JP6816797B2 - Recording method - Google Patents

Description

The present invention relates to a recording method.

The inkjet recording method is a relatively simple device capable of recording high-definition images, and is rapidly developing in various fields. Among them, various studies have been made on obtaining higher quality images. For example, in Patent Document 1, a high-quality color image having high image density and no bleeding is obtained by adhering an appropriate amount of a reaction solution for improving ink fixability to an optimum position on a recording medium. For the purpose of providing an inkjet recording method that can be provided, an ink ejection head for ejecting ink and a reaction liquid ejection head for ejecting a reaction liquid having a property of aggregating the ink are used for ink. In an inkjet recording method for recording an image by forming ink dots and reaction liquid dots on a recording medium based on the recording data and the recording data for a reaction solution, the region on the recording medium on which the ink dots are formed Disclosed is an inkjet recording method characterized in that the reaction liquid dots are formed with a uniform dot size and a recording duty of 100%.

Japanese Unexamined Patent Publication No. 2005-225114

When the reaction solution is not used, the cohesiveness of the obtained recorded material is lowered, and the image quality is deteriorated. On the other hand, if the amount of the reaction solution applied is excessive, there is a problem that an odor is generated from the obtained recorded material and the durability of the recorded material is lowered.

The reaction solution can be applied by roller coating or inkjet coating. Since the coating amount cannot be adjusted by roller coating, Patent Document 1 discloses coating by inkjet coating from the viewpoint of controlling the coating amount of the reaction solution.

However, even according to Patent Document 1, it is not perfect as a solution to the trade-off problem between the improvement of cohesiveness and the durability of odor and recorded matter. Therefore, there is a demand for a recording method that can further exert the effect of improving cohesiveness while reducing the amount of the reaction solution applied.

The present invention has been made to solve at least a part of the above-mentioned problems, and provides a recording method capable of obtaining a recorded material having good cohesiveness and printing durability and less odor of recorded material. With the goal.

The present inventors have diligently studied to solve the above problems. As a result, they have found that the above problems can be solved by a predetermined recording method, and have completed the present invention.

That is, the present invention is as follows.
[1]
A reaction solution containing a flocculant capable of coagulating the components of the colored ink composition is adhered to a recording medium at an adhesion amount of 100 to 1500 nmol / inch ² of the flocculant to form a recording region S1. Adhesion process and
A recording comprising a step of adhering the colored ink composition containing a coloring material and a resin to the recording area S1 to form a recording area S2 within 30 seconds from the adhesion of the reaction solution. Method.
[2]
The recording method according to the preceding item [1], wherein in the reaction liquid adhesion step, the reaction liquid is discharged as droplets and adhered to the recording medium at an adhesion density of 600 dpi or more × 600 dpi or more.
[3]
The recording method according to the preceding item [1] or [2], wherein the recording medium is an absorbable recording medium or a low absorption recording medium.
[4]
The recording method according to any one of [1] to [3] above, wherein the content of the flocculant is 0.090 mol / 1000 g or more and 0.91 mol / 1000 g or less with respect to the total amount of the reaction solution. ..
[5]
The recording method according to any one of the preceding items [1] to [4], wherein the component of the colored ink composition that agglutinates with the coagulant contains at least one of the pigment as the coloring material and the resin. ..
[6]
The recording method according to any one of the above items [1] to [5], wherein the flocculant contains at least one of a polyvalent metal salt and an organic acid [7].
In the reaction liquid adhering step and the colored ink composition adhering step, the reaction liquid or the colored ink composition is ejected from the ink jet head while changing the relative positions of the ink jet head and the recording medium. The recording method according to any one of the preceding items [1] to [6], wherein adhesion is performed by performing scanning once.
[8]
The item according to any one of the preceding items [1] to [7], wherein the temperature of the recording region S1 of the recording medium is maintained at 38 ° C. or lower from the reaction liquid adhesion step to the colored ink composition adhesion step. Recording method.
[9]
In the coloring ink composition adhesion step, the residual ratio of the volatile component of the reaction solution on the recording area S1 is 30% by mass or more with respect to the total mass of 100% by mass of the volatile component contained in the reaction solution before adhesion. The item according to any one of the preceding items [1] to [8], wherein the colored ink composition containing the coloring material and the resin is adhered to the recording area S1 to form the recording area S2. Recording method.

It is a figure which shows the outline of an example of the inkjet recording apparatus which can be used in this embodiment. It is a functional block diagram which shows an example of the structure of the recording apparatus which can be used in this embodiment.

Hereinafter, embodiments of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail with reference to the drawings as necessary, but the present invention is not limited thereto, and a gist thereof. Various deformations are possible within the range that does not deviate from. In the drawings, the same elements are designated by the same reference numerals, and duplicate description will be omitted. Further, unless otherwise specified, the positional relationship such as up, down, left, and right shall be based on the positional relationship shown in the drawings. Furthermore, the dimensional ratios in the drawings are not limited to the ratios shown.

〔Recording method〕
In the recording method of the present embodiment, a reaction solution containing a flocculant capable of coagulating the components of the colored ink composition is adhered to the recording medium at an adhesion amount of 100 to 1500 nmol / inch ² of the flocculant. The reaction liquid adhering step for forming the recording area S1 and the colored ink composition containing the coloring material and the resin are adhered to the recording area S1 within 30 seconds from the adhering of the reaction liquid to form the recording area S2. It has a step of adhering a colored ink composition.

