JP2016193579A - Inkjet recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inkjet printing method capable of obtaining a printed matter on which stickiness unevenness and bead-like ruled lines are suppressed.SOLUTION: An inkjet printing method includes: a resin liquid deposition step of depositing a resin liquid containing a resin having an acid value of 50 mgKOH/g or less onto a printing region of a medium to be printed; a reaction liquid deposition step of depositing a reaction liquid containing a reactant aggregating or thickening components of a coloring ink composition onto the printing region having the resin liquid deposited thereon; and a coloring ink composition deposition step of depositing the coloring ink composition containing a coloring material onto the printing region having the reaction liquid deposited thereon by an inkjet method.SELECTED DRAWING: None

Description

  The present invention relates to an ink jet recording method.

  The ink jet recording method is capable of recording high-definition images with a relatively simple device, and has been rapidly developed in various fields. Among them, various studies have been made on ejection stability and the like. For example, Patent Document 1 discloses a water-based ink for the purpose of providing an image recording method, an ink set, and an ink-jet recorded product that can suppress the occurrence of curling and can record an image with high scratch resistance and high reproducibility. Is an image recording method for recording an image by discharging an ink jet method using an ink jet method, wherein the recording medium contains resin particles having an SP value of 9.5 or more, and allows the solvent contained in the aqueous ink to penetrate into the recording medium. A blocking layer forming step for forming a blocking layer to be blocked; an immobilization treatment step for immobilizing the blocking layer using a material for immobilizing components in water-based ink; and immobilization on the blocking layer. An image recording step of recording an image by ejecting a pigment, resin particles, a water-soluble organic solvent having an SP value in the range of 10 to 14 and water-based ink containing water by an inkjet method in the treated region; You Image recording method is disclosed.

JP 2009-226598 A

  Further, as an advantage of using the resin liquid, in addition to curling suppression of the absorbent recording medium disclosed in Patent Document 1, by suppressing penetration of the reaction liquid into the (low) absorbent recording medium, For example, sufficient reactivity between the reaction liquid and the ink composition can be obtained, and the reaction liquid is prevented from being repelled on the non-absorbable recording medium, thereby improving wettability. However, when the resin reacts with the reaction agent in the reaction solution, the effect of the reaction agent cannot be obtained sufficiently, resulting in the occurrence of bethamra and ruled lines, and the image quality of the obtained recorded matter is deteriorated.

  The present invention has been made to solve at least a part of the above-described problems, and an object of the present invention is to provide an ink jet recording method capable of obtaining a recorded matter in which bethamra and ruled line balls are suppressed.

  The present inventors diligently studied to solve the above problems. As a result, the inventors have found that the above-mentioned problems can be solved by using a predetermined resin liquid, and have completed the present invention.

That is, the present invention is as follows.
[1]
A resin liquid attaching step of attaching a resin liquid containing a resin having an acid value of 50 mgKOH / g or less to a recording area of a recording medium;
A reaction liquid attaching step of attaching a reaction liquid containing a reactive agent that aggregates or thickens the components of the colored ink composition to the recording area to which the resin liquid is attached;
A colored ink composition adhering step of adhering the colored ink composition containing a coloring material to the recording area to which the reaction liquid is adhered by an inkjet method,
Inkjet recording method.
[2]
The inkjet recording method according to item [1], wherein the surface free energy of the dry film in the recording region to which the resin liquid is adhered is 40 mN / m or more.
[3]
The inkjet recording method according to [1] or [2], wherein the resin has a carboxyl group or a base thereof.
[4]
The inkjet recording method according to any one of [1] to [3], wherein a glass transition point of the resin is −35 ° C. or higher.
[5]
The ink jet recording method according to any one of [1] to [4], wherein the acid value of the resin is 2.0 to 40 mgKOH / g.
[6]
6. The ink jet recording method according to any one of [1] to [5], wherein a dry film thickness of the recording region to which the resin liquid is adhered is 0.10 to 1.0 μm.
[7]
The inkjet recording method according to any one of [1] to [6], wherein the elongation of the resin is 5% or more.
[8]
The inkjet recording method according to any one of [1] to [7], wherein a time interval from the end of the reaction liquid adhesion step to the start of the colored ink composition adhesion step is 10 seconds or less.
[9]
The resin liquid further contains water,
The inkjet recording method according to any one of [1] to [8], wherein the resin is a resin dispersion dispersed in water.
[10]
A resin liquid containing a resin having an acid value of 50 mgKOH / g or less, which is used in the ink jet recording method according to any one of [1] to [9].

1 is a side view showing an outline of an example of an inkjet recording apparatus that can be used in the present embodiment.

  Hereinafter, an embodiment of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail with reference to the drawings as necessary. However, the present invention is not limited to this, and the gist thereof is described below. Various modifications are possible without departing from the scope. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, positional relationships such as up, down, left and right are based on the positional relationships shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

[Inkjet recording method]
In the inkjet recording method of the present embodiment, a resin liquid attaching step for attaching a resin liquid containing a resin having an acid value of 50 mgKOH / g or less to a recording area of a recording medium, and the recording area on which the resin liquid is attached A reaction liquid adhering step for adhering a reaction liquid containing a reaction agent for aggregating or thickening the components of the color ink composition, and the coloring ink composition containing a coloring material in the recording area to which the reaction liquid is adhering A colored ink composition adhering step for adhering the ink by an ink jet method.

[Resin liquid adhesion process]
The resin liquid attaching step is a step of attaching a resin liquid containing a resin having an acid value of 50 mgKOH / g or less to the recording area of the recording medium. The means for attaching the resin liquid is not particularly limited, and for example, roller coating, spray coating, and an ink jet method can be used. Thus, by using the resin liquid, it is possible to prevent the reactant from penetrating into the recording medium or to improve the wettability of the reaction liquid to the recording medium. In addition, the reaction between the resin liquid and the reaction liquid can be further suppressed, thereby improving the reaction efficiency between the reaction liquid and the ink composition. As a result, the resulting printed matter is prevented from becoming sticky or ruled lines.

