid is projected along the head moving direction (MS), it is arranged so as to completely overlap with the nozzle row of the inkjet head 29b for ejecting the ink in the nozzle row direction (SS).

[0261] If this arrangement is adopted, the treatment liquid attachment step and the ink attachment step in the above recording method can be performed by scanning while the treatment liquid inkjet head and the ink inkjet head are moved relative to the recording medium, and the treatment liquid and the ink composition are attached to the same scanning area by the same scanning (completely sprayed at the same time). It should be noted that Figure 3 The nozzle array shown is a nozzle array that ejects ink and the like from each inkjet head.

[0262] Figure 4 The inkjet head 29a for ejecting the processing liquid and the inkjet head 29b for ejecting the ink composition are arranged horizontally at the same position in the upstream 1 / 4 of the conveying direction of the recording medium M (T2 direction). In this case, when the nozzle row of the inkjet head 29a for ejecting the processing liquid is projected along the head moving direction (MS), the nozzle row of the inkjet head 29b for ejecting the ink is arranged to overlap with the upstream 1 / 4 of the conveying direction of the recording medium M in the nozzle row direction (SS).

[0263] If this arrangement is adopted, the treatment liquid attachment step and the ink attachment step in the above recording method can be performed by scanning while the treatment liquid inkjet head and the ink inkjet head are moved relative to the recording medium, and the treatment liquid and the ink composition are attached to the same scanning area by the same scanning (forward injection). It should be noted that Figure 4 The nozzle array shown is a nozzle array that ejects ink and the like in each inkjet head.

[0264] Figure 5 The arrangement indicates that the inkjet head 29a for ejecting the processing liquid does not have a part arranged in the horizontal direction at the same position as the inkjet head 29b for ejecting the ink composition relative to the conveying direction (T2 direction) of the recording medium M. In this case, when the nozzle row of the inkjet head 29a for ejecting the processing liquid is projected along the head moving direction (MS), there is no overlap with the nozzle row of the inkjet head 29b for ejecting the ink in the nozzle row direction (SS).

[0265] If this arrangement is adopted, the process liquid attachment step and the ink attachment step are performed by scanning while the process liquid inkjet head and the ink inkjet head are moved relative to the recording medium, so that the process liquid and the ink composition are not attached to the same scanning area by the same scanning. This is not the recording method of this embodiment.

[0266] The main scanning direction is the direction in which the carriage 99 on which the inkjet head 29 is mounted moves. Figure 1 In FIG. 1 , the direction in which the conveying direction of the recording medium M, that is, the sub-scanning direction, intersects with the arrow SS is shown. Figure 2 In the figure, the width direction of the recording medium M, that is, the direction indicated by S1-S2 is the main scanning direction MS, and the direction indicated by T1→T2 is the sub-scanning direction SS. It should be noted that scanning is performed in the main scanning direction, that is, in either direction of arrow S1 or arrow S2, using one scan. Then, the recording medium M is recorded by repeating the main scanning of the inkjet head 29 and the sub-scanning as the conveyance of the recording medium M for multiple times. That is, the treatment liquid attachment process and the ink attachment process are performed by multiple main scannings in which the inkjet head 29 moves in the main scanning direction and multiple sub-scans in which the recording medium M moves in the sub-scanning direction intersecting the main scanning direction.

[0267] The cartridge 129 for supplying ink and the like to the inkjet head 29 includes a plurality of independent cartridges. The cartridge 129 is detachably mounted on the carriage 99 on which the inkjet head 29 is mounted. Each of the plurality of cartridges can be filled with a different type of ink and the like, and the ink and the like are supplied from the cartridge 129 to each nozzle. It should be noted that in the present embodiment, an example in which the cartridge 129 is mounted on the carriage 99 is shown, but the present invention is not limited thereto, and the cartridge 129 may be provided at a location other than the carriage 99 and supplied to each nozzle through a supply pipe not shown.

[0268] The inkjet head 29 can use a conventionally known method for ejecting liquid. In the present embodiment, a method of ejecting liquid droplets using the vibration of a piezoelectric element, that is, an ejection method of forming ink droplets using the mechanical deformation of an electrostrictive element, is used.

[0269] The inkjet recording device 19 includes a ventilation fan 89, an IR heater 391, and a platen heater 49 for drying the ink or the like ejected from the inkjet head 29 and attached to the recording medium M. A primary drying process can be performed by using these ventilation fans 89, IR heaters 391, and platen heaters 49 in appropriate combination. In the primary drying process, the recording medium M does not necessarily need to be heated, and the ventilation fan 89 may be used alone as an implementation of air supply at normal temperature.