There is a problem that the larger the amount of the flocculant adhered to the recording medium, the more the odor generated from the obtained recorded material increases, and the durability of the recorded material decreases. Therefore, it is preferable that the amount of the cohesive agent adhered is close to the minimum amount at which the obtained recorded material has good cohesiveness. However, it is difficult to solve the trade-off problem between the improvement of cohesiveness and the durability of odor and recorded matter by simply reducing the amount of the cohesive agent attached. For example, when the recording medium is an absorbent recording medium or a low absorption recording medium, if the holding time after the reaction solution adheres is long, the reaction solution permeates into the recording medium. It may not be possible to obtain the effect of the reaction solution that had been used. On the other hand, if the amount of the reaction solution adhered is increased, such a problem is less likely to occur, but the odor generated from the obtained recorded material is increased, and the durability of the recorded material is lowered.

On the other hand, in the recording method of the present embodiment, by having the above configuration, regardless of the type of the recording medium, the cohesiveness is improved with a smaller amount of the cohesive agent attached, and the odor and the durability of the recorded material are improved. Can solve the trade-off issues.

[Reaction liquid adhesion process]
In the reaction solution adhesion step, a reaction solution containing a flocculant capable of coagulating the components of the colored ink composition is adhered to the recording medium at an adhesion amount of 100 to 1500 nmol / inch ² of the flocculant, and the recording region S1 Is the process of forming.

The means for adhering the reaction solution is not particularly limited, and for example, roller coating, spray coating, and inkjet coating can be used. In the case of inkjet coating, the reaction solution can be discharged from the nozzle of the line head or the serial head and adhered to the recording medium. In the line method using a line head, the head is fixed and the recording medium is moved (changes the relative position) along the sub-scanning direction (vertical direction and transport direction of the recording medium), and this movement is performed. The recording area S1 can be formed on the recording medium by ejecting ink droplets from the nozzle opening of the head in conjunction with each other. Further, in the serial method using a serial head, the head is moved (relatively positioned) along the main scanning direction (horizontal direction and width direction of the recording medium), and the nozzle of the head is interlocked with this movement. The recording region S1 can be formed on the recording medium by ejecting ink droplets from the opening.

Among these, in the reaction liquid adhesion step, adhesion can be performed by performing a single scan of ejecting the reaction liquid from the ink jet head while changing the relative positions of the ink jet head and the recording medium. preferable. By using the inkjet coating, it is possible to more precisely adjust the type of the reaction solution and the coating amount thereof according to the type of the recording medium, the coating amount at each portion of the recording area S1 and the like. As a result, it tends to be possible to obtain a recorded material having better cohesiveness and printing durability and less odor of the recorded material. Further, when the reaction solution is adhered during scanning (1 pass) only once by the above line method, bleeding and betamura are likely to occur, so that the present invention is particularly useful.

The amount of the flocculant adhered is 100 to 1500 nmol / inch ² , preferably 100 to 1400 nmol / inch ² , and more preferably 100 to 1250 nmol / inch ² . Furthermore, the upper limit is preferably 1000 nmol / inch ² or less, more preferably 500 nmol / inch ² or less, the lower limit is 200 nmol / inch ² or more. When the amount of the cohesive agent adhered is 100 nmol / inch ² or more, the cohesiveness is further improved. Further, when the amount of the coagulant adhered is 1500 nmol / inch ² or less, it is possible to obtain a recorded material having good printing durability and less odor of the recorded material. The above-mentioned adhesion amount of the flocculant is the maximum adhesion amount in the recording region to which the flocculant is adhered in the recording method of the present embodiment.

In the reaction liquid adhesion step, it is preferable to discharge the reaction liquid as droplets and attach them to the recording medium at a predetermined adhesion density. The adhesion density is preferably 600 dpi or more × 600 dpi or more, more preferably 600 dpi or more × 1200 dpi or more, and further preferably 1200 dpi or more × 1200 dpi or more. When the adhesion density is 600 dpi or more × 600 dpi or more, the cohesiveness tends to be further improved. The upper limit of the adhesion density is not limited, but is preferably 3600 dpi or less × 3600 dpi or less. The adhesion density is the adhesion density as droplets, which is the number of droplets attached per predetermined area.

[Reaction solution]
The reaction solution contains a flocculant capable of agglomerating the components of the colored ink composition. The coagulant component in the reaction solution interacts with the ink composition to thicken or insolubilize the ink composition. As a result, it is possible to prevent landing interference and bleeding of the ink composition to be adhered thereafter, and it is possible to uniformly draw lines and fine images. The component of the colored ink composition that aggregates by the flocculant is not particularly limited, but for example, at least one of a pigment and a resin is preferable.

(Coagulant)
The flocculant is not particularly limited, and examples thereof include polyvalent metal salts, organic acids, and organic acid salts. Among these, it is preferable to contain at least one of a polyvalent metal salt and an organic acid. By using a reaction solution containing a polyvalent metal salt, the coagulant effect tends to be more excellent.

(Multivalent metal salt)
The polyvalent metal salt is not particularly limited, but for example, a polyvalent metal salt of an inorganic acid or a polyvalent metal salt of an organic acid is preferable. Such polyvalent metal salts are not particularly limited, but are, for example, alkaline earth metals of the second group of the periodic table (for example, magnesium and calcium) and transition metals of the third group of the periodic table (for example, lanterns). , Salts of earth metals (eg, aluminum), lanthanides (eg, neodymium) from the 13th genus of the periodic table. As the salts of these polyvalent metals, carboxylates (formic acid, acetic acid, benzoate, etc.), sulfates, nitrates, chlorides, and thiocyanates are suitable. Among them, preferably, calcium salt or magnesium salt of carboxylic acid (artic acid, acetic acid, benzoate, etc.), calcium salt or magnesium salt of sulfuric acid, calcium salt or magnesium salt of nitrate, calcium chloride, magnesium chloride, and thiosian acid. Calcium salt or magnesium salt can be mentioned, and more preferably, carboxylate can be mentioned. The present invention is particularly useful because such carboxylates tend to have a strong odor. The polyvalent metal salt may be used alone or in combination of two or more.