  The surface free energy of the dry film in the recording area to which the resin liquid is adhered is preferably 35 mN / m or more, more preferably 40 mN / m or more. Further, the surface free energy of the dry film in the recording area to which the resin liquid is adhered is preferably 60 mN / m or less, and more preferably 55 mN / m or less. When the surface free energy of the dry film in the recording area to which the resin liquid is adhered is within the above range, the wettability of the reaction liquid is further improved, and the image quality of the obtained recorded matter tends to be further improved. The surface free energy can be measured by the method described in Examples. The surface free energy can be increased by increasing the hydrophilicity of the resin used. The hydrophilicity of the resin can be adjusted by the amount of the highly hydrophilic monomer used in the polymerization of the resin and the type of monomer used. Examples of the hydrophilic group of the hydrophilic monomer include a hydroxyl group, an ether group, and an ionic group. The “dry film” refers to a coating film obtained by attaching a resin liquid to a recording area and drying it. However, the recording method of the present embodiment is not limited to attaching the reaction liquid after the resin liquid is dried, and the reaction liquid is attached from above in a state where the recording medium is wet with the resin liquid. May be.

  The film thickness of the dry film in the recording area to which the resin liquid is adhered is preferably 0.10 to 3.0 [mu] m, more preferably 0.10 to 2.0 [mu] m, still more preferably 0.10 to 1. 0 μm. When the film thickness of the dry film is 0.10 μm or more, the resulting printed matter tends to be further suppressed from being sticky and ruled lines. Moreover, when the film thickness of the dry film is 3.0 μm or less, the change in glossiness of the obtained recorded product tends to be further suppressed.

Adhesion amount of the resin to the recording area is preferably 0.01~0.75mg / inch ^2, more preferably 0.02~0.6mg / inch ^2, more preferably 0.05~0.5mg / Inch ² . When the amount of the resin adhering to the recording area is 0.01 mg / inch ² or more, the resulting printed matter tends to be further suppressed from being sticky and ruled lines. Further, when the amount of the resin adhering to the recording area is 0.75 mg / inch ² or less, a change in glossiness of the obtained recorded matter tends to be further suppressed.

[Recording medium]
Examples of the recording medium include an absorptive, low-absorbing, and non-absorbing recording medium. Among these, the recording medium is preferably a low absorption recording medium or a non-absorbing recording medium. When a low-absorbing recording medium or a non-absorbing recording medium is used, the reaction liquid is repelled on the surface of the recording medium, so that it is difficult to uniformly apply the reactants, and therefore, it is more likely to cause bethamra or bleed. However, this embodiment is particularly useful because the reaction liquid can be prevented from being repelled by the resin liquid. In addition, when a low-absorbing recording medium or a non-absorbing recording medium is used, the reactive agent does not penetrate into the recording medium and tends to remain on the surface of the recording medium, so the stickiness of the recording surface and wet friction resistance deteriorate. Tend to. However, in this embodiment, since the amount of the reaction solution can be reduced by using the resin solution, the stickiness of the recording surface can be improved, which is particularly advantageous. The “recording area” refers to an area where an image on the recording medium surface is formed.

Here, the “low-absorbing recording medium” or “non-absorbing recording medium” refers to a recording medium having a water absorption of 10 mL / m ² or less from the start of contact to 30 msec in the Bristow method. . This Bristow method is the most popular method for measuring the amount of liquid absorbed in a short time, and is also adopted by the Japan Paper Pulp Technology Association (JAPAN TAPPI). For details of the test method, refer to Standard No. of “JAPAN TAPPI Paper Pulp Test Method 2000”. 51 "Paper and paperboard-Liquid absorbency test method-Bristow method".

  Further, the non-absorbent recording medium or the low-absorbing recording medium can be classified by the wettability of the recording surface with respect to water. Specifically, a 0.5 μL water droplet is dropped on the recording surface of the recording medium, and the contact angle reduction rate (comparison of the contact angle at 0.5 milliseconds after the landing and the contact angle at 5 seconds) is measured. Can be used to characterize the recording medium. More specifically, as a property of the recording medium, the non-absorbing property of the “non-absorbing recording medium” indicates that the above-described reduction rate is less than 1%, and the low absorption of the “low-absorbing recording medium”. The property indicates that the decrease rate is 1% or more and less than 5%. Moreover, absorptivity means that said reduction rate is 5% or more. In addition, a contact angle can be measured using portable contact angle meter PCA-1 (made by Kyowa Interface Science Co., Ltd.) etc.

  The absorbent recording medium is not particularly limited. For example, plain paper such as electrophotographic paper having high penetrability of the ink composition, inkjet paper (an ink absorbing layer composed of silica particles or alumina particles, or polyvinyl chloride). Art paper used for general offset printing in which the ink composition has a relatively low permeability from an alcohol (PVA) or polyvinyl pyrrolidone (PVP) or other hydrophilic polymer such as an ink-absorbing layer. , Coated paper, cast paper, and the like.

  Although it does not specifically limit as a low absorptive recording medium, For example, the coated paper by which the coating layer for accepting oil-based ink was provided in the surface is mentioned. The coated paper is not particularly limited, and examples thereof include printing paper such as art paper, coated paper, and matte paper.

  The non-absorbable recording medium is not particularly limited. For example, a plastic film that does not have an ink absorbing layer, a substrate such as paper coated with plastic, or a plastic film bonded thereto Etc. Examples of the plastic here include polyvinyl chloride, polyethylene terephthalate, polycarbonate, polystyrene, polyurethane, polyethylene, and polypropylene.

  In addition to the recording medium, a non-ink-absorbing or low-absorbing recording medium such as a plate of metal such as iron, silver, copper, or aluminum, or glass can be used.

  In particular, the recording medium preferably has a roll shape. When recording, the roll-shaped recording medium can be used in such a manner that the head is scanned once relative to the recording medium and wound by a winding roller. When such a recording medium is used, when all the colors cannot be recorded by one feeding due to a large number of types of colored ink to be used, and the recording medium is recorded many times, the recording medium is recorded multiple times. On the other hand, a recorded product can be obtained by repeating the operation of scanning the head relatively once and winding it with a winding roller. However, because of the roll shape, the resin layer tends to crack. When a crack occurs, the image quality of the obtained recorded matter tends to deteriorate due to the reaction liquid penetrating into the crack. On the other hand, the coating film formed with the resin liquid of this embodiment is hard to generate a crack. Therefore, the present invention is particularly useful when a recording medium having such a shape is used.

