JP2016060167A - Recording method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording method capable of providing a recorded article having high picture quality and less odor.SOLUTION: There is provided a recording method by using a composition group containing one or more first color ink composition containing a first coloring agent and water as a volatile component, one or more second color ink composition containing a second coloring agent and water as a volatile component, a reaction liquid composition containing a coagulant, and one or more other ink compositions containing water as the volatile component, the method including a first process of adhering the reaction liquid composition to a medium to be recorded to form a recording area S1, a second process of adhering one or more of the first color ink composition and one or more of the other ink compositions to the recording area S1 to form the recording area S2, a third process of adhering one or more of the second color ink composition to the recording area S2 to form the recording area S3, where in the second process, the total adhered amount of water in an area where total adhered amount of water contained in the first color ink composition and the other ink composition is minimum is 50 mass% or more of an area where the total adhered amount of water is maximum.SELECTED DRAWING: None

Description

  The present invention relates to a 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. For example, Patent Document 1 discloses an ink jet printing method for the purpose of image formation such as realization of ink ejection characteristics and formation of a white image having high concealment when a white image is formed using an ink jet recording method. It is disclosed that recording is performed on an OHP sheet using an ink composition containing a titanium dioxide sol and a reaction solution containing magnesium sulfate.

JP 2002-103783 A

  However, when recording on a recording medium using the inkjet recording method described in Patent Document 1, if the amount of the ink composition applied varies depending on the image area, the image quality varies depending on the area, or bleeding occurs. There is a problem of doing. Further, when the application amount of the ink composition varies depending on the image area, there may be a problem that odor is generated from the obtained recorded matter.

  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 a recording method capable of obtaining a recorded matter with high image quality and less odor.

  The present inventors diligently studied to solve the above problems. As a result, the present invention has been completed by finding that the above-mentioned problems can be solved by a predetermined recording method.

That is, the present invention is as follows.
[1]
One or more first colored ink compositions containing water as the first colorant and volatile component, one or more second colored ink compositions containing water as the second colorant and volatile component, and a flocculant A recording method comprising using a composition group comprising a reaction liquid composition and one or more other ink compositions containing water as a volatile component,
A first step of forming the recording region S1 by adhering the reaction liquid composition to a recording medium;
A second step of forming the recording area S2 by adhering one or more of the first colored ink compositions and one or more of the other ink compositions to the recording area S1;
A third step of forming the recording region S3 by attaching one or more second colored ink compositions to the recording region S2,
In the second step, the total amount of water in the region with the smallest total amount of water contained in the first colored ink composition and the other ink composition is the total amount of water in the region with the largest amount. The recording method which is 50 mass% or more with respect to the adhesion amount.
[2]
One or more first colored ink compositions containing water as the first colorant and volatile component, one or more second colored ink compositions containing water as the second colorant and volatile component, and a flocculant A recording method comprising using a composition group comprising a reaction liquid composition and one or more other ink compositions containing water as a volatile component,
A first step of forming the recording region S1 by adhering the reaction liquid composition to a recording medium;
A second step of forming the recording area S2 by adhering one or more of the first colored ink compositions and one or more of the other ink compositions to the recording area S1;
A third step of forming the recording region S3 by attaching one or more second colored ink compositions to the recording region S2,
In the first step and the second step, the water in the region where the total amount of water contained in the reaction liquid composition, the first colored ink composition, and the other ink composition is the smallest. A recording method in which the total adhesion amount is 50% by mass or more with respect to the total adhesion amount of water in the largest region.
[3]
The recording according to [1] or [2], wherein the other ink composition is a clear ink composition or an ink composition in which the content of the first colorant is less than that of the first color ink. Method.
[4]
One of the first colored ink composition and the second colored ink composition is a white ink composition containing a white colorant,
The recording method according to any one of [1] to [3], wherein the other is a color ink composition containing a colorant other than the white colorant.
[5]
In the third step, one or more of the volatile components contained in the first colored ink composition and the other ink composition remain in the recording area S2 to the recording area S2. The recording method according to any one of [1] to [4], wherein the second colored ink composition is adhered.
[6]
In the first step, the recording region S1 is formed by attaching the reaction solution composition to the recording medium so as to form regions having different amounts of the reaction solution composition attached thereto. [1] The recording method according to any one of [5].
[7]
In the second step, the one or more first colored ink compositions and the other ink composition are attached to the recording area S1 simultaneously or sequentially to form the recording area S2. The recording method according to any one of [1] to [6] above.
[8]
At least one of the first colored ink composition, the second colored ink composition, and the other ink composition includes the water and the organic solvent as the volatile components. The recording method according to any one of the above.

It is a figure which shows the outline of an example of the inkjet recording device which can be used for this embodiment.

  Hereinafter, a mode for carrying out 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, Various modifications are possible without departing from the scope of the invention. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

[Recording Method of First Embodiment]
The recording method of the first embodiment includes one or more first colored ink compositions containing water as a first colorant and a volatile component, and one or more second colors containing water as a second colorant and a volatile component. A recording method comprising a composition group comprising an ink composition, a reaction liquid composition containing a flocculant, and one or more other ink compositions containing water as a volatile component, A first step of depositing the reaction liquid composition on a medium to form a recording area S1, and one or more of the first colored ink composition and one of the other ink compositions to the recording area S1. A second step of forming the recording region S2 by attaching two or more, and a step of forming the recording region S3 by attaching one or more second colored ink compositions to the recording region S2. 3 steps, and in the second step, the first colored ink The total amount of water in the region with the smallest total amount of water contained in the composition and the other ink composition is 50% by mass or more with respect to the total amount of water in the region with the largest amount. .

