JP7094491B2 - Recording method - Google Patents

Description

The present invention relates to a recording method.

The inkjet recording method is a relatively simple device that can record high-definition images, and is rapidly developing in various fields. Among them, various studies have been made on discharge stability and the like. For example, Patent Document 1 aims to provide a water-based inkjet ink composition capable of forming an image having excellent clogging resistance in a head and excellent scratch resistance, and a difference between a resin and an SP value with respect to the resin. Contains 3 or less nitrogen-containing solvent and water, the content of the nitrogen-containing solvent is 2 to 9 parts by mass with respect to 1 part by mass of the resin, and the content of the organic solvent having a standard boiling point of 280 ° C. or higher. A water-based inkjet ink composition in which is 3% by mass or less is disclosed. As in Patent Document 1, by using a predetermined solvent, the resin is sufficiently dissolved in the recording medium to easily form a film and has excellent scratch resistance, and the resin welded in the head is difficult to remove by cleaning and is difficult to recover. There are known ink compositions that do not.

Japanese Unexamined Patent Publication No. 2017-186472

By recording on a wide recording medium using an inkjet printer, it is possible to obtain a recorded material useful for display or the like. Nowadays, when recording with a wide recording medium and a long scanning distance and using a treatment liquid that aggregates ink components to improve image quality, the colors differ depending on the location of the image on the recording medium. There was a problem that would end up.

An object of the present invention is to provide a recording method capable of suppressing the occurrence of a color difference in a recorded object in the above cases.

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 using the basic color ink composition and the special color ink composition in combination, and have completed the present invention.

That is, the present invention is as follows.
[1]
A colored ink composition containing a cyan ink composition, a magenta ink composition, a yellow ink composition, and a special color ink composition having a hue angle different from that of each of the ink compositions is ejected from an inkjet head and recorded. Ink adhesion process to adhere to the medium and
A treatment liquid adhering step of adhering a treatment liquid containing a flocculant that agglomerates the components of the colored ink composition to the recording medium is provided.
The ink adhesion step is performed by performing scanning for ejecting the colored ink composition a plurality of times while changing the position of the inkjet head relative to the recording medium in the scanning direction.
The maximum distance of one scan in the ink adhesion step is 50 cm or more.
Recording method.
[2]
The spot color ink composition comprises at least one of an orange ink composition, a red ink composition, a green ink composition, and a blue ink composition.
The recording method according to [1].
[3]
The colored ink composition further comprises a black ink composition.
The recording method according to [1] or [2].
[4]
The recording medium is a low-absorbency recording medium or a non-absorbent recording medium.
The recording method according to any one of [1] to [3].
[5]
The recording medium is provided with a heating step for heating the recording medium, and the ink adhesion step is performed on the heated recording medium, or the recording medium is subjected to the ink adhesion step.
The ink adhering step comprises a blowing step of blowing air to a region to which the colored ink composition is adhered.
The recording method according to any one of [1] to [4].
[6]
The surface temperature of the recording medium when the colored ink composition is adhered in the ink adhesion step is 30 to 45 ° C.
The recording method according to any one of [1] to [5].
[7]
The maximum time of one scan in the ink adhesion step is 0.8 seconds or more.
The recording method according to any one of [1] to [6].
[8]
The flocculant is one or more of a polyvalent metal salt, an organic acid or a salt thereof, and a cationic resin.
The recording method according to any one of [1] to [7].
[9]
The maximum distance of one scan in the ink adhesion step is 50 to 500 cm.
The recording method according to any one of [1] to [8].
[10]
The recording region to which the colored ink composition and the treatment liquid are adhered has a region in which the adhesion amount of the treatment liquid is 5 to 30% by mass with respect to the adhesion amount of the colored ink composition.
The recording method according to any one of [1] to [9].
[11]
The temperature difference between the surface temperatures of the recording medium in the ink adhesion step is 1 to 10 ° C.
The recording method according to any one of [1] to [10].
[12]
A colored ink composition containing a cyan ink composition, a magenta ink composition, a yellow ink composition, and a special color ink composition having a hue angle different from that of each of the ink compositions is ejected from an inkjet head and recorded. Ink adhesion process to adhere to the medium and
A treatment liquid adhering step of adhering a treatment liquid containing a flocculant that agglomerates the components of the colored ink composition to the recording medium is provided.
The ink adhesion step is performed by performing scanning for ejecting the colored ink composition a plurality of times while changing the position of the inkjet head relative to the recording medium in the scanning direction.
The difference in surface temperature of the recording medium when the colored ink is adhered in the ink adhesion step is 1 to 10 ° C.
Recording method.
[13]
A recording device for recording by the recording method according to any one of [1] to [12].