[Resin liquid]
The resin liquid contains a resin having an acid value of 50 mgKOH / g or less, and may contain water and other components as necessary. In particular, it is preferable that the resin liquid contains water and the resin is in a resin dispersion state in which the resin is dispersed in the water. Such a resin liquid tends to further improve the dispersion stability of a resin having a preferable acid value or functional group.

(resin)
Although it does not specifically limit as resin, For example, (meth) acrylic-type resin, urethane type resin, polyolefin-type resin, and polyester-type resin are mentioned. Among these, the resin preferably contains resin fine particles. In particular, it is preferably contained in the resin liquid in the form of a resin emulsion. Examples of the resin fine particles include polyester resin fine particles (for example, product name “Vylonal MD-1500” manufactured by Toyobo Co., Ltd.), polyethylene resin fine particles (for example, product name “Zyxen A” manufactured by Sumitomo Seika Co., Ltd.), urethane. Resin fine particles (for example, product name “Rezamin D4200” manufactured by Dainichi Seika Kogyo Co., Ltd.). By including such resin fine particles, the amount of treatment liquid used can be reduced, and stickiness, stickiness, and bleed of the recording surface tend to be further suppressed. Resin is used individually by 1 type or in combination of 2 or more types. Hereinafter, examples of each resin will be described.

  Examples of the (meth) acrylic resin include an acrylic resin emulsion. The acrylic resin emulsion is not particularly limited. For example, (meth) acrylic monomers such as (meth) acrylic acid and (meth) acrylic acid esters, or (meth) acrylic monomers are polymerized. And other monomers are copolymerized. These commercially available products are not particularly limited. For example, Movinyl 966A (trade name manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), Microgel E-1002, Microgel E-5002 (above products) Name, manufactured by Nippon Paint Co., Ltd., Boncourt 4001, Boncourt 5454 (above trade name, manufactured by DIC), SAE1014 (trade name, manufactured by Zeon Corporation), Cybinol SK-200 (Trade name, manufactured by SAIDEN CHEMICAL INDUSTRY CO., LTD.), John Krill 7100, John Krill 390, John Krill 711, John Krill 511, John Krill 7001, John Krill 632, John Krill 741, John Krill 450, John Crill 840, John Crill 62J, John Crill 74J, John Crill HRC-1645J, John Crill 734, John Crill 852, John Crill 7600, John Crill 775, John Crill 537J, John Crill 1535, John Crill PDX-7630A, John Crill 352J, John Crill 352D, John Crill PDX-7145, John Krill 538J, Jonkrill 7640, Jonkrill 7641, Jonkrill 631, Jonkrill 790, Jonkrill 780, Jonkrill 7610 (above trade name, manufactured by BASF), NK binder R-5HN (trade name, manufactured by Shin Nakamura Chemical Co., Ltd.) 44% solid content). The term “acrylic resin” includes methacrylic resin and acrylic resin.

  Among these, at least one selected from the group consisting of (meth) acrylic resins and styrene- (meth) acrylic acid copolymer resins is preferable, and from the group consisting of acrylic resins and styrene-acrylic acid copolymer resins. At least one selected is more preferable, and a styrene-acrylic acid copolymer resin is more preferable. In addition, said copolymer may be any form among a random copolymer, a block copolymer, an alternating copolymer, and a graft copolymer.

  An example of the urethane resin is a urethane resin emulsion. The urethane resin emulsion is not particularly limited as long as it is a resin emulsion having a urethane bond in the molecule, a polyether type urethane resin having an ether bond in the main chain, a polyester type urethane resin having an ester bond in the main chain, and a main A polycarbonate type urethane resin containing a carbonate bond in the chain may be mentioned. Although it does not specifically limit as a commercial item of the said urethane resin emulsion, For example, Sancure 2710 (The brand name made from The Lubrizol Corporation), Permarin UA-150 (Sanyo Chemical Industries, Ltd.) .) Trade name), Superflex 460, 470, 610, 700 (above, trade name made by Dai-ichi Kogyo Seiyaku Co., Ltd.), NeoRez R-9660, R-9737, R-940 (above, trade name manufactured by Kusumoto Chemicals, Ltd.), Adekabon titer HUX-380, 290K (above, trade name made by Adeka), Takerak (registered trademark) W-605 , W-635, WS-6021 (Mitsui Chemicals, Inc. trade name), polyether (TAISEI FINECHEM ICAL CO, .LTD) trade name, Tg = 20 ° C.).

  Although it does not specifically limit as polyolefin-type resin, For example, Chemipearl S650, Chemipearl S75N (product name made by Mitsui Chemicals), AQUACER515 (product name made by BYK) etc. are mentioned.

  The polyester resin is not particularly limited, and examples thereof include polybutylene terephthalate, polytrimethylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, copolymers thereof, and fine particles thereof. A sulfopolyester resin (polysulfoester resin) substituted with a sulfo group (sulfonic acid group) can also be preferably used.

  The acid value of the resin is 50 mgKOH / g or less, preferably 45 mgKOH / g or less, more preferably 40 mgKOH / g or less. The acid value of the resin is preferably 2.0 KOH / g or more, more preferably 3.0 KOH / g or more, still more preferably 5.0 KOH / g or more, and still more preferably 10 KOH / g. Or more, more preferably 20 KOH / g or more, particularly preferably 25 KOH / g or more, and particularly preferably 30 KOH / g or more. Among these, the acid value of the resin is most preferably 2 to 40 mgKOH / g. When the acid value of the resin is 50 mgKOH / g or less, it is possible to further suppress the deactivation of the reactant due to the reaction between the resin in the resin solution and the reactant in the reaction solution. More improved. Further, when the acid value of the resin is 2.0 mgKOH / g or more, the storage stability is further improved, and the surface quality change rate of the obtained recorded matter tends to be lower. The acid value of the resin can be adjusted by changing the amount of monomer having an acidic group (usage ratio) among the monomers used for polymerizing the resin or changing the type of such monomer. Examples of acidic groups include carboxyl groups and sulfonic acid groups. Moreover, the acid value of resin can be measured by the method as described in an Example.