  By using the reaction liquid composition containing an aggregating agent, the colorant in the ink composition is aggregated, and bleeding of the recorded matter obtained is suppressed. However, when the amount of the ink composition deposited varies depending on the location of the recorded material, for example, when the ink composition is deposited on the recording medium with a different duty in order to give a gradation, or the ink is deposited on the recording medium. In the case of drawing an image with a composition, there is a problem that the image of the obtained recorded matter varies depending on each part. Specifically, the degree of bleed suppression differs or the glossiness varies depending on the location of the obtained recorded matter.

  Such a problem is caused by a difference in the amount of water present in the recording area (for example, the recording area S1) when the ink composition is applied. In particular, when a plurality of types of ink compositions are used while being superimposed on a recording medium, if the amount of the ink composition deposited earlier is small (low duty), the amount of water on the recording area is reduced, and the flocculant However, the effect of the flocculant on the ink composition to be attached later is reduced.

  On the other hand, in the recording method according to the present embodiment, another ink composition is used for adjusting the water content. That is, the total amount of water in the region with the smallest total amount of water contained in the first colored ink composition and the other ink composition is 50% of the total amount of water in the region with the largest amount. By setting it as mass% or more, the effect of a desired flocculant can be acquired also with respect to a 2nd colored ink composition irrespective of the duty of the 1st colored ink composition made to adhere previously. Therefore, the image quality of the obtained recorded matter is improved. Moreover, since the effect of the flocculant can be obtained more efficiently, it is not necessary to use the flocculant excessively, and the odor derived from the flocculant can also be suppressed.

  Here, 100% duty means that one drop of ink is attached to all pixels. For example, 150% duty means that 1.5 drops of ink drop is attached per pixel. means. It should be noted that even if the duty is 100%, the coverage may not be 100% depending on the volume of the ink droplet and the wet spreading property.

[First step]
The first step is a step of forming the recording area S1 by attaching the reaction liquid composition to the recording medium. In the first step, it is preferable to form the recording area S1 by adhering the reaction liquid composition to the recording medium so as to form areas with different amounts of adhesion of the reaction liquid composition. By doing so, it is possible to form a recording region S1 having a desired density distribution of the flocculant in accordance with the obtained recorded image, thereby improving the image quality of the recorded product that is obtained. There is a tendency. Moreover, since the effect of the flocculant can be obtained more efficiently, it is not necessary to use the flocculant excessively, and the odor derived from the flocculant can also be suppressed.

  The means for attaching the reaction liquid composition is not particularly limited, and for example, roller coating, spray coating, and ink jet coating can be used. In addition, you may further have the process of drying at least one part of the reaction liquid composition apply | coated to the recording medium in the 1st process or after the 1st process.

Adhesion amount to the recording medium of the reaction liquid composition is preferably ^{0.30~5.0mg / inch 2, 0.30~3.0mg / inch} 2 is preferable. When the adhesion amount of the reaction liquid composition is within the above range, the image quality of the obtained recorded product tends to be more excellent.

(Reaction solution composition)
The reaction solution composition includes a flocculant. When the flocculant component in the reaction liquid composition interacts with the ink composition, the ink composition is thickened or insolubilized. 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.

(Flocculant)
The flocculant is not particularly limited, and examples thereof include polyvalent metal salts, organic acids, and organic acid salts. Of these, polyvalent metal salts are preferred. By using a reaction solution composition containing a polyvalent metal salt, the flocculant effect tends to be more excellent.

(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, and examples thereof include alkaline earth metals belonging to Group 2 of the periodic table (for example, magnesium and calcium) and transition metals belonging to Group 3 of the periodic table (for example, 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 or its salt)
Although it does not specifically limit as an organic acid or its salt, For example, phosphoric acid, oxalic acid, malonic acid, a citric acid, or its salt is mentioned. Of these, monovalent or divalent or higher carboxylic acids or salts thereof are preferred. By including such a carboxylic acid or a salt thereof, the flocculant effect tends to be more excellent. In addition, an organic acid or its salt may be used individually by 1 type, and may use 2 or more types together.

  The content of the flocculant is preferably 1.0 to 20 parts by mass, more preferably 2.0 to 10 parts by mass, and further preferably 2.5 to 7 parts by mass with respect to the total amount of the reaction solution composition. .5 parts by mass. When the content is within the above range, the flocculant effect tends to be more excellent.

  The reaction solution composition may contain other components as necessary. Although it does not specifically limit as another component, For example, the water which is a volatile component, the organic solvent which is a volatile component, surfactant, etc. are mentioned.

(water)
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 ink is stored for a long period of time. This tends to improve the storage stability.

  The content of water is preferably 50 to 90% by mass, more preferably 50 to 85% by mass, and further preferably 50 to 80% by mass with respect to the total amount of the reaction solution composition. When the water content is within the above range, the flocculant effect tends to be further improved.

(Organic solvent)
Examples of the organic solvent include, but are not limited to, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,2-butanediol, and 1,2-pentanediol. 1,2-hexanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso -Propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monobutyl ether Ter, diethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, propylene glycol mono- n-butyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-iso-propyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol Butyl methyl Ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, tripropylene glycol dimethyl ether, methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n-butanol, 2-butanol, alcohols or glycols such as tert-butanol, iso-butanol, n-pentanol, 2-pentanol, 3-pentanol, and tert-pentanol; N, N-dimethylformamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, sulfur Examples include holan and 1,1,3,3-tetramethylurea. Of these, water-soluble organic solvents such as 1,2-hexanediol and propylene glycol are preferable.