(Organic acid or salt thereof)
The organic acid or a salt thereof is not particularly limited, and examples thereof include phosphoric acid, oxalic acid, malonic acid, citric acid or a salt thereof. Of these, monovalent or divalent or higher carboxylic acids are preferable. The present invention is particularly useful because such carboxylic acids tend to have a strong odor. The organic acid or a salt thereof may be used alone or in combination of two or more.

The content of the flocculant (mol / 1000 g) is preferably 0.090 to 0.91, more preferably 0.10 to 0.90, still more preferably 0, based on the total amount of the reaction solution. It is 20 to 0.90, more preferably 0.30 to 0.90, and more preferably 0.50 to 0.90. When the content is within the above range, the coagulant effect tends to be more excellent.

The reaction solution may contain other components if necessary. The other components are not particularly limited, and examples thereof include water as a volatile component, an organic solvent as a volatile component, and a surfactant.

(water)
Examples of water include pure water such as ion-exchanged water, ultra-filtered water, reverse osmosis water, and distilled water, and ultrapure water from which ionic impurities have been removed as much as possible. Further, when water sterilized by irradiation with ultraviolet rays or addition of hydrogen peroxide or the like is used, it is possible to prevent the growth of mold and bacteria when the ink is stored for a long period of time. This tends to further improve storage stability.

The content of water is preferably 40 to 80% by mass, more preferably 45 to 75% by mass, and further preferably 50 to 70% by mass with respect to the total amount of the reaction solution. When the water content is within the above range, the viscosity of the ink composition can be reduced.

(Organic solvent)
The organic solvent is not particularly limited, but for example, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,2-butanediol, 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, diethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Diethylene 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, tert-butanol, iso-butanol, n-pentanol, 2-pentanol , 3-Pentanol, and alcohols or glycols such as tert-pentanol; N, N-dimethylformamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, 2-oxazolidone, 1 , 3-Dimethyl-2-imidazolidinone, dimethyl sulfoxide, sulfate Horan and 1,1,3,3-tetramethylurea can be mentioned. Among 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. When the content of the organic solvent is within the above range, the coagulant effect tends to be further improved.

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

The acetylene glycol-based surfactant is not particularly limited, and is, for example, 2,4,7,9-tetramethyl-5-decine-4,7-diol and 2,4,7,9-tetramethyl-5. Selected from alkylene oxide adducts of decine-4,7-diol and alkylene oxide adducts of 2,4-dimethyl-5-decine-4-ol and 2,4-dimethyl-5-decine-4-ol. One or more is preferable. Commercially available products of acetylene glycol-based surfactants are not particularly limited, but for example, E series (trade name manufactured by Air Products Japan, Inc.) such as Orfin 104 series and Orfin E1010, Surfinol 465 and the like. Surfinol 61 (trade name manufactured by Nissin Chemical Industry CO., Ltd.) and the like can be mentioned. The acetylene glycol-based surfactant may be used alone or in combination of two or more.

The fluorine-based surfactant is not particularly limited, and for example, perfluoroalkyl sulfonate, perfluoroalkyl carboxylic acid salt, perfluoroalkyl phosphate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, and per. Fluoroalkylamine oxide compounds can be mentioned. The commercially available fluorine-based surfactant is not particularly limited, but for example, S-144, S-145 (manufactured by Asahi Glass Co., Ltd.); FC-170C, FC-430, Florard-FC4430 (manufactured by Sumitomo 3M Ltd.). FSO, FSO-100, FSN, FSN-100, FS-300 (manufactured by DuPont); FT-250, 251 (manufactured by Neos Co., Ltd.) and the like. The fluorine-based surfactant may be used alone or in combination of two or more.

Examples of the silicone-based surfactant include polysiloxane-based compounds and polyether-modified organosiloxanes. The commercially available silicone-based surfactant is not particularly limited, but specifically, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-347, BYK. -348, BYK-349 (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 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

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

[Colored ink composition adhesion step]
In the coloring ink composition adhering step, the colored ink composition containing the coloring material and the resin is adhered to the recording area S1 (start of adhering) within 30 seconds from the adhering of the reaction solution (the end of adhering), and the colored ink composition is adhering to the recording area S2. Is the process of forming. In the step of adhering the colored ink composition, the colored ink composition can be ejected from the nozzle of the line head or the serial head and adhered to the recording medium by the inkjet method.

Among these, in the coloring ink composition adhering step, the colored ink composition is adhered by performing one scan of ejecting the colored ink composition from the ink jet head while changing the relative positions of the ink jet head and the recording medium. Is preferable. By using the inkjet coating, it is possible to more precisely adjust the type of the reaction solution and the coating amount thereof according to the type of the recording medium, the coating amount at each portion of the recording area S2, and the like. As a result, it tends to be possible to obtain a recorded material having better cohesiveness and printing durability and less odor of the recorded material. Further, when the reaction solution is adhered during scanning (1 pass) only once by the above line method, bleeding and betamura are likely to occur, so that the present invention is particularly useful. It should be noted that it may further have a step of drying at least a part of the colored ink composition applied to the recording medium during the colored ink composition attaching step or after the colored ink composition attaching step.

The amount of the colored ink composition adhered is preferably 1.0 to 10 mg / inch ² , more preferably 3.0 to 9.0 mg / inch ² , and even more preferably 5.0 to 8.0 mg / inch. It is ² . When the amount of the colored ink composition adhered is 1.0 mg / inch ² or more, the odor suppression and durability of the recorded material tend to be further improved. Further, when the amount of the flocculant adhered is 10 mg / inch ² or less, the odor suppression and durability of the recorded material tend to be further improved. The adhesion amount of the colored ink composition is the maximum adhesion amount in the recording region to which the colored ink composition is adhered in the recording method of the present embodiment.