  In particular, the resin preferably has a dispersing group selected from the group consisting of a carboxyl group, a sulfonic acid group, an amino group, or a salt thereof. Among these, it is preferable to have a carboxyl group or its base. By using such a resin, the dispersion stability of the resin tends to be further improved. In particular, by having a carboxyl group or a base thereof, the reaction between the resin and the reactant can be further suppressed, and the resulting printed matter tends to be further suppressed from the betham and the ruled line balls. Furthermore, from the viewpoint of improving dispersion stability, a resin having an anionic functional group is preferable.

  The glass transition point of the resin is preferably −35 ° C. or higher, more preferably 0 ° C. or higher, still more preferably 20 ° C. or higher, still more preferably 35 ° C. or higher, and even more preferably 40 ° C. That's it. The glass transition point of the resin is preferably 70 ° C or lower, more preferably 60 ° C or lower. When the glass transition point of the resin is −35 ° C. or higher, the molecular movement of the resin is less likely to occur due to heat during drying, and the resin is relatively less likely to penetrate into the recording medium. As a result, the resin layer formed on the recording medium tends to have a uniform thickness or the resin tends to be uniformly dispersed. Thereby, the reaction liquid can be uniformly laminated on the resin layer, and the occurrence of unevenness tends to be further suppressed during the interaction between the reaction liquid and the ink composition. In addition, Tg can be calculated | required by the method as described in an Example. Tg can be changed, for example, by changing at least one of the type and composition ratio of monomers used for polymerization of the resin, polymerization conditions, and modification of the resin. For example, the glass transition point can be adjusted by reducing the number of polymerized biofunctional groups and decreasing the resin density of the resin, or by using a monomer having a relatively large molecular weight (a monomer having a large number of carbon atoms). Examples of the polymerization conditions include the temperature during polymerization, the type of medium containing the monomer, the monomer concentration in the medium, the type and amount of polymerization initiator and catalyst used during the polymerization, and the like. The glass transition point of the resin can be measured by a differential scanning calorimetry method (DSC method) based on JIS K7121.

  The elongation of the resin is preferably 5% or more, more preferably 200% or more, and further preferably 350% or more. Further, the elongation of the resin is preferably 1300% or less, more preferably 1000% or less, and further preferably 700% or less. When the elongation of the resin is 5% or more, there is a tendency to prevent cracks that may occur during image printing even when the recording medium is deformed during recording. Further, when the elongation of the resin is 1300% or less, the abrasion resistance tends to be further improved. The elongation of the resin can be measured by the method described in the examples. The elongation can be controlled by adjusting the Tg of the above-mentioned resin, and in particular, the elongation can be adjusted high by decreasing the Tg.

  The resin content is preferably 3.0 to 50 mass%, more preferably 5.0 to 50 mass%, based on the total amount of the resin liquid. The upper limit is further preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less. When the content of the resin is within the above range, a uniform coating film can be formed.

(water)
The content of water is preferably 50 to 95% by mass, more preferably 50 to 90% by mass, and further preferably 75 to 85% by mass with respect to the total amount of the resin liquid. When the water content is within the above range, the storage stability of the resin liquid tends to be further improved.

(Other ingredients)
The resin liquid used in this embodiment is the same surfactant used in the following reaction liquid, the same solvent, dissolution aid, viscosity adjuster, pH adjuster, and antioxidant used in the following reaction liquid. Various additives such as a preservative, an antifungal agent, a corrosion inhibitor, and a chelating agent for capturing metal ions that affect the dispersion can be appropriately added.

[Reaction solution adhesion process]
The reaction liquid attaching step is a step of attaching a reaction liquid containing a reactive agent that aggregates or thickens the components of the colored ink composition to the recording area to which the resin liquid is attached. The means for attaching the reaction solution is not particularly limited, and for example, roller coating, spray coating, or an ink jet method can be used. Among these, it is preferable that the reaction liquid is attached to the recording area to which the resin liquid is attached by an ink jet method. By attaching the reaction solution by an ink jet method, it is likely that the surface quality change of the media is suppressed and the wet friction resistance is improved.

The amount of the reactant attached to the recording area is preferably 0.01 to 1.0 mg / inch ² , more preferably 0.01 to 0.50 mg / inch ² , and still more preferably 0.01 to 0. 1 mg / inch ² . When the adhesion amount of the reactant to the recording area is within the above range, the resulting printed matter tends to be further suppressed from being sticky and ruled lines.

  The time interval from the end of the reaction liquid attaching step to the start of the colored ink composition attaching step is preferably 10 seconds or less, more preferably 0.10 to 10 seconds, and more preferably 0.10 to 8. 0 seconds, more preferably 0.10 to 5.0 seconds, and still more preferably 0.10 to 3.0 seconds. Since the time interval from the end of the reaction liquid adhesion process to the start of the colored ink composition adhesion process is 10 seconds or less, the reaction efficiency between the reaction liquid and the ink composition is further improved, and the image quality of the obtained recorded matter is improved. It tends to improve. In particular, when the film thickness of the resin film is small, it is preferable that the time interval is short.

(Reaction solution)
The reaction solution contains a reactant. When the reactant in the reaction liquid interacts with the ink composition, the components contained in the ink composition are aggregated to thicken or insolubilize the ink composition. Thereby, landing interference and bleeding of the ink composition to be subsequently attached can be prevented, and lines and fine images can be drawn uniformly. Although it does not specifically limit as a reactive agent, For example, a polyvalent metal salt and an organic acid are mentioned, It is preferable that a reactive agent contains at least any one of these. When the reactant contains at least one of a polyvalent metal salt and an organic acid, betalam and bleed tend to be further suppressed. Examples of components contained in the ink composition that aggregates with the reactant include pigments and resin fine particles described later.

(Polyvalent metal salt)
Although it does not specifically limit as a polyvalent metal salt, For example, the polyvalent metal salt of an inorganic acid or the polyvalent metal salt of an organic acid is preferable. Such a polyvalent metal salt is not particularly limited, but examples thereof include alkaline earth metals belonging to Group 2 of the periodic table (eg, magnesium, calcium), and transition metals belonging to Group 3 of the periodic table (eg, lanthanum). And salts of earth metals (eg, aluminum) and lanthanides (eg, neodymium) from group 13 of the periodic table. As these polyvalent metal salts, carboxylate (formic acid, acetic acid, benzoate, etc.), sulfate, nitrate, chloride, and thiocyanate are suitable. Among them, preferably, calcium salt or magnesium salt of carboxylic acid (formic acid, acetic acid, benzoate, etc.), calcium salt or magnesium salt of sulfuric acid, calcium salt or magnesium salt of nitric acid, calcium chloride, magnesium chloride, and thiocyanic acid. A calcium salt or a magnesium salt is mentioned. In addition, a polyvalent metal salt may be used individually by 1 type, and may use 2 or more types together.