  The content of the organic solvent is preferably 10 to 30% by mass, more preferably 12.5 to 30% by mass, and further preferably 15 to 30% by mass with respect to the total amount of the reaction solution composition. . When the content of the organic solvent is within the above range, the flocculant effect tends to be further improved.

(Surfactant)
The surfactant is not particularly limited, but for example, at least one of acetylene glycol surfactants, fluorine surfactants, and silicone surfactants is preferable.

  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 acetylene glycol-type surfactant, For example, E series (A product made by Air Products Japan (Inc)) (Surfinol 465), such as Olfine 104 series and Olfine E1010, Surfynol 61 (trade name, manufactured by Nissin Chemical Industry CO., Ltd.) and the like. 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.

  The content of the surfactant is preferably 0.10 to 5.0 mass%, more preferably 0.10 to 3.0 mass%, based on the total amount of the reaction solution composition. When the content of the surfactant is within the above range, the wettability of the reaction liquid composition attached to the recording medium tends to be further improved.

[Second step]
The second step is a step of forming the recording region S2 by attaching at least one of the one or more first colored ink compositions and the other ink composition to the recording region S1. At this time, the reaction liquid composition and the first colored ink composition react to rapidly aggregate the first colorant in the first colored ink composition. The reaction solution may be dried or not dried. When the reaction solution is not dried, the interval between the first step and the second step can be shortened, and the recording speed can be increased. In addition, you may further have the process of drying at least one part of the reaction liquid apply | coated to the recording medium and the 1st colored ink composition in the 2nd process or after the 2nd process.

  Note that “attaching at least one of the one or more first colored ink compositions and the other ink composition” means that other inks may be used even if only one or more first colored ink compositions are attached. It means that only the composition may be deposited or both may be deposited. Further, on the recording area S2, there are mixed areas where only one or more first colored ink compositions are adhered, areas where only other ink compositions are adhered, and areas where both are adhered. Also good. The ratio of the ink amount to be adhered in the second step is appropriately determined according to the obtained image, and more specifically, the first colored ink composition on the recording area. It is determined in accordance with the duty.

The adhesion amount of the first colored ink composition in the second step is preferably 0 to 20 mg / inch ² , more preferably 0 to 15 mg / inch ² . When the adhesion amount of the first colored ink composition is within the above range, an image having light and shade within a desired duty range tends to be obtained.

The adhesion amount of the other ink composition in the second step is preferably 0 to 20 mg / inch ² , more preferably 0 to 15 mg / inch ² . When the adhesion amount of the other ink composition is within the above range, an image having a light and shade within a desired duty range tends to be obtained.

  In the second step, the total amount of water in the region where the total amount of water contained in the first colored ink composition and the other ink composition is the smallest is the total amount of water in the region where the total amount of water is the largest. In contrast, the recording area S2 is formed so as to be 50% by mass or more. The total amount of water in the region where the total amount of water is the smallest is 50% by mass or more, preferably 55 to 100% by mass, more preferably the total amount of water in the region where the water is the most. It is 60-100 mass%. When the total water deposition amount in the region where the total water deposition amount is the smallest is 50% by mass or more, the image quality of the obtained recorded matter is further improved.

  In the second step, the recording region S2 may be formed by attaching one or more first colored ink compositions and another ink composition to the recording region S1 simultaneously or sequentially. .

  In the second step, the first colored ink composition and the other ink composition can be ejected from the nozzles of the line head or the serial head by the ink jet method and adhered onto the recording medium. In the line method using a line head, the head is fixed and the recording medium is moved along the sub-scanning direction (the longitudinal direction of the recording medium, the conveyance direction), and the nozzle opening of the head is interlocked with this movement. By ejecting ink droplets, an image can be recorded on the recording medium. In the serial system using a serial head, the head is moved along the main scanning direction (the horizontal direction and the width direction of the recording medium), and ink droplets are ejected from the nozzle openings of the head in conjunction with this movement. Thus, an image can be recorded on the recording medium.

[First colored ink composition]
The first colored ink composition contains water as a first colorant and a volatile component. The first colored ink composition may be used alone or in combination of two or more. The first colored ink composition is attached to the recording area S1 with a desired duty so that a desired recorded image can be obtained.

(First colorant)
Although it does not specifically limit as a 1st colorant, For example, a pigment is mentioned.

  Although it does not specifically limit as a pigment used for black ink, For example, it is No. 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B, etc. (Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, etc. (above, Columbia Carbon, Carbon 1 Rubbi 400, Carbon Co. 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, white inorganic pigments of titanium oxide, zinc oxide, zinc sulfide, antimony oxide, and zirconium oxide. In addition to the white inorganic pigment, white organic pigments such as white hollow resin particles and polymer particles can also be used.

  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 (Ca), 48 (Mn), 57 (Ca), 57: 1, 88, 112, 114, 122, 123, 144, 146, 149, 150, 166, 168 170, 171, 175, 176, 177, 178, 179, 184, 185, 187, 202, 209, 219, 224, 245, or 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.

  In addition, the pigment used in color inks other than magenta, cyan, and yellow is 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 pigment may be obtained by dispersing a pigment dispersion obtained by dispersing in water with a dispersant, or by dispersing a self-dispersed surface-treated pigment into which hydrophilic groups are introduced by utilizing a chemical reaction on the surface of pigment particles in water. It is preferable to add to the ink composition as a pigment dispersion obtained by dispersing the pigment obtained by coating with a polymer in water.