It is a schematic sectional drawing which shows the structure of the recording apparatus used in this embodiment. It is a partial side view of the recording apparatus in the ink adhesion process, (a) shows the aspect in which a carriage is not arranged, (b) shows the aspect in which a carriage is arranged. It is a schematic perspective view which shows the structural example around the carriage of the recording apparatus used in this embodiment. It is a front view which shows an example of the fan which the recording apparatus used in this embodiment has.

Hereinafter, embodiments of the present invention (hereinafter referred to as “the present embodiments”) will be described in detail with reference to the drawings as necessary, but the present invention is not limited thereto and is 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. In addition, the positional relationship such as up, down, left, and right shall be based on the positional relationship shown in the drawings unless otherwise specified. 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 colored ink composition containing a cyan ink composition, a magenta ink composition, a yellow ink composition, and a special color ink composition having a hue angle different from that of each of the ink compositions is used. The ink adhering step of ejecting from the inkjet head and adhering to the recording medium and the processing liquid adhering step of adhering the treatment liquid containing the coagulant for aggregating the components of the colored ink composition to the recording medium are provided. The ink adhesion step is performed by performing scanning for ejecting the colored ink composition a plurality of times while changing the position of the ink jet head relative to the recording medium in the scanning direction, and one scanning in the ink adhesion step. The maximum distance is 50 cm or more.

As described above, it has been found that the recording method in which the distance of one scan is long has a unique problem that the color difference becomes large. Examples of recording devices having a long scanning distance include large format printers.

When the treatment liquid is used, the ink droplets adhering to the recording medium can be fixed at an early stage, so that the image quality is improved. Therefore, it is presumed that the color difference will be large. On the other hand, when the reaction solution is not used, it is presumed that the ink droplets that have adhered to each other are more agglomerated before they are fixed and the color difference becomes larger. The color difference is a color difference depending on the location even though an image of the same color is to be recorded in one recording medium. In particular, when a recording medium having a wide width in the scanning direction is used, the distance of one scanning becomes long and a color difference in the scanning direction tends to occur. It is presumed that when the distance of one scan is long, the influence that causes the color difference described later is large. The color difference is also referred to as an in-plane color difference.

Further, in a recording device having a wide scanning direction of a recording medium, the scanning time of one pass is long, and in such a case, recording can be performed by increasing the moving speed of the carriage in order to improve productivity and image quality. Will be done. However, at the same time, the influence of the wind due to the movement becomes stronger, and the influence may affect the color difference.

In addition to or instead of using the treatment liquid, the image quality is improved by increasing the heating temperature in order to accelerate the drying of the ink. Further, when recording is performed on a low-absorbency recording medium or a non-absorbent recording medium, it is effective to promote drying by heating during recording, which is effective in improving the image quality. However, it has become clear that the color difference tends to increase due to drying during recording. This is a recording device having a wide scanning direction of a recording medium such as a large format printer, in which temperature unevenness is likely to occur in the width direction when a heater is provided on the back surface of the recording medium or when wind is applied as a drying means. It is presumed that this is due to the fact that it cannot be ignored from the viewpoint of color difference. In particular, when the width in the scanning direction is wide, the number of heater joints and wind outlets is large, and there are many places where in-plane temperature difference is likely to occur due to the configuration of the device, and the temperature difference becomes large. There is also a factor in being easy. As a result, a color difference occurs due to temperature unevenness depending on the heating location described above.

Further, as the drying in the vicinity of the nozzle progresses due to heating, the weight of the ejected dots itself may change, or the impact deviation may occur due to the non-uniformity of the meniscus. In a recording method using a recording device having a wide scanning direction, it is presumed that color difference is likely to occur due to such a complex factor.

On the other hand, in the present embodiment, the color difference can be reduced by using the basic color ink composition and the special color ink composition in combination. This is because when the color of the spot color area is recorded using the spot color ink composition, the dot gathering state on the recording surface may fluctuate slightly due to landing deviation, etc., or the difference in how the dots spread due to uneven drying. Even if it occurs, it is presumed that it is difficult to appear as a color difference. This makes it possible to record with a small color difference from the basic color area to the spot color area. Hereinafter, each step will be described in detail. The spot color area is a part to be recorded by the spot color of the image.