(Organic acid)
The organic acid is not particularly limited, and examples thereof include maleic acid, acetic acid, phosphoric acid, oxalic acid, malonic acid, and citric acid. Among these, monovalent or divalent or higher carboxylic acids are preferable. By including such a carboxylic acid, the aggregation effect of the resin fine particles (A) is further improved, and as a result, the color developability tends to be more excellent. In addition, an organic acid may be used individually by 1 type, and may use 2 or more types together.

  The content of the reactant is preferably 5.0 to 20% by mass, more preferably 7.5 to 17.5% by mass, and still more preferably 10 to 15% by mass with respect to the total amount of the reaction solution. When the content of the reactive agent is within the above range, betalam and bleed tend to be further suppressed.

  The reaction solution may contain other components as necessary. Although it does not specifically limit as another component, For example, surfactant, a solvent, etc. are mentioned.

(Surfactant)
The reaction solution preferably contains a surfactant. The surfactant is not particularly limited, and examples thereof include acetylene glycol surfactants, fluorine surfactants, and silicone surfactants.

  The acetylene glycol-based surfactant is not particularly limited, and examples thereof include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl-5- Selected from alkylene oxide adducts of decyne-4,7-diol and alkylene oxide adducts of 2,4-dimethyl-5-decyn-4-ol and 2,4-dimethyl-5-decyn-4-ol One or more are preferred. Although it does not specifically limit as a commercial item of an acetylene glycol type surfactant, For example, E series (A product made by Air Products Japan (Inc)) (Surfinol 104, etc.), such as Olfine 104 series and Olfine E1010, 465, 61 (trade name manufactured by Nissin Chemical Industry CO., Ltd.). One acetylene glycol surfactant may be used alone, or two or more acetylene glycol surfactants may be used in combination.

  The fluorosurfactant is not particularly limited. For example, perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, perfluoroalkyl betaine, A fluoroalkylamine oxide compound is mentioned. Although it does not specifically limit as a commercial item of a fluorochemical surfactant, For example, S-144, S-145 (Asahi Glass Co., Ltd. product); FC-170C, FC-430, Fluorard-FC4430 (Sumitomo 3M Co., Ltd. product) FSO, FSO-100, FSN, FSN-100, FS-300 (manufactured by Dupont); FT-250, 251 (manufactured by Neos Co., Ltd.) and the like. A fluorine-type surfactant may be used individually by 1 type, and may use 2 or more types together.

  Examples of silicone surfactants include polysiloxane compounds and polyether-modified organosiloxanes. Although it does not specifically limit as a commercial item of a silicone type surfactant, Specifically, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK -348, BYK-349 (above trade name, manufactured by Big 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, KF-6017 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. A silicone type surfactant may be used individually by 1 type and may use 2 or more types together.

  The content of the surfactant is preferably 0.050 to 2.5 parts by mass, more preferably 0.050 to 1.0 parts by mass with respect to the total amount of the reaction solution. When the content of the surfactant is within the above range, the wettability of the reaction liquid adhering to the recording medium tends to be further improved.

(solvent)
Although it does not specifically limit as a solvent, For example, an organic solvent or water can be used.

  Examples of water include water from which ionic impurities have been removed as much as possible, such as pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, and distilled water, and ultrapure water. In addition, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is used, generation of mold and bacteria can be prevented when the reaction solution is stored for a long time. This tends to improve the storage stability.

  The organic solvent is not particularly limited. For example, hydrocarbon solvents such as toluene, hexane, cyclohexane, benzene, octane and isooctane; ester solvents such as ethyl acetate, butyl acetate and γ-butyrolactone; acetone, methyl ethyl ketone and methyl isobutyl Ketone solvents such as ketone and cyclohexanone; alcohol solvents such as methanol, ethanol, propanol, isopropanol and butanol; halogen solvents such as dichloroethane and chloroform; ether solvents such as diethyl ether and tetrahydrofuran; N, N-dimethylformamide N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, N-methyl-ε-caprolactam, hexamethylphosphoramide, etc. Examples include amide solvents, glycerin, triethylene glycol, triethylene glycol monobutyl ether, and water-soluble organic solvents.

[Colored ink composition adhesion step]
The colored ink composition attaching step is a step of attaching the colored ink composition containing a coloring material to the recording area to which the reaction liquid is attached by an inkjet method.

[Ink composition]
The ink composition contains a color material, and may contain a resin dispersion, water, a penetrating solvent, a humectant, and other components as necessary. A pigment is preferable as the color material. The ink composition is preferably a water-based ink composition in which a resin dispersion is dispersed in water. By using such an ink composition, there is a tendency that the abrasion resistance of the obtained recorded matter is further improved.

(Color material)
A pigment can be used as the color material. Although it does not specifically limit as a pigment, For example, the following are mentioned.

  The carbon black used for the black ink is not particularly limited. 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B (Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, etc. Rega1 330R, Rega1 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. (Cabot Corp. CA Kol. , Color B lack FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color B1ack S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, Special Black 5, Special Black 4A , Special Black 4 (manufactured by Degussa).

  Although it does not specifically limit as a pigment used for white ink, For example, C.I. I. Pigment white 6, 18, 21, titanium oxide, zinc oxide, zinc sulfide, antimony oxide, zirconium oxide, white hollow resin particles and polymer particles.

  Although it does not specifically limit as a pigment used for yellow ink, For example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 37, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 99, 108, 109, 110, 113, 114, 117, 120, 124, 128, 129, 133, 138, 139, 147, 151, 153, 154, 167, 172, 180.

  Although it does not specifically limit as a pigment used for a magenta ink, For example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 2, 48: 5, 57: 1, 88, 112, 114, 122, 123, 144, 146, 149, 150, 166, 168, 170, 171, 175, 176, 177, 178, 179, 184, 185, 187, 202, 209, 219, 224, 245, or C.I. I. Pigment violet 19, 23, 32, 33, 36, 38, 43, 50.