In the recording method of the present embodiment, as described above, the colored ink composition is adhered to the recording region S1 within 30 seconds from the adhesion of the reaction solution to form the recording region S2. During the time T (hereinafter, also referred to as holding time T) from the adhesion of the reaction solution to the recording medium (end of adhesion) to the adhesion of the colored ink composition to the recording medium (start of adhesion), the recording medium. Can be prepared for the next adhesion of the colored ink composition by transporting the ink or moving the head, or the recording medium can be left unattended. The time T is 30 seconds or less, preferably 20 seconds or less, more preferably 17.5 seconds or less, still more preferably 15 seconds or less, still more preferably 10 seconds or less, and particularly preferably. Within 7 seconds. Further, the lower limit of the time T is 0 seconds or more, which is not limited, but is preferably more than 0 seconds, preferably 0.001 seconds or more, and further 0, from the viewpoint of ease of performing the coloring ink composition adhesion step. More preferably, it is 01 seconds or longer, further 0.1 seconds or longer, further 1 second or longer, and further preferably 2 seconds or longer. When the holding time T is 30 seconds or less, the cohesiveness is further improved.

From the reaction liquid adhesion step to the colored ink composition adhesion step, it is preferable to keep the temperature of the recording region S1 of the recording medium at a predetermined temperature. The temperature is preferably 45 ° C. or lower, more preferably 40 ° C. or lower, still more preferably 38 ° C. or lower, even more preferably 35 ° C. or lower, particularly preferably 30 ° C. or lower, and more particularly. It is preferably 25 ° C. or lower. The lower limit is preferably 10 ° C. or higher, and more preferably 15 ° C. or higher. When the recording medium is heated to dry the reaction solution at an early stage before the coloring ink composition adhesion step or during the coloring ink composition adhesion step, the reaction solution is placed on the recording medium before the reaction solution permeates the recording medium. Can be dried, thereby suppressing permeation. Therefore, the reaction between the reaction solution and the colored ink composition can be carried out relatively efficiently. However, as the recording medium is heated, the nozzle of the inkjet head receives heat, and the colored ink composition in the nozzle tends to thicken to generate a non-ejection nozzle. Therefore, the above temperature is preferably the above temperature or lower. On the other hand, when the recording medium is adhered at room temperature without heating before the coloring ink composition attaching step or during the coloring ink composition attaching step, it is preferable that the occurrence of ejection defects can be reduced, and if the present invention is used, the reaction The reaction between the liquid and the colored ink composition can be efficiently carried out. It should be noted that the generation of the non-ejection nozzle can also occur in the inkjet head for the reaction solution. Further, setting the temperature of the recording region S1 of the recording medium within the above range from the reaction liquid adhering step to the colored ink composition adhering step allows the colored ink composition adhering step to be continuously accelerated from the reaction liquid adhering step to the colored ink composition adhering step. It is preferable in that it is carried out.

In the coloring ink composition adhesion step, the residual ratio of volatile components in the reaction solution on the recording area S1 is 30% by mass or more with respect to 100% by mass of the total mass of volatile components contained in the reaction solution before adhesion. Therefore, it is preferable that the colored ink composition containing the coloring material and the resin is adhered to the recording region S1 to form the recording region S2. The residual ratio of volatile components is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, based on the total amount of volatile components contained in the reaction solution before adhesion. , Even more preferably 75% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. The upper limit is 100% by mass or less. When the residual ratio of the volatile component is 30% by mass or more, the cohesiveness tends to be further improved, and it is advantageous in that the recording time is shortened and it is not necessary to heat the recording medium to dry the reaction solution. Is. Here, the “reaction liquid before adhesion” means a state before adhesion of the reaction liquid to be applied to the recording medium in the reaction liquid adhesion step. The amount of volatile components volatile can be determined by the method described in Examples.

[Colored ink composition]
The colored ink composition contains a coloring material and a resin. The colored ink composition agglomerates by reacting with a coagulant, and the cohesiveness of the resulting recorded material is further improved.

(Color material)
The coloring material is not particularly limited, and examples thereof include pigments.

The pigment used for the black ink is not particularly limited, but for example, No. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, No. 2200B, etc. (above, manufactured by Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, etc. (above, Columbia Carbon (Carbon Colomb)) Rega1 330R, Rega1 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. (Cabot Corporation (CABOTC) , Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color B1ack S150, Color Black S160, Color Black Black S170, Color Black Mitsubishi Chemical Examples thereof include Black 4A and Special Black 4 (all manufactured by Degussa).

The pigment used in the white ink is not particularly limited, but for example, C.I. I. Pigment White 6, 18, 21, titanium oxide, zinc oxide, zinc sulfide, antimony oxide, and zirconium oxide white inorganic pigments. In addition to the white inorganic pigment, white organic pigments such as white hollow resin particles and polymer particles can also be used.

The pigment used for the yellow ink is not particularly limited, but 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 can be mentioned.

The pigment used in the magenta ink is not particularly limited, but 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.

The pigment used for the cyan ink is not particularly limited, but 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 can be mentioned.

The pigment used for color inks other than magenta, cyan, and yellow is not particularly limited, but for example, C.I. 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 above pigment can be used as a pigment dispersion liquid obtained by dispersing in water with a dispersant, or by dispersing a self-dispersing surface-treated pigment in which a hydrophilic group is introduced on the surface of pigment particles by utilizing a chemical reaction. It is preferably added to the ink composition as a pigment dispersion obtained by dispersing the obtained or polymer-coated pigment in water.