On the other hand, when the color of the special color region is reproduced on the recording medium as a secondary color by densely mixing the dots of two colors of ink, the fluctuation of the state of the dots gathered on the recording surface and the spread of the dots are performed. It is presumed that the color difference will be large if there is a difference between the two or if the ink adhesion order is different.

[Ink adhesion process]
In the ink adhesion step, a colored ink composition containing a cyan ink composition, a magenta ink composition, a yellow ink composition, and a special color ink composition having a hue angle different from that of each of the ink compositions is obtained from an inkjet head. This is a step of ejecting and adhering to a recording medium. Here, the inkjet head is a head for ejecting an ink composition toward a recording medium for recording, and the head is for a cavity for ejecting the contained ink composition from a nozzle and an ink composition. It has a discharge drive unit that applies a discharge drive force, and a nozzle that discharges the ink composition to the outside of the head. The discharge drive unit is formed by using an electromechanical conversion element such as a piezoelectric element that changes the volume of the cavity by mechanical deformation, or an electronic heat conversion element that generates bubbles in the ink to discharge heat by generating heat. be able to.

Further, the ink adhesion step is performed by performing scanning for ejecting the ink composition a plurality of times while changing the position of the inkjet head relative to the recording medium in the scanning direction. That is, the inkjet head is preferably a serial head. In the serial method using a serial head, the head is moved along the main scanning direction (horizontal direction and width direction of the recording medium), and ink droplets are ejected from the nozzle opening of the head in conjunction with this movement for recording. Images can be recorded on the medium. Scanning may be performed by moving the carriage in the main scanning direction, such as by mounting the head on the carriage. In the present invention, scanning is also referred to as main scanning.

Then, by alternately repeating scanning and sub-scanning, the recording medium is gradually moved along the sub-scanning direction (longitudinal direction and transport direction of the recording medium) to advance recording.

The maximum distance of one scan is 50 cm or more, preferably 50 to 500 cm, more preferably 50 to 400 cm, still more preferably 55 to 300 cm, still more preferably 60 to 200 cm. Further, it is particularly preferably 70 to 190 cm, more particularly preferably 100 to 180 cm, and further particularly preferably 130 to 170 cm.

When the distance is 50 cm or more, it can be a useful record for display or the like. On the other hand, the color difference of the obtained recorded matter is likely to occur, but according to the present invention, the color difference can be reduced, and the present invention is particularly useful. Further, the upper limit of the distance is not particularly limited, but 500 cm or less is preferable from the viewpoint of the configuration of the recording device and the reduction of the color difference is more excellent.

The "maximum distance of one scan" means the distance at which one point of the inkjet head faces the recording medium in one scan when the recording medium is temporarily recorded from one end to the other in the scanning direction. When performing the recording method, scanning that is shorter than the maximum distance of the above-mentioned one scan may be performed depending on the image to be recorded.

In addition to the above, the cause of the color difference of the recorded material obtained when the maximum distance of one scan is long is that there is a portion that floats from the platen to the recording medium when the recording medium is conveyed, and the ink It is presumed that the landing deviation (positional deviation) may occur. Furthermore, the floating of the recording medium also causes a temperature difference in the surface temperature of the recording medium.

It is preferable to use a recording medium in which the width of the recording medium in the scanning direction is within the range of the maximum distance of the above-mentioned one scan. In this case, it is preferable that the maximum distance of one scan can be set to the above.

The maximum time of one scan in the ink adhesion step is preferably 0.8 seconds or more. It is preferably 0.8 to 5 seconds or less, more preferably 0.8 seconds or more and 4 seconds or less, still more preferably 0.8 seconds or more and 3 seconds or less, and particularly preferably 1.5 to 2.5 seconds. Seconds. It is preferable that the maximum time of one scan is within the above range, which is suitable for recording on a recording medium in which the width of the recording medium is within the above range. Further, although the color difference of the obtained recorded matter is likely to occur, the present invention is particularly useful in that the color difference can be reduced. The "maximum time of one scan" is the time during which one point of the inkjet head faces the recording medium in one scan when recording is performed from one end to the other in the scanning direction of the recording medium. Say. When performing the recording method, scanning for a time shorter than the maximum time of the above-mentioned one scanning may be performed depending on the image to be recorded.
The average scanning speed in the ink adhesion step is preferably 60 to 100 cm / sec.