  Although it does not specifically limit as a pigment used for cyan ink, For example, C.I. I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15:34, 15: 4, 16, 18, 22, 25, 60, 65, 66, C.I. I. Bat Blue 4, 60.

  The pigments other than those described above are not particularly limited. I. Pigment green 7,10, C.I. I. Pigment brown 3, 5, 25, 26, C.I. I. Pigment orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63.

  The content of the pigment is preferably 0.2 to 10% by mass, more preferably 1.0 to 7.5% by mass, and further preferably 2.5 to 7% by mass with respect to the total amount of the ink composition. 5% by mass. When the pigment content is within the above range, the color developability tends to be further improved.

(Resin dispersion)
By using the resin dispersion, the resin dispersion, the resin, and the pigment are fused to each other to fix the pigment to the recording medium, thereby further improving the abrasion resistance and adhesion of the image portion of the recorded matter. Can be good. Among the resin dispersions, urethane resins, acrylic resins, and polyethylene resins are preferable.

  Examples of the resin dispersion are the same as those exemplified for the resin liquid. A resin dispersion may be used individually by 1 type, and may be used in combination of 2 or more type.

  The ink composition used in this embodiment includes the same surfactant as the above reaction liquid, the same solvent as the above reaction liquid, a dissolution aid, a viscosity adjusting agent, a pH adjusting agent, an antioxidant, an antiseptic, and an antifungal agent. Various additives such as a corrosion inhibitor and a chelating agent for capturing metal ions that affect the dispersion can also be appropriately added. Moreover, you may further contain water-soluble resin. The water-soluble resin also has a function similar to that of the above-described resin dispersion, and can further improve the abrasion resistance and adhesion of the image portion of the recorded matter.

[Resin liquid]
The resin liquid of the present embodiment is used for a vapor ink jet recording method, and includes a resin having an acid value of 50 mgKOH / g or less. As a result, a recorded matter in which bethamra and ruled line balls are suppressed is obtained. Further, when the reaction liquid and the ink composition are attached to the recording medium, it is preferable that the permeation rate of the resin film is decreased as the time interval becomes longer. In order to slow down the permeation rate of the resin film, it is conceivable to increase the film thickness of the resin film. In this case, however, there may be a problem that the surface quality of the recording medium changes. On the other hand, by using the resin liquid of the present embodiment, the surface quality change (gloss change) of the recording medium can be suppressed. Therefore, the problem caused by thickening the resin film as described above can be solved.

[Recorded material]
The recorded matter obtained by the above recording method preferably has a low gloss change rate. The gloss change rate here refers to the change rate between the gloss of the recording medium before recording and the gloss of the recording surface after resin coating. As described above, the recorded matter obtained by the recording method of the present embodiment can solve the problem caused by thickening the resin film, and the surface quality change due to the application of the resin liquid is suppressed. It will be a thing.

[Recording device]
Next, a recording apparatus that can be used in the recording method of the present embodiment will be described. It is assumed that the resin liquid adheres to the recording medium before setting the recording medium in the recording apparatus. FIG. 1 is a side view showing an outline of an example of an inkjet recording apparatus 1 that can be used in the present embodiment. As shown in FIG. 1, the inkjet recording apparatus 1 includes a recording medium feeding unit 10, a transport unit 20, a recording unit 30, a drying device 90, and a discharge unit 70.

  Among these, the drying device 90 includes a first drying unit 40 that dries the reaction liquid, and a second drying unit 50 that dries the recorded matter obtained by the recording method according to the present embodiment.

  Further, the feeding unit 10 is provided so that the roll-shaped recording medium F can be fed to the transport unit 20. Specifically, the feeding unit 10 includes a roll medium holder 11, and the roll medium holder 11 holds a roll-shaped recording medium F. Then, by rotating the roll-shaped recording medium F, the recording medium F can be fed to the conveyance unit 20 on the downstream side in the feeding direction Y.

  Further, the transport unit 20 is provided so that the recording medium F sent from the feeding unit 10 can be transported to the recording unit 30. Specifically, the transport unit 20 includes a first feed roller 21 and is configured to be able to transport the sent recording medium F further to the recording unit 30 on the downstream side in the feed direction Y.

  The recording unit 30 is provided so that a reaction liquid is applied to the recording medium F sent from the transport unit 20 and an ink composition is ejected for recording. Specifically, the recording unit 30 includes heads 31 and 32 that perform a reaction liquid attaching process, a recording head 33 that performs an ink composition attaching process, and a platen 34 as a medium support part.

  Among these, the platen 34 is provided so that the recording medium F can be supported from the back surface. The platen 34 is provided with a first drying unit 40 that dries the reaction liquid adhering to the recording medium F and the ink composition adhering to the recording medium F. Further, a second feed roller 43 is provided downstream of the platen 34 in the feed direction Y. The second feed roller 43 is configured to send the recorded recording medium F to the second drying unit 50 on the downstream side in the feed direction Y.

  The second drying unit 50 is configured to further dry the reaction liquid adhering to the recording medium F and the ink composition adhering to the recording medium F. Further, a third feed roller 65 is provided in the vicinity of the outlet 64 of the second drying unit 50. The third feed roller 65 is disposed so as to be in contact with the back surface of the recording medium F, and is configured to be able to feed the recording medium F to the discharge unit 70 on the downstream side in the feeding direction Y.

  Further, the discharge unit 70 is provided so that the recording medium F sent from the second drying unit 50 can be further sent downstream in the feed direction Y and discharged to the outside of the inkjet recording apparatus 1. Specifically, the discharge unit 70 includes a fourth feed roller 71, a fifth feed roller 72, a sixth feed roller 73, a seventh feed roller 74, and a take-up roller 75. Among these, the 4th feed roller 71 and the 5th feed roller 72 are arrange | positioned so that the surface of the recording medium F may be contacted. Moreover, the 6th feed roller 73 and the 7th feed roller 74 are arrange | positioned so that a roller pair may be comprised. The recording medium F discharged by the sixth feed roller 73 and the seventh feed roller 74 is provided so as to be taken up by the take-up roller 75.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited in any way by the following examples.