  Examples of the dispersant include, but are not limited to, polymer dispersants (such as glue, gelatin, casein, albumin protein, gum arabic, tragacanth rubber, saponin glucosides, alginic acid and propylene glycol ester, alginic acid. Triethanolamine, alginate fermented ammonium alginate methylcellulose, carboxymethylcellulose, cellulose derivatives of ethylhydroxycellulose, polyvinyl alcohols, polypyrrolidones, polyacrylic acid, acrylic acid-acrylonitrile copolymer, potassium acrylate-acrylonitrile copolymer Polymer, vinyl acetate-acrylic acid ester copolymer, acrylic resin of acrylic acid-acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene -Methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-m-methylstyrene-acrylic acid copolymer styrene-acrylic resin, styrene-maleic acid copolymer, styrene-maleic anhydride Copolymer, vinyl naphthalene-acrylic acid copolymer, vinyl acetate-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate-maleic acid ester copolymer, vinyl acetate-croton copolymer, acetic acid Vinyl acetate copolymers of vinyl-acrylic acid copolymers and salts thereof) and surfactants (various anionic surfactants, nonionic surfactants, amphoteric surfactants) can be used.

  The self-dispersing surface-treated pigment having the hydrophilic group introduced therein can be dispersed or dissolved in water without a dispersant by a surface treatment in which a carboxyl group and a salt thereof are directly bonded to the surface of the pigment. It is. Specifically, it is obtained by grafting functional groups or molecules containing functional groups onto the surface of the pigment by physical treatment of vacuum plasma or chemical treatment using an oxidizing agent of sodium hypochlorite or ozone. Can do. The functional group grafted on one pigment particle may be single or plural kinds. The type and degree of the functional group to be grafted may be appropriately determined in consideration of the dispersion stability in the ink, the color density, and the drying property on the front surface of the inkjet head.

  The pigment coated with the polymer is not particularly limited. For example, after dispersing the pigment using a dispersant having a polymerizable group, a monomer copolymerizable with the dispersant (copolymerizable monomer). And a radical photopolymerization initiator, and can be obtained by emulsion polymerization in water. Among these polymers, monomers and oligomers having at least one of acryloyl group, methacryloyl group, vinyl group, and allyl group as double bonds are polymerized according to a known polymerization method using a photoradical polymerization initiator However, it can be preferably used. A general method can be used for the above emulsion polymerization, and the polymerization proceeds by free radicals generated by thermal decomposition of a water-soluble photoradical polymerization initiator in the presence of an emulsifier.

  The pigment and the dispersant constituting the pigment dispersion may be used alone or in combination of two or more.

  The content of the colorant is preferably 2.0 to 15% by mass, more preferably 2.0 to 14% by mass, and further preferably 2.0 to 12% with respect to the total amount of the color ink composition. % By mass.

(water)
As water, what was illustrated by the reaction liquid composition can be used, for example. The content of water is preferably 50 to 80% by mass, more preferably 55 to 75% by mass, and further preferably 60 to 70% by mass with respect to the total amount of the first colored ink composition.

(Organic solvent)
Further, the first colored ink composition may contain an organic solvent as a volatile component. Although it does not specifically limit as an organic solvent, For example, what was illustrated by the reaction liquid composition can be used. The content of the organic solvent is preferably 10 to 30% by mass, more preferably 12.5 to 27.5% by mass, and further preferably 15 to 25% with respect to the total amount of the first colored ink composition. % By mass. When the content of the organic solvent is within the above range, the recorded material is more excellent in water resistance and rubbing resistance, and the viscosity of the ink tends to be lowered.

(Surfactant)
Further, the first colored ink composition may include a surfactant. Although it does not specifically limit as surfactant, For example, what was illustrated by the reaction liquid composition can be used. The content of the organic solvent is preferably 0.10 to 5.0% by mass and more preferably 0.10 to 3.0% by mass with respect to the total amount of the first colored ink composition. When the content of the surfactant is within the above range, the wettability of the first colored ink composition attached to the recording medium tends to be further improved. In addition, since the resin is contained, a resin film is formed on the recording medium, so that the ink composition can be sufficiently fixed on the recording medium and the rub resistance of the recorded matter can be improved. .

(resin)
The resin that can be included in the first colored ink composition is not particularly limited, and examples thereof include resin fine particles and water-soluble resins. By using the resin fine particles, the resin in the resin fine particles, the resin and the pigment are fused to each other to fix the pigment to the recording medium. It can be made even better. Among resin fine particles, urethane resin, acrylic resin, and polyethylene resin are preferable.

  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.).

  Examples of the 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. Although it does not specifically limit as a commercial item of acrylic resin microparticles | fine-particles, For example, Mobile 966A (Nippon Synthetic Chemical Industry Co., Ltd. brand name), Microgel E-1002, Microgel E-5002 (Trade name, manufactured by Nippon Paint Co., Ltd.), Boncourt 4001, Boncourt 5454 (tradename, 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 Jonkrill 450, Jonkrill 840, Jonkrill 62J, Jonkrill 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, Jonkrill 538J, Jonkrill 7640, Jonkrill 7641, Jonkrill 631, Jonkrill 790, Jonkrill 780, Jonkrill 7610 (above trade name, manufactured by BASF), NK binder R-5HN (made by Shin-Nakamura Chemical Co., Ltd.) Product name, solid content 44%).

  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.

  The resin fine particles may be used alone or in combination of two or more.