The dispersant is not particularly limited. Triethanolamine, alginate fermented product of ammonium alginate Methyl cellulose, carboxyl methyl cellulose, cellulose derivative of ethyl hydroxy cellulose, polyvinyl alcohols, polypyrrolidones, polyacrylic acid, acrylic acid-acrylic nitrile copolymer, potassium acrylate-acrylic nitrile Polymer, vinyl acetate-acrylic acid ester copolymer, acrylic acid-acrylic acid ester copolymer acrylic resin, 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, vinylnaphthalene-acrylic acid copolymer, acetic acid Vinyl acetate-based copolymer of vinyl-ethylene copolymer, vinyl acetate-fatty acid vinyl ethylene copolymer, vinyl acetate-maleic acid ester copolymer, vinyl acetate-croton copolymer, vinyl acetate-acrylic acid copolymer And their salts) and surfactants (various anionic surfactants, nonionic copolymers, amphoteric copolymers) can be used.

The self-dispersing type surface-treated pigment into which the above-mentioned hydrophilic group is introduced can be dispersed or dissolved in water without a dispersant by surface treatment in which a carboxyl group and a salt thereof are directly bonded to the surface of the pigment. Is. Specifically, it is obtained by grafting a functional group or a molecule containing a functional group onto the surface of a pigment by physical treatment of vacuum plasma or chemical treatment using an oxidizing agent of sodium hypochlorite or ozone. Can be done. The functional group grafted on one pigment particle may be a single type or a plurality of types. The type and degree of the functional group to be grafted may be appropriately determined in consideration of dispersion stability in the ink, color density, and dryness on the front surface of the inkjet head.

The pigment coated with the polymer is not particularly limited, but for example, a monomer (copolymerizable monomer) that is copolymerizable with the dispersant after the pigment is dispersed using a dispersant having a polymerizable group. And, it can be obtained by carrying out emulsion polymerization in water using a photoradical polymerization initiator. Among these polymers, a monomer or oligomer having at least one of an acryloyl group, a methacryloyl group, a vinyl group, and an allyl group as a double bond is 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 coloring material is preferably 0.50 to 5.0% by mass, more preferably 1.0 to 4.0% by mass, based on the total amount of the colored ink composition.

(resin)
The resin that can be contained in the 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 resins in the resin fine particles, the resin, and the pigment are fused to each other to fix the pigment to the recording medium, so that the scratch resistance and adhesion of the image portion of the recorded material can be improved. It can be made even better. Among the resin fine particles, urethane-based resin, acrylic-based resin, and polyethylene-based resin are preferable.

Examples of the urethane-based resin include urethane resin emulsions. The urethane resin emulsion is not particularly limited as long as it is a resin emulsion having a urethane bond in the molecule, and is 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 Examples thereof include a polycarbonate type urethane resin having a carbonate bond in the chain. The commercially available urethane resin emulsion is not particularly limited, but for example, Sancure 2710 (trade name manufactured by The Lubrizol Corporation), Permarin UA-150 (Sanyo Chemical Industries, Ltd.) (Product name), Superflex 460, 470, 610, 700 (above, product name manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), NeoRez R-9660, R-9637, R-940 (above, product name manufactured by Kusumoto Chemicals, Ltd.), Adeka Bontiter HUX-380, 290K (above, product name manufactured by Adeka), Takelac (registered trademark) W-605 , W-635, WS-6021 (above, Mitsui Chemicals, Inc. product name), polyether (TAISEI FINECHEMICAL CO, .LTD product name, Tg = 20 ° C.). ..

Examples of the acrylic resin include an acrylic resin emulsion. The acrylic resin emulsion is not particularly limited, and for example, a polymerized (meth) acrylic monomer such as (meth) acrylic acid or (meth) acrylic acid ester, or a (meth) acrylic monomer is used. And other monomers are copolymerized with each other. Commercially available products of acrylic resin fine particles are not particularly limited, but for example, Movinyl 966A (trade name manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), Microgel E-1002, Microgel E-5002. (Product name, manufactured by Nippon Paint Co., Ltd.), Boncoat 4001, Boncoat 5454 (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 Krill 840, John Krill 62J, John Krill 74J, John Krill HRC-1645J, John Krill 734, John Krill 852, John Krill 7600, John Krill 775, John Krill 537J, John Krill 1535, John Krill PDX -7630A, John Krill 352J, John Krill 352D, John Krill PDX-7145, John Krill 538J, John Krill 7640, John Krill 7641, John Krill 631, John Krill 790, John Krill 780, John Krill 7610 (trade name, BASF) NK binder R-5HN (trade name manufactured by Shin-Nakamura Chemical Co., Ltd., solid content 44%).

Among these, at least one selected from the group consisting of (meth) acrylic resin and styrene- (meth) acrylic acid copolymer resin is preferable, and more than the group consisting of acrylic resin and styrene-acrylic acid copolymer resin. At least one selected is more preferable, and a styrene-acrylic acid copolymer resin is further preferable. The above-mentioned copolymer may be in any form of 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 above-mentioned resin fine particles, it is particularly preferable to contain a cohesive resin. Since the ink composition contains a cohesive resin, betamura and bleeding tend to be more 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) using water as a medium, and the aqueous solution is also water. It means that the dispersion liquid is also included.) And a 0.085 mol / L calcium nitrate aqueous solution (hereinafter, also simply referred to as “calcium nitrate aqueous solution”) are preferably those having the property of aggregating when mixed, and among them, the above. It is more preferable that 3 mL of the resin aqueous solution and 3 mL or less of the calcium nitrate aqueous solution are mixed, and 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 agglomerating are more preferable. The volume of the above-mentioned mixed calcium nitrate aqueous solution is not limited, but can be 0.1 mL or more.

Such cohesive resins are not particularly limited, but include, for example, polyethylene-based resins (for example, Mitsui Kagaku Co., Ltd. product name "Chemipal S650"), polyethylene-based resins (for example, BYK Co., Ltd. product name "AQ515"). Examples thereof include polyester resins (for example, product name “KT8701” manufactured by Unitica).