〔界面活性剤〕
サーフィノール１０４（日信化学工業社製、アセチレングリコール系界面活性剤）
〔有機溶剤〕
ジエチレングリコール [Material for resin liquid]
The main materials for the resin liquid used in the following examples and comparative examples are as follows.
〔resin〕
The resin used is shown in Table 1 below.

[Surfactant]
Surfynol 104 (Nisshin Chemical Industry Co., Ltd., acetylene glycol surfactant)
〔Organic solvent〕
Diethylene glycol

[Resin Production Examples 1 to 9]
Of the resins in the production examples in the table, the urethane resin is synthesized as a urethane resin synthesis example described in the examples of JP-A-2010-053328 and used as a raw material for the urethane resin at this time. The acid value, glass transition temperature, and elongation of the resin were adjusted by changing the type and ratio of the product to be used. Thus, the resins of Production Examples 2 and 6 to 9 were produced as resin emulsion liquids. Further, among the resins of the production examples in the table, the acrylic resin was synthesized as in the polymer fine particle preparation example described in the examples of JP-A-2009-2221459. The acid value, glass transition temperature, and elongation of the resin were adjusted by changing the type and ratio of materials used as raw materials. Thus, the resin of the manufacture examples 3-5 was manufactured as a resin emulsion liquid. In addition, among the resins of production examples in the table, polysulfoesters are produced by producing a polyvalent carboxylic acid and a polyol compound by a known polyester resin production method with reference to the examples in JP2011-94288. By using a polyol compound having a sulfonic acid group as a polyol compound, a polyester resin having a sulfonic acid group is obtained, and by changing the type and use ratio of a polyvalent carboxylic acid or a polyol compound, the resin acid Value, glass transition temperature, and elongation were prepared. Thus, the resin of Production Example 1 was produced as a resin emulsion liquid.

[Preparation of resin solution]
Each material was mixed with the composition shown in the following Table 2, and stirred sufficiently to obtain each resin liquid. In Table 2 below, the numerical unit is mass%, and the total is 100.0 mass%. The resin has a solid mass.

(Measurement of acid value)
The acid value means the number of mg of KOH required to neutralize 1 g of resin solid content, and was measured based on JIS K 2501-2003 “Petroleum products and lubricating oil-neutralization number test method”. Specifically, it was measured using a potentiometric titrator (AT-710M, manufactured by Kyoto Electronics Industry Co., Ltd.).

(Measurement of glass transition point)
The glass transition point (Tg) was measured using a differential scanning calorimeter (DSC) thermal analyzer. As the thermal analyzer, for example, SSC5000 manufactured by Seiko Electronics Co., Ltd. was used.

(Elongation)
A resin film (resin film) having a film thickness of 500 μm after drying was prepared. A resin liquid (aqueous dispersion) is applied onto a polytetrafluoroethylene sheet, dried at room temperature for 15 hours, further dried at 80 ° C. for 6 hours, and 120 ° C. for 20 minutes, and then peeled off from the sheet. A resin film (resin film) was used. The elongation of the obtained resin film was measured at a measurement temperature of 20 ° C. and a measurement speed of 200 mm / min using a 76 Tensilon universal testing machine RTC-1225A (manufactured by Orientec Co., Ltd.). It is the ratio of the stretched length to the length in the length direction of the resin film before being stretched by measuring the length in the length direction before the resin film breaks.

(Measurement of surface free energy)
The surface free energy of the dried film (thickness 1 μm) after coating and drying the resin liquid was measured at 25 ° C. For the measurement, an automatic contact angle meter DMs-400 manufactured by Kyowa Interface Chemical Co., Ltd. was used.

[Storage stability]
After preparing the resin solution, it was put in a container, sealed, and stored at 50 ° C. for 7 days. And the viscosity change in 25 degreeC before and behind storage was calculated | required. An E-type viscometer was used as the viscometer. It is presumed that the smaller the change in viscosity, the better the dispersion stability of the resin fine particles. Therefore, quality does not deteriorate during storage or use.
(Evaluation criteria)
○: The viscosity change was 1 mPa · s or less.
Δ: Viscosity change was more than 1 mPa · s and 4 mPa · s or less.
X: The viscosity change exceeded 4 mPa · s.

[Reaction liquid materials]
The main materials for reaction solutions used in the following examples and comparative examples are as follows.
(Reactant)
Calcium acetate maleic acid (surfactant)
Surfynol 104 (Nisshin Chemical Industry Co., Ltd., acetylene glycol surfactant)
〔Organic solvent〕
Diethylene glycol monobutyl ether Diethylene glycol

[Preparation of reaction solution]
Each material was mixed with the composition shown in Table 3 below and stirred sufficiently to obtain a reaction solution. In Table 3 below, the numerical unit is mass%, and the total is 100.0 mass%.

[Material for ink composition]
The main materials for the ink compositions used in the following examples and comparative examples are as follows.
[Colorant]
P. B15: 3 (Pigment Black 15: 3)
[Penetration solvent]
1.2-Hexanediol [surfactant]
BYK348 (Bic Chemie Japan, silicone surfactant)
[Humectant]
Propylene glycol

[Preparation of ink composition]
Each material was mixed with the composition shown in Table 4 below and stirred sufficiently to obtain an ink composition. In Table 4 below, the numerical unit is mass%, and the total is 100.0 mass%.

(Create recorded material)
Apply the resin liquid to the recording area of the recording medium (N mirror 73 (manufactured by Oji Paper Co., Ltd.), surface free energy: 37 mN / m) using a roll coater, heat dry at 70 ° C. for 2 minutes, and touch It was confirmed that there was no stickiness. In addition, the application amount (adhesion amount) of the resin liquid was as follows in terms of the adhesion amount of the resin of the resin liquid. The thickness of the resin layer after drying is measured and shown in Table 5.
Dry resin thickness Resin adhesion amount 0.1μm 0.02mg / inch ²
1.0 μm 0.2 mg / inch ²
3.0μm 0.6mg / inch ²

A modified PX-G930 (manufactured by Epson) was prepared. The head was filled with the reaction liquid and the colored ink composition prepared above at 1 nozzle row / 1 liquid. The nozzle density of the nozzle row of the head was 360 dpi, and the number of nozzles in one nozzle row was 360. The above-mentioned recording medium with the resin liquid adhered was set, and the reaction liquid was adhered at an adhesion amount of 1 mg / inch ² on the area where the resin liquid was adhered to form two 5 cm × 5 cm solid patterns.