It is preferable that the recording medium is provided with a heating step for heating the recording medium, and the ink adhesion step is performed on the recording surface of the heated recording medium. A heating mechanism such as a platen heater, a hot air heater, or an IR heater can be used to heat the recording medium. The surface temperature of the recording medium when the ink composition is adhered in the ink adhesion step is preferably 20 to 60 ° C, more preferably 20 to 50 ° C, still more preferably 25 to 45 ° C, and further. The temperature is preferably 30 to 40 ° C, particularly preferably 32 to 38 ° C. By heating the recording medium and raising the surface temperature, the image quality of the obtained recorded matter tends to be improved. Further, when the surface temperature of the recording medium is 60 ° C. or lower, the ejection stability and the nozzle clogging recovery tend to be further improved.

Further, in the heating step, the surface temperature of the recording medium may be higher than the normal temperature due to the recording medium receiving heat generated by the recording device itself. That is, it means that the surface temperature of the recording medium is higher than normal temperature.

The surface temperature of the recording medium is the temperature of the entire surface of the recording medium supported by the platen during the main scanning of the head of the recording medium, and the temperature of the surface of the recording medium during recording in the region is measured. Let it be our highest temperature.

The temperature of the surface of the recording medium during recording in the region may cause a temperature difference due to a portion having a temperature lower than the maximum temperature. The temperature difference tends to be larger as the maximum distance of one scan is longer. The reason for this is that it is difficult to uniformly heat the recording medium over the entire scanning direction.

The temperature difference between the maximum temperature and the minimum temperature of the total temperature of the regions that can face each other during the main scan of the head of the recording medium supported by the platen is preferably 10 ° C or lower, more preferably 7 ° C or lower, and more preferably 5 ° C or lower. More preferred. The temperature difference is preferably 1 ° C. or higher, more preferably 2 ° C. or higher, and even more preferably 3 ° C. or higher. When the temperature difference is within the above range, it is preferable in that the reduction of the color difference is more excellent and the degree of freedom in designing the recording device is increased. Further, the lower the surface temperature of the above-mentioned recording medium, the smaller the temperature difference tends to be, which is preferable in terms of reducing the color difference.

By accelerating the drying of the ink by the heating step, it is more excellent in suppressing density unevenness and also in suppressing color difference. The surface temperature of the recording medium at the time of ink adhesion is preferably equal to or higher than the above range in this respect. On the other hand, it is preferable that the surface temperature of the recording medium is below the above range in that the color difference suppression is more excellent by suppressing the occurrence of temperature unevenness that causes the color difference.

Further, in the ink adhesion step, it is preferable to include a blowing step of blowing air to the region to which the ink composition is adhered. The blowing method is not particularly limited, but for example, a blower provided in a recording device or the like is used. By having the ventilation step, the ink composition adhering to the recording medium can be efficiently dried, and the roughness and density unevenness of the obtained recorded matter tend to be further suppressed.

The temperature of the air in the blowing step may be warm air that heats the recording medium, and in this case, the air may be blown as the heating step for heating the recording medium. In this case, it is preferable in that the image quality of the obtained recording medium is further improved. Alternatively, the wind may be sent as normal temperature air that does not heat the recording medium. This case is also preferable in that the image quality of the recording medium obtained by promoting the evaporation of the ink components is further improved and the ink ejection stability from the head is excellent. The temperature of the blown air may be the temperature of the surface temperature of the recording medium in the heating step of heating the recording medium. Alternatively, the temperature of the air to be sent is specifically preferably 70 ° C. or lower, more preferably 50 ° C. or lower, further preferably 40 ° C. or lower, further preferably 35 ° C. or lower, and particularly preferably 30 ° C. or lower. The lower limit of the wind temperature is not limited, but is preferably 20 ° C. or higher. On the other hand, when the ventilation process is provided, the difference in the surface temperature of the recording medium tends to occur.

The recording region to which the colored ink composition and the treatment liquid are adhered preferably has a region in which the total adhesion amount of the colored ink composition is 5 to 30 mg / inch ² , and preferably has a region of 7 to 25% by mass. It is more preferable to have a region of 9 to 20% by mass. By having a region of such an adhesion amount, it is possible to make a record material useful for display and the like. Further, it is also preferable that the total adhesion amount of the region where the total adhesion amount of the colored ink composition in the recording region is the maximum is in the above range.