  Among the resin fine particles described above, it is particularly preferable to include a cohesive resin. When the ink composition contains an aggregating resin, betaram and bleeding tend to be further suppressed. The resin fine particles are a resin aqueous solution containing 1% by mass of the resin fine particles (hereinafter, also simply referred to as “resin aqueous solution”. The resin aqueous solution means a resin liquid (resin aqueous medium liquid) containing water as a medium. And a dispersion solution) and a 0.085 mol / L calcium nitrate aqueous solution (hereinafter, also simply referred to as “calcium nitrate aqueous solution”) are preferable. It is more preferable that 3 mL of the resin aqueous solution and 3 mL or less of the calcium nitrate aqueous solution are aggregated. This is defined as a cohesive resin, and 3 mL of the resin aqueous solution and 1.0 mL or less of the calcium nitrate aqueous solution are mixed. Those having the property of sometimes aggregating are more preferred. The volume of the calcium nitrate aqueous solution to be mixed is not limited, but can be 0.1 mL or more.

  Such a cohesive resin is not particularly limited. For example, polyethylene resin (for example, product name “Chemical S650” manufactured by Mitsui Chemicals), polyethylene resin (for example, product name “AQ515” manufactured by BYK), Examples thereof include polyester resins (for example, product name “KT8701” manufactured by Unitika Ltd.).

  The resin content is preferably 0.5 to 7.5% by mass, more preferably 1.0 to 7.0% by mass, and even more preferably 1.5% with respect to the total amount of the ink composition. It is -6.5 mass%. By being within the above range, the recorded material tends to have better water resistance and abrasion resistance, and the ink composition has excellent long-term storage stability, and in particular, lowers the viscosity of the ink composition. Tend to be able to.

(Other ingredients)
The first colored ink composition has a storage aid and a viscosity modifier in order to maintain good storage stability and ejection stability from the head, to improve clogging, or to prevent deterioration of the ink composition. Various additives such as a pH adjuster, an antioxidant, an antiseptic, an antifungal agent, a corrosion inhibitor, and a chelating agent for capturing metal ions that affect dispersion can be added as appropriate. .

[Other ink compositions]
Other ink compositions contain water as a volatile component. Other ink compositions may be used alone or in combination of two or more. The other ink composition is used for adjusting the amount of water in accordance with the duty of the first colored ink composition adhering to the recording area S1. From such a viewpoint, the other ink composition is preferably a clear ink composition or an ink composition having a first colorant content less than that of the first color ink composition.

  The “clear ink composition” is not an ink composition used for coloring a recording medium but an ink composition used for other purposes. Other purposes include adjusting the glossiness of the recording medium, improving characteristics such as the abrasion resistance of the recorded material, and improving the fixability and color development of the color ink composition. The clear ink composition preferably has a colorant content of 0.1% by mass or less, and more preferably is an ink composition that does not contain a coloring material.

  When the other ink composition is an ink composition in which the content of the first colorant is less than that of the first color ink, the content of the first colorant contained in the other ink composition is different from that of the other ink composition. Preferably it is 0.5-8 mass% with respect to the total amount of a thing, More preferably, it is 1.0-8.0 mass%, More preferably, it is 1.5-6 mass%.

(water)
The water content is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and still more preferably 60 to 85% by mass with respect to the total amount of other ink compositions.

(Organic solvent)
Other ink compositions may also contain an organic solvent as a volatile component. As an organic solvent, what was illustrated by the reaction liquid composition can be used, for example. The content of the organic solvent is preferably 10 to 30% by mass, more preferably 12.5 to 27.5% by mass, and further preferably 15 to 25% by mass with respect to the total amount of other ink compositions. %. When the content of the organic solvent is within the above range, the recorded material is more excellent in water resistance and rubbing resistance, and further tends to be able to lower the viscosity of the ink.

(Surfactant)
In addition, the other ink composition may contain a surfactant. Although it does not specifically limit as surfactant, For example, what was illustrated by the reaction liquid composition can be used. The content of the organic solvent is preferably 0.10 to 5.0% by mass and more preferably 0.10 to 3.0% by mass with respect to the total amount of the other ink composition. When the content of the surfactant is within the above range, the wettability of the other ink composition attached to the recording medium tends to be further improved.

  Other components that can be included in other ink compositions are not particularly limited, and include the optional components exemplified in the first colored ink composition.

[Third step]
The third step is a step of forming the recording region S3 by attaching one or more second colored ink compositions to the recording region S2. That is, the third step is a step of attaching the second ink from above the first colored ink composition and the other ink composition. At this time, the reaction solution is preferably dried. Further, the first colored ink composition and the other ink composition may not be completely dried. By attaching the second colored ink composition in a state where the first colored ink composition and the other ink composition are not completely dried, the recording speed can be increased. Before the third step, there may be a step of drying at least part of the reaction liquid, the first colored ink composition, and the other ink composition applied to the recording medium. Moreover, you may have the process of drying the 2nd colored ink composition apply | coated to the recording medium during the 3rd process or after the process.

Adhesion amount of the second colored ink composition in the third step is preferably ^{0.1~12.5mg / inch 2, 0.1~10mg / inch} 2 is preferable. When the adhesion amount of the second colored ink composition is within the above range, the resulting recorded matter tends to be more excellent in bleed resistance, clogging reliability, and stickiness.

  In the third step, one or more second colored ink compositions are transferred to the recording area S2 in a state where the volatile components contained in the first colored ink composition and the other ink composition remain in the recording area S2. Is preferably attached. By doing so, bleeding tends to be further suppressed.