[0270] It should be noted that, if the IR heater 391 is used, the recording medium M can be radiantly heated by infrared radiation from the inkjet head 29 side. As a result, the inkjet head 29 is also easily heated at the same time, but compared with the case of heating the back side of the recording medium M such as the platen heater 49, the temperature can be increased without being affected by the thickness of the recording medium M. In addition, various fans (such as a ventilation fan 89) are also provided, and the various fans blow hot air or air at the same temperature as the environment onto the recording medium M to dry the ink on the recording medium M.

[0271] The platen heater 49 can heat the recording medium M via the platen 119 at a position opposite to the inkjet head 29, so that the ink etc. ejected from the inkjet head 29 can be dried as soon as possible from the time when the ink etc. are attached to the recording medium M. The platen heater 49 can heat the recording medium M in a conductive manner, thereby making the ink etc. adhere to the heated recording medium M.

[0272] It should be noted that, when heating is performed by the IR heater 391 and the platen heater 49 or when no heating is performed, the upper limit of the surface temperature of the recording medium M is preferably 45° C. or lower, more preferably 40° C. or lower, further preferably 35° C. or lower, and further preferably 30° C. or lower. Furthermore, it is preferably 25° C. or lower. The lower limit is preferably 20° C. or higher, more preferably 30° C. or higher, and further preferably 35° C. or higher.

[0273] In the recording apparatus according to the present embodiment, from the viewpoint of improving clogging recovery, it is preferred that drying with heating is not performed in the attachment step, and it is preferred that the IR heater 391 and the platen heater 49 are not provided.

[0274] The heater 59 is a heater for drying and curing the ink etc. attached to the recording medium M, that is, a heater for secondary heating or secondary drying. The heater 59 can be used in the secondary drying process. By heating the recording medium M with the image recorded thereon by the heater 59, the water etc. contained in the ink etc. evaporates and disperses more quickly. In this way, the ink film is firmly fixed or bonded on the recording medium M, the film forming property is excellent, and an excellent high-quality image can be obtained in a short time.

[0275] The upper limit of the surface temperature of the recording medium M heated by the heater 59 is preferably 120° C. or less, more preferably 100° C. or less, and further preferably 80° C. or less. In addition, the lower limit of the surface temperature of the recording medium M is preferably 50° C. or more, more preferably 60° C. or more, and further preferably 70° C. or more. By setting the temperature within the above range, there is a tendency that a high-quality image can be obtained in a short time.

[0276] The inkjet recording device 19 may include a cooling fan 69. After the ink or the like recorded on the recording medium M is dried, the ink or the like on the recording medium M is cooled by the cooling fan 69, so that an ink coating film can be formed on the recording medium M with good adhesion.

[0277] The inkjet recording device 19 may include a preheater 79 for preheating the recording medium M before the ink or the like is attached to the recording medium M. The inkjet recording device 19 may include a ventilation fan 89 for drying the ink or the like attached to the recording medium M more efficiently.

[0278] Below the carriage 99, there are provided: a platen 119 for supporting the recording medium M; a carriage moving mechanism 139 for moving the carriage 99 relative to the recording medium M; and a conveying unit 149, which is a roller for conveying the recording medium M in the sub-scanning direction. The operations of the carriage moving mechanism 139 and the conveying unit 149 are controlled by the control unit CONT.

[0279] 2.2 Horizontal recording device

[0280] Figure 6 FIG. 1 is a front view schematically showing an example of a horizontal recording device. Figure 6 as well as Figure 7In order to clarify the configuration relationship of each part of the device, the XYZ orthogonal coordinates with the Z axis as the vertical axis are recorded. In addition, in the following description, the direction of each coordinate axis (arrow) is appropriately treated as the positive direction, and the opposite direction is appropriately treated as the negative direction. It should be noted that Figure 6 The recording device shown is a method in which the recording medium is transported in the direction of the axis along the scanning direction, and therefore it is particularly also called a transverse recording device.

[0281] The recording device 100 includes a host device 200 that generates print data based on image data (bitmap data) received from an external device such as a personal computer, and a printer unit 300 that prints an image based on the print data received from the host device 200. The printer unit 300 prints an image on the surface of a long sheet S using an inkjet method while conveying the long sheet S in a roll-to-roll manner.

[0282] like Figure 6 As shown, the printer unit 300 includes a main body housing 1 having a substantially rectangular parallelepiped shape. The main body housing 1 includes: a delivery unit 2 for delivering a sheet S from a roll R1 on which the sheet S is wound; a printing chamber 3 for ejecting ink onto the surface of the delivered sheet S to perform printing; a drying unit 4 for drying the sheet S to which the ink is attached; and a winding unit 5 for winding the dried sheet S into a roll R2.