(Post-heating process)
After the ink adhesion step, it is preferable to have a post-heating step of further heating the recording medium. The heating method is not particularly limited, and examples thereof include a platen heater, a hot air heater, and an IR heater. The heating temperature can be preferably 60 ° C. or higher. It is preferably 70 to 110 ° C, more preferably 80 to 100 ° C.

(Colored ink composition)
The colored ink composition includes a cyan ink composition, a magenta ink composition, a yellow ink composition, and a spot color ink composition having a hue angle different from that of each of the three ink compositions. Here, the "hue angle" refers to the hue angle of the CIE color system when an image is recorded and the color is measured with the ink composition. Specifically, an image is recorded using one ink each, and the color of the recording unit is measured. The image used here may be an image in which the hue angle of the recording unit due to the adhesion of ink can be confirmed. For example, an ink adhered to a white recording medium at an adhesion amount of 10 mg / inch ² can be mentioned.

The cyan ink composition, the magenta ink composition, and the yellow ink composition have different hue angles from each other. In the present embodiment, the hue angle (∠H °) of the cyan ink composition is 230 ° to 260 °, and the hue angle (∠H °) of the magenta ink composition is 330 ° to 360 °, which is yellow. The hue angle (∠H °) of the ink composition is preferably 80 ° to 110 °. The cyan ink composition, the magenta ink composition, the yellow ink composition, and the spot color ink composition are chromatic inks capable of recording chromatic colors having the above-mentioned hue angles, respectively.

The special color ink composition is not particularly limited as long as the hue angle is different from the cyan ink composition, the magenta ink composition, and the yellow ink composition used in the recording method. For example, the orange ink composition and the red ink are not limited. At least one of a composition, a green ink composition, and a blue ink composition can be mentioned. The spot color ink composition may be used alone or in combination of two or more. By using the spot color ink composition, the color difference is suppressed. The hue angle of the spot color ink is not limited, but is preferably in the range described later. Further, for example, the above-mentioned cyan ink composition, magenta ink composition, and yellow ink composition may be out of the range of preferable hue angles.

In addition to the above, the colored ink composition may further contain a black ink composition. By using the black ink composition, the color expression region of the obtained recorded matter tends to be further expanded. The spot color ink composition is not a black ink composition.

Each ink composition contained in the colored ink composition contains a coloring material. It preferably contains a solvent, and may contain a resin, a wax, an antifoaming agent, and a surfactant, if necessary. It preferably contains resin fine particles and an organic solvent. It is preferably a water-based ink composition. The aqueous composition is a composition containing water as one of the main solvent components, and the content of water is preferably 45% by mass or more. Each ink composition contained in the colored ink composition can independently exemplify the same basic composition except that the hue angle is different due to a difference in the type of coloring material used or the like. Hereinafter, each component will be described.

(Color material)
Examples of the coloring material include pigments and dyes. Pigments are preferable because they have excellent light resistance.
The pigment used in the cyan ink composition 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, 25, 65, 66, C.I. I. Bat blue 4, 60 can be mentioned. The hue angle (∠H °) of the cyan ink composition is preferably 230 ° to 260 °.

The pigment used in the magenta ink composition 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, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48 (Ca), 48 (Mn), 53, 57 (Ca), 57: 1, 88, 114, 122, 123, 144, 146, 150, 166, 168, 170, 171 176, 179, 184, 185, 187, 202, 209, 219, 224, 245, or C.I. I. Pigment Violet 33, 43, 50, and the like. The hue angle (∠H °) of the magenta ink composition is preferably 330 ° to 360 °.

The pigment used in the yellow ink composition 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 hue angle (∠H °) of the yellow ink composition is preferably 80 ° to 110 °.

The carbon black used in the black ink composition 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. Rega1 330R, Rega1 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. , Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color B1ack S150, Color Black S160, Color Black Black S170, Color Black Black Examples thereof include Black 4A and Special Black 4 (all manufactured by Degussa).

The pigment used in the orange ink composition is not particularly limited, but for example, C.I. I. Pigment Orange 5,43,62. The hue angle (∠H °) of the orange ink composition is preferably 30 ° to 80 °.

The pigment used in the red ink composition is not particularly limited, but for example, C.I. I. Pigment Red 17, 49: 2, 112, 117, 175, 177, 178, 188, 254, 255, 264, 149. The hue angle (∠H °) of the red ink composition is preferably 0 ° to 30 °.