The content of the resin is preferably 0.50 to 5.0% by mass, more preferably 1.0 to 4.0% by mass, based on the total amount of the ink composition. Within the above range, the water resistance and abrasion resistance of the recorded material tend to be more excellent, the ink composition is excellent in long-term storage stability, and the ink composition is particularly low in viscosity. It tends to be possible.

(water)
As the water, for example, those exemplified in the reaction solution composition can be used. The content of water is preferably 50 to 90% by mass, more preferably 60 to 90% by mass, and further preferably 60 to 85% by mass with respect to the total amount of the colored ink composition.

(Organic solvent)
Further, the colored ink composition may contain an organic solvent as a volatile component. The organic solvent is not particularly limited, but for example, those exemplified in the reaction solution composition can be used. The content of the organic solvent is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and further preferably 15 to 25% by mass with respect to the total amount of the colored ink composition. When the content of the organic solvent is within the above range, the scratch resistance of the recorded material is excellent and the viscosity of the ink can be reduced.

(Surfactant)
Further, the colored ink composition may contain a surfactant. The surfactant is not particularly limited, but for example, those exemplified in the reaction solution composition can be used. The content of the organic solvent is preferably 0.10 to 5.0% by mass, more preferably 0.10 to 3.0% by mass, based on the total amount of the colored ink composition. When the content of the surfactant is within the above range, the wettability of the colored ink composition adhering to the recording medium tends to be further improved. Further, since the resin is contained, the resin film is formed on the recording medium, so that the ink composition can be sufficiently fixed on the recording medium and the scratch resistance of the recorded material can be improved. ..

(Other ingredients)
The colored ink composition has a dissolution aid, a viscosity regulator, and a pH 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 regulators, antioxidants, preservatives, fungicides, corrosion inhibitors, and chelating agents for capturing metal ions that affect dispersion can also be added as appropriate.

[Recording medium]
Examples of the recording medium include an absorbent recording medium, a low absorption recording medium, and a non-absorbable recording medium. Among these, the absorbent recording medium or the low-absorbent recording medium has a relatively high absorbency of the reaction solution, so that the recording method of the present invention is particularly useful, and the present invention is particularly useful when the absorbent recording medium is used. Is useful.

The absorbent recording medium is not particularly limited, but is, for example, plain paper such as electrophotographic paper having high ink permeability, inkjet paper (an ink absorbing layer composed of silica particles or alumina particles, or polyvinyl alcohol (polyvinyl alcohol). From PVA) and special inkjet paper with an ink absorbing layer composed of hydrophilic polymers such as polyvinylpyrrolidone (PVP), art paper and coated paper used for general offset printing with relatively low ink permeability. Examples include cast paper.

The low-absorbency recording medium is not particularly limited, and examples thereof include coated paper provided with a coating layer on the surface for receiving oil-based ink. The coated paper is not particularly limited, and examples thereof include printed paper such as art paper, coated paper, and matte paper.

The non-absorbent recording medium is not particularly limited, but for example, a film or plate of plastics such as polyvinyl chloride, polyethylene, polypropylene, polyethylene terephthalate (PET), and metals such as iron, silver, copper, and aluminum. Examples thereof include a plate, a metal plate produced by vapor deposition of various metals thereof, a plastic film, and an alloy plate such as stainless steel or true cast.

Here, the "low-absorbing recording medium" or the "non-absorbable recording medium" refers to a recording medium having a water absorption amount 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 Pulp and Paper Technology Association (JAPAN TAPPI). For details of the test method, refer to the standard No. of "JAPAN TAPPI Pulp and Paper Test Method 2000 Edition". It is described in 51 "Paper and Paperboard-Liquid Absorption Test Method-Bristow Method". The low-absorption recording medium refers to a recording medium having the above-mentioned water absorption amount of 5 mL / m ² or more and 10 mL / m ² or less. On the other hand, the absorbent recording medium refers to a recording medium having a water absorption amount of more than 10 mL / m ² .

[Recording device]
FIG. 1 is a diagram showing an outline of an example of an inkjet recording device 1 that can be used in the present embodiment. As shown in FIG. 1, the inkjet recording device 1 includes a feeding unit 10 of a recording medium, a conveying unit 20, a recording unit 30, a drying device 90, and a discharging unit 70. Further, the inkjet recording device 1 is also provided with a preheater (not shown) as needed, and the recording medium F is heated from the beginning as needed.

Of these, the drying device 90 includes a first drying unit 40 for drying the recording medium and a second drying unit 50 for drying the recorded material obtained by the recording method according to the present embodiment, if necessary. Have.

Further, the feeding unit 10 is provided so that the roll-shaped recording medium F can be fed to the conveying unit 20. Specifically, the feeding unit 10 has 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 transport unit 20 on the downstream side in the feed direction Y.

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

Further, the recording unit 30 is provided so that the reaction liquid can be applied to the recording medium F sent from the transport unit 20 and the ink composition can be ejected and recorded. Specifically, the recording unit 30 includes heads 31 and 32 that perform a reaction liquid adhering step, a recording head 33 that performs a colored ink composition adhering step, and a platen 34 as a medium support portion.

Of 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 section 40 for drying the reaction liquid applied to the recording medium F and the ink composition ejected to the recording medium F as necessary. Further, a second feed roller 43 is provided on the downstream side of the platen 34 in the feed direction Y. The second feed roller 43 is configured to be able to feed the recorded recording medium F to the second drying portion 50 on the downstream side of the feed direction Y.