[0283] More specifically, the main body housing 1 is divided into upper and lower parts along the Z-axis direction by a flat plate-shaped base 6 arranged parallel to the XY plane (i.e., horizontally), and the upper side of the base 6 serves as the printing chamber 3. A platen 30 is fixed to the upper surface of the base 6 in a substantially central portion of the printing chamber 3. The platen 30 has a rectangular shape, and supports the sheet S from the lower side by its upper surface parallel to the XY plane. Then, the recording unit 31 prints on the surface of the sheet S supported on the platen 30.

[0284] On the other hand, the delivery section 2, the drying section 4, and the winding section 5 are arranged below the base 6. The delivery section 2 is arranged below the platen 30 in the negative direction of the X axis ( Figure 6 The take-up section 5 is disposed on the lower side of the platen 30 in the positive direction of the X axis ( Figure 1 The drying section 4 is disposed directly below the platen 30 between the delivery section 2 and the winding section 5 in the X-axis direction and is provided with a rotatable winding shaft 51. The sheet S is wound on the winding shaft 51 and supported by the roller R2.

[0285] The sheet S fed from the feed shaft 21 of the feed section 2 passes through the printing chamber 3 and the drying section 4 in sequence while being guided by the rollers 71 to 77, and is then wound up by the winding shaft 51 of the winding section 5. It should be noted that the rollers 72 and 73 are arranged straightly (i.e., horizontally) in the X-axis direction so as to sandwich the platen 30, and the positions are adjusted so that the tops of the rollers 72 and 73 are at the same height as the upper surface of the platen 30 (the surface supporting the sheet S). Therefore, the sheet S wound up on the roller 72 moves horizontally (in the X-axis direction) while in sliding contact with the upper surface of the platen 30 before reaching the roller 73.

[0286] In the printing chamber 3, a printing process is performed on the sheet S by a recording unit 31 disposed on the upper side of the platen 30. The recording unit 31 prints an image on the surface of the sheet S by ejecting a processing liquid and an ink composition onto the surface of the sheet S. Here, at the end ( Figure 6 A cartridge mounting portion 8 is provided at the left end portion of the sheet S, and a treatment liquid cartridge 81 storing the treatment liquid and a plurality of ink cartridges 82 storing the ink composition are detachably mounted on the cartridge mounting portion 8. In addition, the recording unit 31 can eject the treatment liquid supplied from the treatment liquid cartridge 81 and the ink composition supplied from the ink cartridge 82 onto the surface of the sheet S by inkjet method.

[0287] Figure 7 is a bottom view partially showing the structure of the recording unit. Figure 6 as well as Figure 7 The recording unit 31 is described in detail. The recording unit 31 includes a carriage 32, a flat support plate 33 mounted on the lower surface of the carriage 32, a treatment liquid inkjet head 34 mounted on the lower surface of the support plate 33, and an inkjet head 35 for ink. On the lower surface of the support plate 33, four inkjet heads 35 for ink and one treatment liquid inkjet head 34 are arranged at equal intervals along the X-axis direction, and in each of the inkjet heads 34 and 35, a plurality of nozzles N (nozzle rows) are arranged in parallel along the Y-axis direction. Then, the treatment liquid inkjet head 34 ejects the treatment liquid from the nozzle N, and the four inkjet heads 35 eject inks of different colors, that is, ink compositions, from the nozzles N, respectively.

[0288] The length of the nozzle array in the Y-axis direction of the treatment liquid inkjet head 34 and the ink inkjet head 35 is preferably greater than the length in the Y-axis direction of the sheet S (recording medium). If the inkjet head has such a length, recording can be performed in one pass, and the recording speed is excellent, but since the amount of ink attached increases, it is easy to cause uneven bleeding. In contrast, according to the recording device involved in this embodiment, since the above-mentioned recording method is used, there is a tendency to make the image quality (uneven bleeding) excellent even when recording is performed in one pass.

[0289] exist Figure 7 In the figure, when the nozzle array of the processing liquid possessed by the inkjet head 34 for ejecting the processing liquid is projected along the head moving direction (X-axis direction), it is configured to completely overlap with the nozzle array of the ink possessed by the inkjet head 35 for ejecting ink in the nozzle array direction (Y-axis direction).