  In the third step, the volatilization amount of the volatile components contained in the first colored ink composition and the other ink composition attached to the recording medium at the time of attaching the second colored ink composition is determined before the attachment. Preferably it is 80 mass% or less with respect to the total amount of the volatile component contained in the 1st coloring ink composition of this, and another ink composition, More preferably, it is 5-70 mass%, More preferably, it is 10-50. % By mass. When the volatilization amount is 80% by mass or less, the recording speed tends to be further improved. Moreover, when the volatilization amount is 5% by mass or more, bleeding tends to be further suppressed. Here, “the first colored ink composition and the other ink composition before adhesion” refers to the first colored ink composition and other ink composition to be applied to the recording medium in the second step. Means state. In addition, the volatilization amount of a volatile component can be calculated | required by the method as described in an Example.

  In the third step, the second colored ink composition can be ejected from the nozzles of the line head or serial head and deposited on the recording medium by an inkjet method. In the line method using a line head, the head is fixed and the recording medium is moved along the sub-scanning direction (the longitudinal direction of the recording medium, the conveyance direction), and the nozzle opening of the head is interlocked with this movement. By ejecting ink droplets, an image can be recorded on the recording medium. In the serial system using a serial head, the head is moved along the main scanning direction (the horizontal direction and the width direction of the recording medium), and ink droplets are ejected from the nozzle openings of the head in conjunction with this movement. Thus, an image can be recorded on the recording medium.

[Second colored ink composition]
The second colored ink composition contains water as a second colorant and a volatile component. The second colored ink composition may be used alone or in combination of two or more.

(Second colorant)
Although it does not specifically limit as a 2nd colorant, For example, the pigment illustrated by the 1st colorant is mentioned. The second colorant and the first colorant may be the same or different. Among these, one of the first colored ink composition and the second colored ink composition is a white ink composition containing a white colorant, and the other is a color ink composition containing a colorant other than the white colorant. Preferably there is. By adopting such a combination, the color developability of transparent media, colored media and the like tends to be further improved.

  The content of the second colorant is preferably 0.5 to 7.5% by mass, more preferably 1.0 to 7.0% by mass, based on the total amount of the second color ink composition, More preferably, it is 1.5-6.5 mass%.

(water)
The content of water is preferably 50 to 90% by mass, more preferably 60 to 85% by mass, and further preferably 60 to 80% by mass with respect to the total amount of the second colored ink composition.

(Organic solvent)
The second colored ink composition may contain an organic solvent as a volatile component. As an organic solvent, what was illustrated by the reaction liquid composition can be used, for example. The content of the organic solvent is preferably 10 to 30% by mass, more preferably 12.5 to 27.5% by mass, and further preferably 15 to 25% with respect to the total amount of the second colored ink composition. % By mass. When the content of the organic solvent is within the above range, the recorded material is more excellent in water resistance and rubbing resistance, and further tends to be able to lower the viscosity of the ink.

(Surfactant)
The second colored ink composition may contain a surfactant. Although it does not specifically limit as surfactant, For example, what was illustrated by the reaction liquid composition can be used. The content of the organic solvent is preferably 0.10 to 5.0% by mass and more preferably 0.10 to 3.0% by mass with respect to the total amount of the second colored ink composition. When the content of the surfactant is within the above range, the wettability of the second colored ink composition attached to the recording medium tends to be further improved.

(resin)
The second colored ink composition may contain a resin. The resin content is preferably 0.5 to 5.0% by mass, more preferably 1.0 to 4.5% by mass, and still more preferably 1.5%, based on the total amount of the ink composition. It is -3.5 mass%. By being within the above range, the recorded material tends to have better water resistance and abrasion resistance, and the ink composition has excellent long-term storage stability, and in particular, lowers the viscosity of the ink composition. Tend to be able to.

(Other ingredients)
Other components that can be contained in the second colored ink composition are not particularly limited, and include the optional components exemplified in the first colored ink composition.

[Recording Method of Second Embodiment]
The recording method of the second embodiment includes one or more first colored ink compositions containing water as a first colorant and a volatile component, and one or more second colors containing water as a second colorant and a volatile component. A recording method comprising a composition group comprising an ink composition, a reaction liquid composition containing a flocculant, and one or more other ink compositions containing water as a volatile component, A first step of depositing the reaction liquid composition on a medium to form a recording area S1, and one or more of the first colored ink composition and one of the other ink compositions to the recording area S1. A second step of forming the recording region S2 by attaching two or more, and a step of forming the recording region S3 by attaching one or more second colored ink compositions to the recording region S2. 3 steps, and in the first step and the second step, The total amount of water in the region where the total amount of water in the region with the smallest total amount of water contained in the reaction liquid composition, the first colored ink composition, and the other ink composition is the largest. It is 50 mass% or more with respect to quantity.

  In the recording method of the second embodiment, in the second step, the total adhesion amount of water in the region where the total adhesion amount of water contained in the first colored ink composition and the other ink composition is the smallest is the largest. Instead of forming the recording area S2 so as to be 50% by mass or more with respect to the total amount of water in the area, in the first step and the second step, the reaction liquid composition, the first colored ink composition, In addition, the total amount of water in the region where the total amount of water contained in the other ink composition is the smallest is recorded so as to be 50% by mass or more with respect to the total amount of water in the region where the most water is present. The recording method is the same as that of the first embodiment except that the areas S1 and S2 are formed.

  That is, in the recording method of the first embodiment, when each ink composition is recorded after the reaction liquid composition is dried, the volatile component contained in the reaction liquid composition is negligible. In the recording method of the embodiment, it is shown that the volatile component contained in the reaction liquid composition is taken into account when each ink composition is recorded before the reaction liquid composition is dried. In the recording method of the second embodiment, the printing speed can be further improved because the drying step of the reaction liquid composition can be omitted.