The pigment used in the green ink composition is not particularly limited, but for example, C.I. I. Pigment Greens 7 and 36 can be mentioned. The hue angle (∠H °) of the green ink composition is preferably 110 ° to 230 °.

The pigment used in the blue ink composition is not particularly limited, but for example, C.I. I. Pigment Blue 21, 22, 60, 64, C.I. I. Pigment Violet 3, 19, 23, 32, 36, 38. The hue angle (∠H °) of the blue ink composition is preferably 260 ° to 330 °.

Further, as a dye, C.I. I. Acid Yellow, C.I. I. Acid Red, C.I. I. Acid Blue, C.I. I. Acid Orange, C.I. I. Acid Violet, C.I. I. Acid dyes such as acid black; C.I. I. Basic Yellow, C.I. I. Basic Red, C.I. I. Basic blue, C.I. I. Basic Orange, C.I. I. Basic Violet, C.I. I. Basic dyes such as basic black; C.I. I. Direct Yellow, C.I. I. Direct Red, C.I. I. Direct Blue, C.I. I. Direct Orange, C.I. I. Direct Violet, C.I. I. Direct dyes such as Dilekdo Black; C.I. I. Reactive Yellow, C.I. I. Reactive Red, C.I. I. Reactive Blue, C.I. I. Reactive Orange, C.I. I. Reactive Violet, C.I. I. Reactive dyes such as reactive black; C.I. I. Disperse Yellow, C.I. I. Disperse thread, C.I. I. Disperse Blue, C.I. I. Disperse Orange, C.I. I. Disperse Violet, C.I. I. Disperse dyes such as Disperse Black can be mentioned. The coloring material may be used alone or in combination of two or more.

When the coloring material is a pigment, it can be used in the state of a pigment dispersion liquid. The pigment dispersion liquid may contain a dispersant, if necessary, in addition to the pigment and the solvent. Examples of the solvent include water and hydrophilic solvents such as diethylene glycol. Further, examples of the dispersant include a styrene-acrylic acid copolymer. Although not particularly limited, the acid value of the dispersant is preferably 20 mgKOH / g or more from the viewpoint of its dispersibility.

The content of the coloring material in each colored ink composition may be different, but is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, based on the total amount of the ink composition. %, More preferably 1 to 4% by mass, still more preferably 1.5 to 4% by mass.

(solvent)
Examples of the solvent include water and organic solvents. 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 ink composition.

The organic solvent is not particularly limited, but specifically, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,2-butanediol, 1,2. -Pentylene diol, 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, 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 ethylmethyl ether, diethylene glycol butylmethyl 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 -Alcohols or glycols such as pentanol, 3-pentanol, and tert-pentanol can be mentioned. The organic solvent may be used alone or in combination of two or more.

The content of the organic solvent is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, and further preferably 15 to 30% by mass with respect to the total amount of the ink composition.

(Nitrogen-containing solvent)
Further, it is also preferable to use a nitrogen-containing solvent as the organic solvent. By containing the nitrogen-containing solvent, the effect of promoting the softening of the resin particles of the nitrogen-containing solvent tends to further improve the rubbing resistance even when the heating temperature is low. Further, when the recording medium is a low-absorbency recording medium or a non-absorbent recording medium, the adhesion tends to be further improved by the effect of softening the surface of the recording medium. The nitrogen-containing solvent is not particularly limited, and examples thereof include pyrrolidone-based solvents, imidazolidinone-based solvents, amide ether-based solvents, pyridine-based solvents, pyrazine-based solvents, and pyridone-based solvents.

Further, as the nitrogen-containing solvent, an amide-based solvent is preferable. Examples of the amide-based solvent include cyclic amide-based solvents and non-cyclic amide-based solvents. Examples of the cyclic amide-based solvent include the above-mentioned pyrrolidone-based solvents. Examples of the acyclic amide solvent include the above-mentioned amide ether solvent. Pyrrolidone-based solvents are particularly preferable, and examples thereof include 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone. The nitrogen-containing solvent may be used alone or in combination of two or more.

From the above viewpoint, the content of the nitrogen-containing solvent is preferably 3 to 25% by mass, more preferably 5 to 23% by mass, and further preferably 10 to 21% by mass with respect to the total amount of the ink composition. Is.