[0290] If such an arrangement is adopted, the processing liquid attachment process and the ink attachment process in the above-mentioned recording method can be performed by scanning while moving the processing liquid inkjet head and the ink inkjet head relative to the recording medium, and the processing liquid and the ink composition can be attached to the same scanning area by utilizing the same scanning (completely sprayed simultaneously).

[0291] return Figure 6 The description continues. The carriage 32 of the recording unit 31 configured as described above can move integrally with the support plate 33 and the inkjet head 34 for the processing liquid and the inkjet head 35 for the ink. That is, an X-axis guide rail 37 extending parallel to the X-axis direction is provided in the printing chamber 3, and the carriage 32 moves in the X-axis direction along the X-axis guide rail 37 when receiving the driving force of the X-axis motor.

[0292] Then, the recording unit 31 moves (scans) the carriage 32 in the X-axis direction (main scanning direction) above the platen 30, ejects the processing liquid from the processing liquid inkjet head 34, ejects the ink from the inkjet head 35, and makes the processing liquid and the ink composition adhere to the same scanning area by the same scanning, thereby printing an image on the surface of the sheet S stopped on the upper surface of the platen 30. Thus, a two-dimensional image of one frame of the distance scanned in the X-axis direction is printed on the surface of the sheet S with the length of the nozzle row in the Y direction. In addition, the coloring material of the ink constituting the two-dimensional image is condensed by the action of the processing liquid and fixed on the surface of the sheet S.

[0293] While the sheet S is intermittently moved in the X-axis direction, the printing of one frame as described above is repeatedly performed. Specifically, a specified range of substantially the entire area of ​​the upper surface of the platen 30 becomes the printing area. Then, the sheet S is intermittently conveyed in the X-axis direction in units of a distance (intermittent conveying distance) corresponding to the length of the printing area in the X-axis direction, and one frame of printing is performed on the sheet S stopped on the upper surface of the platen 30 during the intermittent conveying. In other words, if the printing of one frame of the sheet S stopped on the platen 30 is completed, the sheet S is conveyed in the X-axis direction by the intermittent conveying distance, and the unprinted surface of the sheet S stops on the platen 30. Next, one frame of printing is re-executed on the unprinted surface, and when the printing is completed, the sheet S is again conveyed in the X-axis direction by the intermittent conveying distance. Then, this series of actions is repeatedly performed.

[0294] It is also possible to print one frame by one scan. In this case, the number of scans is one. Alternatively, it is also possible to print one frame by two or more scans. In this case, the recording medium is not conveyed during the two or more scans for printing one frame. After printing one frame, the recording medium is conveyed.

[0295] It should be noted that, in order to keep the sheet S stopped on the upper surface of the platen 30 during intermittent conveyance flat, the platen 30 may also be provided with a mechanism for sucking the sheet S stopped on its upper surface. Specifically, a plurality of suction holes, not shown, are provided on the upper surface of the platen 30, and a suction unit 38 is installed on the lower surface of the platen 30. In addition, by the operation of the suction unit 38, negative pressure is generated in the suction holes on the upper surface of the platen 30, and the sheet S is sucked onto the upper surface of the platen 30. In addition, while the sheet S is stopped on the platen 30 for printing, the sheet S is kept flat by sucking the sheet S by the suction unit 38. On the other hand, when printing is finished, the suction unit 38 stops sucking the sheet S, so that the sheet S can be smoothly conveyed.

[0296] It should be noted that a heater 39 may be installed on the lower surface of the platen 30. The heater 39 may heat the platen 30 to a predetermined temperature (e.g., 30° C.) as required. Thus, the sheet S may be dried once by the heat of the platen 30 while being printed by the inkjet head 34 for the processing liquid and the inkjet head 35 for the ink.

[0297] In addition, in the recording device involved in this embodiment, the recording medium can also be heated by a heating mechanism (such as heater 39) for heating the recording medium provided by a member supporting the recording medium, or a heating mechanism (not shown) for heating the recording medium from above, at a place on the platen 30 to which the ink composition is attached. As the heating mechanism for heating the recording medium from above, for example, a blower or an IR heater can be cited.

[0298] In addition, even in the case of the ink being deposited, the surface temperature of the recording medium can be Figure 1 The same is true for the recording device example.

[0299] This makes it easy to adjust the surface temperature of the recording medium at the time of ink adhesion to 35° C. or less, and there is a tendency that more excellent clogging recovery properties can be obtained.

[0300] Thus, the sheet S having one frame of printing is moved from the platen 30 to the drying unit 4 as the sheet S is intermittently conveyed. The drying unit 4 can perform a post-heating process for completely drying the processing liquid or ink composition landed on the sheet S using air heated for drying.