Further, the second drying unit 50 is configured so that the reaction liquid applied to the recording medium F and the ink composition ejected to the recording medium F can be further dried. Further, a third feed roller 65 is provided in the vicinity of the outlet 64 of the second drying portion 50. The third feed roller 65 is arranged 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 feed 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 to the downstream side in the feed direction Y and discharged to the outside of the inkjet recording device 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. Of these, the fourth feed roller 71 and the fifth feed roller 72 are arranged so as to be in contact with the surface of the recording medium F. Further, the 6th feed roller 73 and the 7th feed roller 74 are arranged so as to form a roller pair. The recording medium F discharged by the 6th feed roller 73 and the 7th feed roller 74 is provided so as to be wound by the take-up roller 75.

FIG. 2 shows a functional block diagram showing an example of the configuration of the recording device that can be used in the present embodiment. A printer driver is installed in the computer 130, and in order to have the inkjet recording device 1 (hereinafter, also referred to as a printer 1) record an image, print data corresponding to the image is output to the printer 1. The printer 1 has an ink supply unit 10, a transfer unit 20, a head unit 30, a drying unit 40, a maintenance unit 50, a detector group 110, a memory 123, an interface 121, and a controller 120. The controller 120 has a CPU 122 and a unit control circuit 124. The printer 1 that receives the print data from the computer 130, which is an external device, controls each unit by the controller 120 to control various recording conditions, and records an image on the recording medium according to the print data. The situation in the printer 1 is monitored by the detector group 110, and the detector group 110 outputs the detection result to the controller 120. The controller 120 controls each unit based on the detection result output from the detector group 110, and stores the print data input via the interface 121 in the memory 123. Control information for controlling each unit is also stored in the memory 123. The drying unit 40 includes a heater, air blowing means, and the like, and dries a composition such as ink adhering to a recording medium. The computer 130 may be included in the recording device.

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

[Materials for reaction solution and ink]
The main materials for the reaction solution and ink used in the following examples and comparative examples are as follows.
[Coagulant]
Calcium nitrate / tetrahydrate Calcium acetate / monohydrate Succinic acid [pigment]
Carbon black [cohesive resin]
Polyethylene resin (manufactured by Big Chemie, product name AQUACER507)
〔Organic solvent〕
1,2 Hexanediol Propylene glycol [surfactant]
Silicone-based surfactant (manufactured by Big Chemie, product name BYK348)

[Preparation of reaction solution and ink]
Each material was mixed with the composition (mass%) shown in Table 1 below and sufficiently stirred to obtain a reaction solution and a colored ink composition, respectively.

[Examples 1 to 12, Comparative Examples 1 to 6]
PX-G930 (manufactured by Epson Corporation) is filled with the reaction solution and the colored ink composition prepared above, and the reaction solution is discharged from the head by an inkjet method under the recording conditions shown in Table 2, and Lintec Corporation, which is a recording medium. A solid pattern (recording area S1) was formed on the NP-coated paper (reaction liquid adhesion step). The head nozzle density used was 1200 dpi.

Next, the colored ink composition was ejected from each head by an inkjet method under the recording conditions shown in Table 2 at an adhesion amount of 7 mg / inch ² to form a recording region S2 on the recording region S1 (colored ink composition adhesion step). Then, it was dried at 60 ° C. for 10 minutes. In the reaction liquid adhering step and the colored ink composition adhering step, the surface temperature of the recording medium was controlled to be as follows.
(Surface temperature condition of recording medium)
1: The surface temperature of the recording medium was maintained at 25 ° C. in each step from the reaction liquid adhering step to the colored ink composition adhering step.
2: The surface temperature of the recording medium was maintained at 40 ° C. in each step from the reaction liquid adhesion step to the colored ink composition adhesion step.

[Residual rate of volatile components]
The residual rate (drying rate) of the volatile components of the reaction solution in the recording area S1 before the colored ink composition adheres (when the recording medium is conveyed to a position facing the head for the colored ink composition) is as follows. It was calculated by the formula of.

Here, Af is the total amount (mg) of the reaction solution to be applied to the recording medium. Further, Ae is the amount of residue of the reaction solution on the recording medium in a state where the reaction solution is dried (volatilized) to a state sufficient for using the recorded material. Further, A is the total mass of the reaction solution on the recording medium immediately before the colored ink composition is attached.
Residual rate of volatile components% = 100-((Af-A) / (Af-Ae)) x 100

Af can be obtained as the amount of the reaction solution to be applied from the discharge data of the printer and the mass per dot. A can be obtained by measuring the mass of the recording medium at the time when the coloring ink composition starts to adhere and the mass of the recording medium before the reaction liquid adhesion step and taking a difference. When measuring the volatile amount of the volatile component, it is convenient to use the 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 amount of volatilization when the reaction solution is applied and then dried by heating with a platen is determined. When recording with a recording device, it is desirable that the time from the application of the reaction solution to the application of the colored ink composition is any time of the relationship between the drying time and the volatilization amount obtained above. Can be volatile.

In Examples and Comparative Examples other than Example 11, the residual rate of volatile components was 90% or more. Moreover, in Example 11, the residual rate of the volatile component was about 50%.

[Evaluation]
[Cohesiveness (solid image quality)]
The recording area S2 was visually observed and evaluated according to the following evaluation criteria.
◯: There is no unevenness inside the pattern Δ: There is some unevenness inside the pattern.
X: There is considerable unevenness inside the pattern.