  In the first step and the second step, the total amount of water in the region where the total amount of water contained in the reaction liquid composition, the first colored ink composition, and the other ink composition is the smallest, It is 50 mass% or more with respect to the total adhesion amount of the water of the largest area | region. The total amount of water in the region where the total amount of water is the smallest is 50% by mass or more, preferably 55 to 100% by mass, more preferably the total amount of water in the region where the water is the most. It is 60-100 mass%. When the total amount of water in the region where the total amount of water adheres is within the above range, bleeding can be further suppressed.

  In the third step, the volatile component contained in the reaction liquid composition, the first colored ink composition, and the other ink composition attached to the recording medium at the time of attaching the second colored ink composition. The volatilization amount is preferably 80% by mass or less with respect to the total amount of volatile components contained in the reaction liquid composition, the first colored ink composition, and the other ink composition before adhesion, and more preferably 5 to 5%. It is 70 mass%, More preferably, it is 10-50 mass%. When the volatilization amount is 80% by mass or less, the recording speed tends to be further improved. Moreover, when the volatilization amount is 5% by mass or more, bleeding tends to be further suppressed. Here, “the reaction liquid composition before adhering, the first colored ink composition, and the other ink composition” means the reaction liquid composition applied to the recording medium in the first step and the second step, It means a state before adhesion of one colored ink composition and another ink composition. In addition, the volatilization amount of a volatile component can be calculated | required by the method as described in an Example.

[Recording medium]
Examples of the recording medium include an absorptive recording medium, a low-absorbing recording medium, and a non-absorbing recording medium.

  The absorbent recording medium is not particularly limited. For example, plain paper such as electrophotographic paper having high ink permeability, ink jet paper (an ink absorbing layer composed of silica particles or alumina particles, or polyvinyl alcohol ( Art paper, coated paper, etc. used for general offset printing with relatively low ink permeability, such as PVA) and polyvinyl pyrrolidone (PVP). Examples include cast paper.

  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, films and plates of plastics such as polyvinyl chloride, polyethylene, polypropylene, and polyethylene terephthalate (PET), and metals such as iron, silver, copper, and aluminum are used. Examples thereof include a plate, a metal plate produced by vapor deposition of these various metals, a plastic film, a plate made of an alloy such as stainless steel or brass.

[Recording device]
FIG. 1 is a diagram showing an outline of an example of an ink jet 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. The inkjet recording apparatus 1 also includes a preheater (not shown), and the recording medium F is heated from the beginning.

  Among these, the drying device 90 includes a first drying unit 40 that performs a process of drying the recording medium, and a second drying unit 50 that dries a 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 the reaction liquid composition can be applied to the recording medium F sent from the transport unit 20 and each ink composition can be discharged and recorded. Specifically, the recording unit 30 includes a head 31 that performs the first step, a head 32 that performs the second step, a recording head 33 that performs the third step, and a platen 34 as a medium support unit.

  Among these, the platen 34 is provided so that the recording medium F can be supported from the back surface. Further, the platen 34 is provided with a first drying unit 40 that dries the reaction liquid composition applied to the recording medium F and the ink composition discharged 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 composition applied to the recording medium F and the ink compositions discharged 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.

[Reaction liquid and ink materials]
The main materials for the reaction liquid and ink used in the following Examples and Comparative Examples are as follows.
[Flocculant]
Calcium acetate monohydrate [pigment]
Titanium dioxide: Metal oxide NanoTek® Slurry CII Kasei Co., Ltd. Cyan pigment: C.I. I. Pigment Blue 15: 3
〔resin〕
Styrene-acrylic acid copolymer (manufactured by BASF, Joncrill 62J)
〔Organic solvent〕
1,2 hexanediol propylene glycol [surfactant]
BYK348 (silicone surfactant, manufactured by Big Chemie Japan)

[Preparation of reaction liquid and ink]
Each material is mixed with the composition (mass%) shown in Tables 1 to 3 below, and sufficiently stirred, and the reaction liquid composition, the first colored ink composition, the other ink composition, and the second colored ink composition are mixed. Respectively.

[Preparation of composition group]
The obtained reaction liquid composition, first colored ink composition, other ink composition, and second colored ink composition were combined as shown in Tables 1 to 3 to obtain composition groups.

[Examples 1-4, Comparative Example 1, Reference Examples 1-3]
PX-G930 (manufactured by Epson) is filled with the composition group prepared above, and the reaction liquid composition is ejected from the head by the ink jet method under the recording conditions shown in Tables 1 to 3, and the recording medium is Toray A solid pattern (recording area S1) was formed on a PET film “Lumirror S10” (trade name, thickness 100 μm) and dried (first step). The resolution was 720 × 720 dpi.

  Next, the first colored ink composition and the other ink composition were ejected from each head by the ink jet method under the recording conditions shown in Tables 1 to 3 to form the recording area S2 on the recording area S1 (second step). . The resolution was 720 × 720 dpi.

  Finally, the first colored ink composition and the other ink composition on the recording area S2 are dried so that the drying rates shown in Tables 1 to 3 are obtained, and the second colored ink composition is ejected from the first colored ink composition by the inkjet method. The recording area S3 was formed on the recording area S2, and then dried at 60 ° C. for 20 minutes (third step). The resolution was 720 × 720 dpi.

  In the above recording method, a high duty area of 100% duty and a low duty area of 30% duty were formed.