[0301] In the drying section 4, the surface temperature of the sheet S is set to Figure 1 The same recording apparatus example may be used, and the temperature is preferably 30.0°C to 120.0°C, preferably 40.0°C to 100.0°C, more preferably 50.0°C to 95°C, and further preferably 70°C to 90°C.

[0302] Then, the sheet S that has been dried reaches the winding section 5 as the sheet S is intermittently conveyed, and is wound up as a roll R2.

[0303] 3. Example

[0304] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. % below refers to mass basis unless otherwise specified.

[0305] 3.1 Preparation of treatment liquid and ink composition

[0306] The treatment liquid and ink composition used in each embodiment or each comparative example are as shown in Table 1 ( Figure 8 ) is obtained by mixing the components, and the ink composition is obtained by mixing the components according to Table 2 ( Fig. 9 ) is obtained by mixing the components. It should be noted that the composition is expressed in mass % in Table 1 and Table 2. In addition, the coloring material (pigment) and resin particles in the table represent the solid content (active ingredient) respectively. Pure water is added so that the total mass of the treatment liquid or ink is 100 mass %.

[0307] In addition, in the ink composition, an aqueous pigment dispersion is prepared in advance as follows, and this is used for the preparation of the ink.

[0308] In a reaction vessel equipped with a reflux tube, a gas introduction device, a thermometer, and a stirring device, 198.2 parts of diethylene glycol monobutyl ether, 1.0 part of iodine, 3.7 parts of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 66.1 parts of tricyclodecyl methacrylate, and 0.17 parts of diphenylmethane as a catalyst were added. Polymerization was carried out at 45°C for 5 hours while passing nitrogen gas, to obtain a solution of polymer block A.

[0309] Next, the polymerization temperature was lowered to 40°C, and 44.0 parts of tricyclodecyl methacrylate, 17.2 parts of methacrylic acid, and 1.2 parts of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) were added to the solution of the A polymer block obtained above. The polymerization was then carried out for 4 hours, and then heated to 70°C for 1 hour to form the B polymer block, thereby obtaining a solution of the AB block polymer.

[0310] After cooling the solution of the AB block polymer obtained above, 66.1 parts of diethylene glycol monobutyl ether was added, and the mixture was dried at 150° C. for 1 hour to obtain a polymer having a solid content of 33.0%.

[0311] 341 parts of the above polymer, 163.6 parts of butyl carbitol, and 450 parts of CI Pigment Blue 15:3 as a cyan pigment or CI Pigment Black 7 as a black pigment were mixed and stirred with a disperser. Then, the pigment was fully dispersed with a horizontal media disperser to obtain an oily pigment dispersion. Then, while stirring 700 parts of the above-obtained oily pigment dispersion with a disperser, a mixed solution consisting of 4.0 parts of potassium hydroxide and 341 parts of water was slowly added to neutralize and phase inversion was performed. Then, the pigment was fully dispersed again with a horizontal media disperser to obtain an aqueous pigment dispersion.

[0312] Regarding Tables 1 and 2 ( Figure 8 , 9) are supplemented as follows.

[0313] <Water-soluble low molecular weight organic compounds>

[0314] PG (propylene glycol, standard boiling point is 188°C, 25°C properties: liquid)

[0315] 1,2HD (1,2-hexanediol, standard boiling point 223°C, properties at 25°C: liquid)

[0316] <Surfactant>

[0317] BYK-348 (trade name manufactured by BYK-Chemie JAPAN Co., Ltd., silicone-based surfactant)

[0318] <Coagulant>

[0319] ・CATIO MASTER PD-7 (trade name of Yokkaichi Kogyo Co., Ltd., amine-epichlorohydrin copolymer cationic resin)

[0320] <Resin particles>

[0321] ·Joncryl 631 (trade name of BASF JAPAN Co., Ltd., styrene acrylic resin emulsion)

[0322] 3.2 Recording conditions

[0323] The recording conditions in the evaluation test were as follows.

[0324] Printing press: to be described later

[0325] Resolution: 1200×1200dpi

[0326] Printing pattern: solid pattern (cyan or black)

[0327] Scan times: Table 3, 4 ( Fig.10 , Fig.11 )

[0328] Paper surface temperature: Table 3, 4 ( Fig.10 , Fig.11 )

[0329] Secondary drying temperature: 70℃

[0330] Recording medium: Table 3, 4 ( Fig.10 , Fig.11 Each type of recording medium will be described later.

[0331] Continuous printing time: Table 3, 4 ( Fig.10 , Fig.11 The time for recording by scanning and conveying the recording medium is continuously performed.