After the reaction solution is attached, the recording medium is set again in the recording apparatus, and the ink composition is attached to each of the two solid pattern regions to which the reaction solution is attached at an adhesion amount of 8 mg / inch ^2. A ruled line pattern having a width of 100 μm was formed. The surface temperature of the recording medium was set to 25 ° C. during the adhesion of the reaction liquid and the ink. In addition, the dot resolution of adhesion was set to 720 × 720 dpi for the reaction solution and 1440 × 1440 dpi for the colored ink. Furthermore, a stop time was provided as necessary so that the time interval from the end of the adhesion of the reaction liquid to the start of the adhesion of the ink composition became the time in Table 5.

  After the ink composition was adhered, the recording medium was discharged and dried by heating in an oven at 60 ° C. for 10 minutes, and the following evaluation was performed. The results are shown in Table 5.

[Gloss change rate]
Glossiness of the recording medium and the adhesion area of the recording medium that has been subjected to the resin liquid adhesion process is measured at 60 ° using a gloss meter GM-268Plus (manufactured by Konica Minolta Co., Ltd.), before the resin liquid adhesion process. The change rate% of the glossiness of the adhered area to the glossiness of the recording medium was calculated. A smaller change rate is preferable because there is no sense of incongruity in the attached region.

[Image quality (Bethamra)]
The solid pattern portion of the obtained recorded matter was visually observed, and the image quality (betamula) was evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: No unevenness inside the pattern (coloring by ink appears uneven), no bleeding around the pattern.
○: No unevenness inside the pattern. Bleed around the pattern.
Δ: Some unevenness appears in the pattern ×: Considerable unevenness appears in the pattern

[Image quality (ruled line ball)]
The ruled line pattern portion of the obtained recorded matter was visually observed, and the image quality (ruled line ball) was evaluated according to the following evaluation criteria.
(Evaluation criteria)
○: Even when observed with a magnifying glass, a ball-like ruled line (ruled line ball) cannot be seen.
Δ: A ruled ball cannot be seen by visual observation, but a ruled ball can be seen when observed with a magnifying glass.
X: A ruled ball can be seen visually.

[Crack resistance]
Surepress L-4033A (Seiko Epson) modified machine was prepared. A line printer that performs one-pass recording while fixing the line head and transporting the recording medium to the line head was used. The line head can be filled with reaction liquid and colored ink. A recording medium (N mirror 73 (manufactured by Oji Paper Co., Ltd.) is used as a roll recording medium having a width of 15 cm, and a recording medium subjected to a resin liquid coating process is prepared. The recording medium was fed to the take-up roller at a speed of 10 m / min, and the recording medium was heated at 50 ° C. in the drying area in the path. Then, the sheet was fed again to the winding unit at the same speed.

  The above operation assumes the case where all colors cannot be recorded by one feeding and recording is performed many times because of the large number of types of colored inks used for recording. If the dry resin film is free of cracks and cracks, it is advantageous in that a clean recording can be obtained when a roll-shaped recording medium is used, and that the reaction liquid penetrates through the cracked part and the image quality does not deteriorate. . In particular, since the line printer often uses a roll recording medium and has a high recording medium conveyance speed, it is useful that there is no crack.

The roll recording medium obtained as described above was observed, and crack resistance was evaluated according to the following evaluation criteria.
(Evaluation criteria)
○: No cracks or cracks are observed in the resin liquid adhesion region even when observed with a magnifying glass.
Δ: Cracks and cracks are confirmed in the resin liquid adhesion region with a loupe, but are not visually confirmed.
X: Cracks and cracks are visually confirmed in the resin liquid adhesion region.

  As described above, in Comparative Example 1 using a resin solution having an acid value exceeding 50 mgKOH / g, the reaction solution and the resin solution reacted with each other. On the other hand, in Comparative Example 2 in which no resin solution was used, the resin solution was repelled on the recording medium, resulting in a sticky line and ruled line balls.

  DESCRIPTION OF SYMBOLS 1 ... Inkjet recording apparatus, 10 ... Feed part, 11 ... Roll medium holder, 20 ... Conveyance part, 21 ... 1st feed roller, 30 ... Recording part, 31 ... Head, 32 ... Head, 33 ... Recording head, 34 ... Platen 40 ... first drying section 43 ... second feeding roller 50 ... second drying section 64 ... exit 65 ... third feeding roller 70 ... discharge section 71 ... fourth feeding roller 72 ... fifth Feed roller 73 ... Sixth feed roller, 74 ... Seventh feed roller, 75 ... Winding roller, 90 ... Drying device, F ... Recording medium, Y ... Feed direction.

Claims (10)

A resin liquid attaching step of attaching a resin liquid containing a resin having an acid value of 50 mgKOH / g or less to a recording area of a recording medium;
A reaction liquid attaching step of attaching a reaction liquid containing a reactive agent that aggregates or thickens the components of the colored ink composition to the recording area to which the resin liquid is attached;
A colored ink composition adhering step of adhering the colored ink composition containing a coloring material to the recording area to which the reaction liquid is adhered by an inkjet method,
Inkjet recording method.   The inkjet recording method according to claim 1, wherein the surface free energy of the dry film in the recording region to which the resin liquid is adhered is 40 mN / m or more.   The inkjet recording method according to claim 1, wherein the resin has a carboxyl group or a base thereof.   The inkjet recording method according to claim 1, wherein the resin has a glass transition point of −35 ° C. or higher.   The ink jet recording method according to claim 1, wherein the acid value of the resin is 2.0 to 40 mg KOH / g.   The inkjet recording method according to any one of claims 1 to 5, wherein a film thickness of the dry film in the recording region to which the resin liquid is adhered is 0.10 to 1.0 µm.   The inkjet recording method according to claim 1, wherein the elongation of the resin is 5% or more.   The ink jet recording method according to any one of claims 1 to 7, wherein a time interval from the end of the reaction liquid attaching step to the start of the colored ink composition attaching step is 10 seconds or less. The resin liquid further contains water,
The inkjet recording method according to claim 1, wherein the resin is a resin dispersion dispersed in the water.   A resin liquid containing a resin having an acid value of 50 mgKOH / g or less, which is used in the ink jet recording method according to claim 1.

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