[Drying rate]
Volatile components of the first colored ink composition and other ink compositions in the recording region S2 after the second step and before the third step (when the recording medium is conveyed to a position facing the second colored ink head) The volatilization amount (drying rate) was calculated by the following formula. The drying rate is a value calculated in a high duty region.

Here, Af is the total applied amount (mg) of the first colored ink composition and the other ink composition applied to the recording medium in an overlapping manner. Ae represents the first colored ink composition and the like on the recording medium in a state where the first colored ink composition and the other ink composition are dried (volatilized) to a state sufficient to use the recorded matter. The total amount of residual ink composition. Furthermore, A is the total amount of the first colored ink composition and other ink compositions on the recording medium immediately before the third step.
Volatile component volatilization amount% = ((Af−A) / (Af−Ae)) × 100

  Af can be obtained from the discharge data of the printer and the mass per dot as the application amount of the first colored ink composition and the other ink composition. A can be obtained by measuring the difference between the mass of the recording medium at the start of the third step and the mass of the recording medium before the first step. When measuring the volatilization amount of the volatile component, it is convenient to use a recording medium prepared for the measurement. The measurement was performed with an electronic balance. At the time of measurement, the relationship between the drying time and the volatilization amount when the first colored ink composition and the other ink composition are applied and then dried by heating with a platen is determined. When recording with a recording apparatus, the time from application of the first colored ink composition and other ink composition to application of the second colored ink composition is determined by the drying time and volatilization amount obtained above. The desired volatilization amount can be obtained by setting the time in any one of the relationships.

[Evaluation]
[Bleed]
The boundary between the recording area S2 and the recording area S3 was visually observed and evaluated according to the following evaluation criteria.
(Evaluation criteria)
A: No bleed was seen.
B: Although bleed was seen, when it carried out similarly with the adhesion amount of the 2nd coloring ink composition in Tables 1-3 being halved, no bleed was seen.
C: Bleed was observed even when the amount of the second colored ink composition in Tables 1 to 3 was halved and the same procedure was performed.

[Odor of recorded material]
The odor of the recorded matter was evaluated by sensory evaluation of the recording area S3 according to the following evaluation criteria.
(Evaluation criteria)
A: There is no odor.
B: There is a slight odor.
C: There is an odor.

  In addition, although the Example of the state which the reaction liquid composition was almost completely dried was shown in the said Example, the same result is obtained even if the reaction liquid is not dried. That is, the same effect can be obtained by considering the water contained in the reaction solution composition.

  From Comparative Example 1, when the second colored ink composition is adhered, if there is little remaining water in the first colored ink composition layer deposited earlier, the flocculant oozes from the reaction liquid layer to the first colored ink composition layer. It was found that the second colored ink composition could not react and the image quality deteriorated. In particular, since the amount of water adhering to the low duty region is small, the amount of remaining water is small and image quality deteriorates.

  On the other hand, from each of the examples, it was shown that the image quality can be improved by adjusting the amount of water adhering to the low duty region using other ink.

  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 (8)

One or more first colored ink compositions containing water as the first colorant and volatile component, one or more second colored ink compositions containing water as the second colorant and volatile component, and a flocculant A recording method comprising using a composition group comprising a reaction liquid composition and one or more other ink compositions containing water as a volatile component,
A first step of forming the recording region S1 by adhering the reaction liquid composition to a recording medium;
A second step of forming the recording area S2 by adhering one or more of the first colored ink compositions and one or more of the other ink compositions to the recording area S1;
A third step of forming the recording region S3 by attaching one or more second colored ink compositions to the recording region S2,
In the second step, the total amount of water in the region with the smallest total amount of water contained in the first colored ink composition and the other ink composition is the total amount of water in the region with the largest amount. The recording method which is 50 mass% or more with respect to the adhesion amount. One or more first colored ink compositions containing water as the first colorant and volatile component, one or more second colored ink compositions containing water as the second colorant and volatile component, and a flocculant A recording method comprising using a composition group comprising a reaction liquid composition and one or more other ink compositions containing water as a volatile component,
A first step of forming the recording region S1 by adhering the reaction liquid composition to a recording medium;
A second step of forming the recording area S2 by adhering one or more of the first colored ink compositions and one or more of the other ink compositions to the recording area S1;
A third step of forming the recording region S3 by attaching one or more second colored ink compositions to the recording region S2,
In the first step and the second step, the water in the region where the total amount of water contained in the reaction liquid composition, the first colored ink composition, and the other ink composition is the smallest. A recording method in which the total adhesion amount is 50% by mass or more with respect to the total adhesion amount of water in the largest region.   The recording method according to claim 1, wherein the other ink composition is a clear ink composition or an ink composition having a content of the first colorant less than that of the first color ink. One of the first colored ink composition and the second colored ink composition is a white ink composition containing a white colorant,
The recording method according to claim 1, wherein the other is a color ink composition containing a colorant other than the white colorant.   In the third step, one or more of the volatile components contained in the first colored ink composition and the other ink composition remain in the recording area S2 to the recording area S2. The recording method according to claim 1, wherein the second colored ink composition is adhered.   The recording region S1 is formed by attaching the reaction solution composition to the recording medium so as to form regions with different attachment amounts of the reaction solution composition in the first step. The recording method according to any one of 1 to 5.   In the second step, the one or more first colored ink compositions and the other ink composition are attached to the recording area S1 simultaneously or sequentially to form the recording area S2. The recording method according to any one of claims 1 to 6.   At least one of the first colored ink composition, the second colored ink composition, and the other ink composition includes the water and an organic solvent as the volatile components. 2. The recording method according to item 1.

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