[0332] It should be noted that the “paper surface temperature” refers to the surface temperature of the recording medium at a position facing the inkjet head. Also, the “secondary drying temperature” refers to the surface temperature of the recording medium after passing through the platen and undergoing the secondary drying process.

[0333] It should be noted that Tables 3 and 4 ( Fig.10 , Fig.11 ) in the nozzle arrangement, each arrangement in the nozzle arrangement is described as follows.

[0334] "Arrangement 1": As a printer (recording device), a modified L-4533AW (manufactured by Seiko Epson Corporation) was prepared. Figure 6 The lateral recording device shown. The inkjet head is Figure 7 The inkjet head arrangement described in is a method in which the processing liquid attachment step and the ink attachment step are performed in the same scan so that the processing liquid and the ink composition are attached to the same scan area (completely ejected simultaneously).

[0335] "Arrangement 2": In Arrangement 1, one frame of printing is performed by performing a scan to attach only the treatment liquid, followed by a scan to attach only the ink. After printing one frame, the recording medium is transported, and the next frame of printing is performed in the same manner. The treatment liquid attachment step and the ink attachment step are methods in which the treatment liquid and the ink composition are not attached to the same scan area by the same scan.

[0336] "Arrangement 3": In Arrangement 1, the recording device is further modified, and the inkjet head is fixed near the center of the platen to form a line head. It is a line printer that has a line head that has a width greater than the recording width of the recording medium. The following recording method is adopted: while the recording medium is relatively moved relative to the line head in a scanning direction that intersects the width direction, ink is ejected from the line head to the recording medium. It should be noted that in the line printer, the nozzle does not move but is fixed, and recording is performed in one pass (single pass). During recording, the inkjet head (line head) does not move.

[0337] "Arrangement 4": In arrangement 5, it is Figure 4 The inkjet head arrangement described in is a method in which the processing liquid attachment step and the ink attachment step are performed in the same scan so that the processing liquid and the ink composition are attached to the same scan area (front ejection).

[0338] "Arrangement 5": As a printer (recording device), a modified SC-R5050 (manufactured by Seiko Epson Corporation) was prepared. Figure 1 Such a serial recording device. The inkjet head is Figure 3 The inkjet head arrangement described in is a method in which the processing liquid attachment step and the ink attachment step are performed in the same scan so that the processing liquid and the ink composition are attached to the same scan area (completely ejected simultaneously).

[0339] "Arrangement 6": In Arrangement 1, make the inkjet head Figure 5 The inkjet head arrangement described in . For the same scanning area of ​​the recording medium, the scanning for attaching the treatment liquid is first performed, and then the scanning for attaching the ink is performed to perform printing. The treatment liquid attaching step and the ink attaching step are methods of not attaching the treatment liquid and the ink composition to the same scanning area by the same scanning.

[0340] In addition, Tables 3 and 4 ( Fig.10 , Fig.11 ), "M1" represents PET50A (trade name manufactured by Lintec Co., Ltd., PET film). "M2" represents Orajet 3165G-010 (trade name manufactured by ORAFOL JAPAN Co., Ltd., vinyl chloride film). "M3" represents BR9708 (trade name manufactured by Ahlstrom Co., Ltd., wool wallpaper, absorbent recording medium).

[0341] 3.3 Evaluation test

[0342] 3.3.1 Image quality (uneven bleeding)

[0343] The processing liquid and ink composition (cyan ink) obtained above were filled in a recording device, and a cyan solid pattern was printed on a recording medium (the adhesion amount is shown in Tables 3 and 4). The printed matter was visually evaluated based on the following criteria.

[0344] (Judgment Criteria)

[0345] AA: No uneven seepage is visible at a distance of 20 cm

[0346] A: Uneven seepage can be seen at a distance of 20 cm, but not at a distance of 50 cm

[0347] B: Uneven seepage can be seen at a distance of 50 cm, but no uneven seepage can be seen at a distance of 80 cm

[0348] C: Uneven seepage can be seen even at a distance of 80 cm (NG)

[0349] 3.3.2 Image Quality (Filling)

[0350] The processing liquid and ink composition (black ink) obtained above were filled in a recording device, and black 3 pt characters were printed on a recording medium (the adhesion amount is shown in Tables 3 and 4). The printed matter was visually evaluated based on the following criteria.