[Recorded material durability]
The abrasion resistance of the recording area S2 was evaluated using a Gakushin type friction fastness tester AB-301 (trade name, manufactured by Tester Sangyo Co., Ltd.). Specifically, the recording area S2 was rubbed 50 times back and forth with a friction element attached with a white cotton cloth (JIS L 0803 compliant) under a load of 500 g. Then, the stain on the white cotton cloth and the peeling condition of the image (coating film) were visually observed. The white cotton cloth used was soaked in water, squeezed and watered. Recorded material durability tends to deteriorate due to moisture absorption of the coagulant remaining unreacted.
◯: No peeling in the image △: Some peeling is observed in a part of the image ×: Peeling is observed in the image

[Odor (sensory evaluation)]
The odor of the recorded material was evaluated in the recording area S2 by the sensory evaluation according to the following evaluation criteria.
○: No odor △: Slight odor ×: Odor

[Discharge stability]
Recording was continuously performed for 30 minutes under the condition of creating a recorded material, and it was inspected from the recorded material whether or not the nozzle of the colored ink head during recording had a ejection failure.
◯: The number of non-ejection nozzles is 3 or less in one head (1200 nozzles) constituting the line head.
Δ: The number of non-ejection nozzles is 4 or more in one head (1200 nozzles) constituting the line head.

Examples 1 to 12, which are examples of this embodiment, were excellent in cohesiveness, durability of recorded materials, and reduction of odor. It was found that the cohesiveness was lowered in Comparative Examples 1 and 3 in which the amount of the cohesive agent applied was too small, or in Comparative Example 5 in which the holding time was too long. Further, in Comparative Examples 2 and 4 in which the amount of the cohesive agent applied was too large, the cohesiveness was excellent, but the durability of the recorded material or the reduction of odor was inferior. On the other hand, in Comparative Example 6, although the cohesiveness was good despite the holding time being too long, it was found that the durability of the recorded material was poor probably because the amount of the cohesive agent applied was too large.

1 ... Inkjet recording device, 10 ... Feeding unit, 11 ... Roll medium holder, 20 ... Conveying unit, 21 ... First feed roller, 30 ... Recording unit, 31 ... Head, 32 ... Head, 33 ... Recording head, 34 ... Platen, 40 ... 1st drying section, 43 ... 2nd feed roller, 50 ... 2nd drying section, 64 ... outlet, 65 ... 3rd feed roller, 70 ... discharge section, 71 ... 4th feed roller, 72 ... 5th Feed roller, 73 ... 6th feed roller, 74 ... 7th feed roller, 75 ... take-up roller, 90 ... drying device, F ... recording medium, Y ... feed direction. 10 ... Ink supply unit, 20 ... Conveying unit, 30 ... Head unit, 40 ... Drying unit, 50 ... Maintenance unit, 110 ... Detector group, 120 ... Controller, 121 ... Interface, 122 ... CPU, 123 ... Memory, 124 ... Unit control circuit, 130 ... computer.

Claims (14)

A reaction in which a reaction solution containing a flocculant capable of coagulating the components of a colored ink composition is adhered to a recording medium at an adhesion amount of 100 to 1000 nmol / inch ² of the flocculant to form a recording region S1. Liquid adhesion process and
A step of heating the recording medium to dry the adhered reaction solution, and
The time from the end of adhesion of the reaction solution to a certain position of the recording medium to the start of adhesion of the colored ink to the position is within 30 seconds, and the colored ink composition containing the coloring material and the resin is used. It has a coloring ink composition attaching step of adhering to the recording area S1 to form a recording area S2.
In the coloring ink composition attaching step, the residual ratio of the volatile components of the reaction solution on the recording area S1 dried by the drying step is 100% by mass of the total mass of the volatile components contained in the reaction solution before adhesion. The colored ink composition containing the coloring material and the resin was adhered to the recording area S1 in a state of 30 to 50% by mass to form the recording area S2 .
In the drying step, the temperature of the recording region of the recording medium is 45 ° C. or lower.
A recording method in which the reaction solution has a water content of 40 to 80% by mass with respect to the total mass of the reaction solution . The recording method according to claim 1, wherein in the reaction liquid adhesion step, the reaction liquid is discharged as droplets and adhered to the recording medium at an adhesion density of 600 dpi or more × 600 dpi or more. The recording method according to claim 1 or 2, wherein the recording medium is an absorbable recording medium or a low absorption recording medium. The recording method according to any one of claims 1 to 3, wherein the content of the flocculant is 0.090 mol / 1000 g or more and 0.91 mol / 1000 g or less with respect to the total amount of the reaction solution. The recording method according to any one of claims 1 to 4, wherein the component of the colored ink composition that aggregates by the flocculant contains at least one of a pigment as the coloring material and the resin. The recording method according to any one of claims 1 to 5, wherein the flocculant contains at least one of a polyvalent metal salt and an organic acid. In the reaction liquid adhering step and the colored ink composition adhering step, the reaction liquid or the colored ink composition is ejected from the ink jet head while changing the relative positions of the ink jet head and the recording medium. The recording method according to any one of claims 1 to 6, wherein adhesion is performed by performing scanning once. The recording method according to any one of claims 1 to 7, wherein the reaction liquid is discharged from the inkjet head in the reaction liquid adhesion step. The recording method according to any one of claims 1 to 8, further comprising a step of heating the recording medium to dry the reaction solution in the step of adhering the colored ink composition. The recording method according to any one of claims 1 to 9, wherein the flocculant contains a polyvalent metal salt, and the polyvalent metal salt contains either a carboxylate or a sulfate. The recording method according to any one of claims 1 to 10, wherein the recording medium is a low-absorption recording medium or a non-absorbent recording medium. The recording method according to any one of claims 1 to 11, wherein in the reaction liquid adhesion step, the reaction liquid is discharged as droplets and adhered to the recording medium at an adhesion density of 1200 dpi or more × 1200 dpi or more. .. The recording method according to any one of claims 1 to 12, wherein the period from the end of adhesion of the reaction solution to the certain position to the start of adhesion of the colored ink to the position is within 20 seconds. The recording method according to any one of claims 1 to 12, wherein in the drying step, the temperature of the recording region of the recording medium is 40 ° C. or lower.

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