[0351] (Judgment Criteria)

[0352] AA: No white spots can be seen at a distance of 20 cm

[0353] A: White spots can be seen at a distance of 20 cm, but not at a distance of 50 cm

[0354] B: White spots can be seen at a distance of 50 cm, but not at a distance of 80 cm

[0355] C: White spots can be seen even at a distance of 80 cm (NG)

[0356] 3.3.3 Mixed liquid blockage recovery

[0357] The processing liquid and ink composition obtained above were filled in the recording device, and recording was performed under the printing conditions in Tables 3 and 4. At this time, the nozzle voltage was set to 30V, and the amount of mist generation was set to be large. After recording, three cleanings were performed, and the number of ink nozzles that finally fell off was determined based on the following judgment criteria. It should be noted that one cleaning was to discharge 1g of ink from the nozzle column.

[0358] (Judgment Criteria)

[0359] AA: All nozzles are restored by preparatory ejection only

[0360] A: Restore all nozzles by cleaning once

[0361] B: Restore all nozzles by cleaning 3 times

[0362] C: Nozzles still not restored after cleaning 3 times (NG)

[0363] 3.3.4 Whitening of printed materials

[0364] The processing liquid and ink composition (black ink) obtained above were filled in a recording apparatus, a black solid pattern was printed on a recording medium (the adhesion amount is shown in Tables 3 and 4), and the printed matter was visually evaluated based on the following criteria.

[0365] (Judgment Criteria)

[0366] A: No whitening of printed materials is seen

[0367] B: The printed material is slightly bleached, but not noticeable

[0368] C: The printed material is noticeably whitened (NG)

[0369] 3.3.5 Abrasion resistance

[0370] The processing liquid and ink composition obtained above were filled in a recording device, and a solid pattern was printed on a recording medium (the adhesion amount is shown in Tables 3 and 4). After standing at room temperature for 30 minutes, the ink adhesion portion was cut into a 25×150 mm rectangle, and the ink peeling degree was visually evaluated based on the following judgment criteria when the plain woven cloth moistened with water was wiped 100 times with a Gakushin type abrasion resistance tester (load 500 g).

[0371] (Judgment Criteria)

[0372] AA: No peeling

[0373] A: Less than 20% peeling relative to the evaluation area

[0374] B: Delamination of more than 20% and less than 50% of the evaluation area

[0375] C: More than 50% of the evaluation area is peeled off

[0376] 3.4 Evaluation results

[0377] The evaluation results are shown in Tables 3 and 4. Fig.10 , Fig.11 ) as shown.

[0378] From Tables 3 and 4 ( Fig.10 , Fig.11) shows that: a recording method comprises: a treatment liquid attachment step, in which a treatment liquid containing a coagulant is ejected from an inkjet head for treatment liquid to be attached to a recording medium; and an ink attachment step, in which an aqueous ink composition containing a coloring material is ejected from an inkjet head for ink to be attached to a recording medium, the treatment liquid attachment step and the ink attachment step are performed by scanning while moving the inkjet head for treatment liquid and the inkjet head for ink relative to the recording medium, the treatment liquid and the ink composition are attached to the same scanning area by the same scanning, the coagulant is a calcium salt, the content of the calcium salt relative to the total mass of the treatment liquid is 0.35 mol / kg or less, and in the treatment liquid attachment step, the maximum amount of the calcium salt attached in the area of ​​the recording medium to which the treatment liquid and the ink composition are attached is in the range of 0.6 μmol / inch 2 Next, in the treatment liquid attachment process and the ink attachment process, there is an air supply process for supplying air to the recording medium. In each embodiment using the above-mentioned recording method, the nozzle clogging recovery, image quality (suppressing uneven bleeding) and whitening reduction of the printed matter are all excellent.

[0379] On the other hand, in each comparative example that does not satisfy the above-mentioned configuration, at least any one of the nozzle clogging recovery property, the image quality (blurring unevenness), and the whitening reduction property of the printed matter is poor.

[0380] It should be noted that in Reference Examples 1, 3, and 4, the treatment liquid is attached before the ink composition, and the treatment liquid and the ink composition are not attached to the same scan area by the same scan. In Reference Examples 1 and 4, although the content of calcium salt relative to the total mass of the treatment liquid exceeds, the nozzle clogging recovery is not bad. However, since the treatment liquid and the ink composition are not attached to the same scan area by the same scan, it is useless to record the time spent.

[0381] In reference example 2 using a line printer, although the calcium salt content relative to the total mass of the treatment liquid exceeded, the nozzle clogging recovery was not bad. However, during recording, the line head did not move to a position not facing the recording medium, which was useless.

[0382] The following contents can be derived from the above-mentioned embodiments.

[0383] One way of recording a method is a recording method having:

[0384] a treatment liquid attachment step of ejecting a treatment liquid containing a coagulant from an inkjet head for the treatment liquid so as to attach the treatment liquid to the recording medium; and

[0385] In the ink attaching step, an aqueous ink composition containing a coloring material is ejected from an inkjet head to attach the composition to a recording medium.

[0386] The process liquid attaching step and the ink attaching step are performed by scanning while the process liquid inkjet head and the ink inkjet head are moved relative to the recording medium.

[0387] By the same scanning, the treatment liquid and the ink composition are attached to the same scanning area,

[0388] The coagulant is a calcium salt,

[0389] The content of the calcium salt relative to the total mass of the treatment liquid is 0.35 mol / kg or less,

[0390] In the treatment liquid attachment step, the maximum value of the amount of the calcium salt attached in the region of the recording medium to which the treatment liquid and the ink composition are attached is in the range of 0.6 μmol / inch. 2 the following,

[0391] The processing liquid attaching step and the ink attaching step include an air supply step of supplying air to the recording medium.

[0392] Alternatively, in one embodiment of the above recording method,

[0393] The wind speed of the air in the air supply step is 1.5 m / s or more.

[0394] Alternatively, in any of the above recording methods,

[0395] The recording using the above recording method is performed continuously for 1 hour or more.

[0396] Alternatively, in any of the above recording methods,

[0397] The number of scans for making the ink composition adhere to the same scan area is 10 times or less.

[0398] Alternatively, in any of the above recording methods,

[0399] In the treatment liquid attaching step and the ink attaching step, the surface temperature of the recording medium to which the ink is attached is 35° C. or less.

[0400] Alternatively, in any of the above recording methods,

[0401] The air temperature of the air sent in the air sending step is 35° C. or less.

[0402] Alternatively, in any of the above recording methods,

[0403] The calcium salt is a calcium salt of an organic acid.

[0404] One method of recording the device is,

[0405] A recording device, which records on the recording medium using any of the above recording methods,

[0406] The invention comprises the treatment liquid, the ink composition, an inkjet head for the treatment liquid, and an inkjet head for the ink.

[0407] The present invention is not limited to the above-mentioned embodiments, and various modifications are possible. For example, the present invention includes a structure that is substantially the same as the structure described in the embodiments, such as a structure with the same function, method and result, or a structure with the same purpose and effect. In addition, the present invention includes a structure that replaces a non-essential part of the structure described in the embodiments. In addition, the present invention includes a structure that has the same effect as the structure described in the embodiments, or a structure that can achieve the same purpose. In addition, the present invention includes a structure in which a known technology is added to the structure described in the embodiments.

Claims

1. A recording method, characterized in that: have: a treatment liquid attachment step of ejecting a treatment liquid containing a coagulant from a treatment liquid inkjet head to attach the treatment liquid to a recording medium; as well as In the ink attaching step, an aqueous ink composition containing a coloring material is ejected from an inkjet head to attach the composition to a recording medium. The process liquid attaching step and the ink attaching step are performed by scanning while the process liquid inkjet head and the ink inkjet head are moved relative to the recording medium. By the same scanning, the treatment liquid and the ink composition are attached to the same scanning area, The coagulant is a calcium salt, The content of the calcium salt relative to the total mass of the treatment liquid is 0.35 mol / kg or less, and in the treatment liquid attachment step, the maximum amount of the calcium salt attached to the area of ​​the recording medium to which the treatment liquid and the ink composition are attached is in the range of 0.6 μmol / inch 2 the following, The processing liquid attaching step and the ink attaching step include an air supply step of supplying air to the recording medium.

2. The recording method according to claim 1, wherein: The wind speed of the air in the air supply step is 1.5 m / s or more.

3. The recording method according to claim 1 or 2, wherein: The recording using the above recording method is performed continuously for 1 hour or more.

4. The recording method according to claim 1 or 2, wherein: The number of scans for making the ink composition adhere to the same scan area is 10 times or less.

5. The recording method according to claim 1 or 2, wherein: In the treatment liquid attaching step and the ink attaching step, the surface temperature of the recording medium to which the ink is attached is 35° C. or less.

6. The recording method according to claim 1 or 2, wherein: The air temperature of the air sent in the air sending step is 35° C. or less.

7. The recording method according to claim 1 or 2, wherein: The calcium salt is a calcium salt of an organic acid.

8. A recording device, characterized in that: Recording on the recording medium using the recording method according to claim 1, The invention comprises the treatment liquid, the ink composition, an inkjet head for the treatment liquid, and an inkjet head for the ink.

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