The content of the organic solvent other than the nitrogen-containing solvent among the organic solvents is preferably 1 to 20% by mass, more preferably 5 to 20% by mass, and further preferably 8 to 16% by mass. Among the organic solvents other than the nitrogen-containing solvent, polyols and alkylene glycol ethers are preferable. Polyols are organic solvents having two or more hydroxyl groups in the molecule. The number of hydroxyl groups is preferably 2 to 3. The alkylene glycol ethers are mono or diethers of alkylene glycol. The ether is preferably an alkyl ether, more preferably an alkyl ether having 1 to 5 carbon atoms. The alkylene glycol preferably has 2 to 5 carbon atoms.

The organic solvent preferably contains a standard boiling point of 180 to 280 ° C., more preferably 200 to 260 ° C., and even more preferably 210 to 250 ° C. In this case, it is preferable in that various image quality of the image is more excellent.

The content of the organic solvent with respect to the composition having a standard boiling point of more than 280 ° C. is preferably 1% by mass or less, more preferably 0.5% by mass or less, and 0.1% by mass or less. The lower limit may be 0% by mass. In this case, it is preferable in that various image quality of the image is more excellent.

(resin)
Examples of the resin include those that dissolve in the ink composition and those that disperse in the form of fine particles such as emulsions. By using such a resin, it tends to be possible to obtain a recorded material having better scratch resistance. In particular, it tends to contribute to the improvement of the bondability (rubbing resistance) between the recording medium and the ink coating film. Such resins are not particularly limited, but are, for example, acrylic resins, vinyl acetate resins, vinyl chloride resins, butadiene resins, styrene resins, polyester resins, crosslinked acrylic resins, crosslinked styrene resins, benzoguanamine resins, phenol resins, and silicone resins. , Epoxy resin, urethane resin, paraffin resin, fluororesin, and water-soluble resin, and copolymers in which the monomers constituting these resins are combined. The copolymer is not particularly limited, and examples thereof include styrene butadiene resin and styrene acrylic resin. Further, as the resin, a polymer latex containing these resins can be used. For example, a polymer latex containing fine particles of acrylic resin, styrene acrylic resin, styrene resin, crosslinked acrylic resin, and crosslinked styrene resin can be mentioned. The resin may be used alone or in combination of two or more.

The acrylic resin is a resin which is a homopolymer or a copolymer obtained by polymerizing at least an acrylic monomer as a monomer. Examples of the acrylic monomer include (meth) acrylate, (meth) acrylic acid, acrylamide, acrylonitrile and the like. When the acrylic resin is a copolymer, examples thereof include acrylic-vinyl resin using a vinyl-based monomer as another monomer, and among them, styrene acrylic resin using styrene as a vinyl-based monomer and the like can be mentioned.
As the resin, acrylic resin, urethane resin, polyester resin and the like are easily available, and it is preferable to obtain a resin having desired characteristics.

The content of the resin is preferably 1 to 12.5% by mass, more preferably 2 to 10% by mass, and further preferably 3 to 7.5% by mass with respect to the total amount of the ink composition. .. When the content of the resin is 1% by mass or more, the abrasion resistance tends to be further improved as described above. Further, when the content of the resin is 12.5% by mass or less, the viscosity of the ink is lowered, the ejection stability is excellent, and the clogging recovery tends to be excellent.

(wax)
Examples of the wax include those that dissolve in the ink composition and those that disperse in the form of fine particles such as emulsions. By using such a wax, it tends to be possible to obtain a recorded material having better scratch resistance. In particular, it tends to contribute to the improvement of scratch resistance due to uneven distribution on the surface of the ink coating film (the interface between air and the ink coating film) on the recording medium. Such a wax is not particularly limited, and is, for example, an ester wax, a paraffin wax, a microcrystalline wax, an olefin wax, or a mixture thereof of a higher fatty acid and a higher monohydric alcohol or a dihydric alcohol (preferably a monohydric alcohol). Can be mentioned.

The wax content is preferably 0.1 to 5% by mass, preferably 0.2 to 4% by mass, and preferably 0.3 to 3% by mass with respect to the total amount of the ink composition. .. When the wax content is 0.1% by mass or more, the abrasion resistance tends to be further improved as described above. Further, when the wax content is 5% by mass or less, the viscosity of the ink is lowered, the ejection stability is excellent, and the clogging recovery is excellent.

(Surfactant)
The surfactant is not particularly limited, and examples thereof include an acetylene glycol-based surfactant, a fluorine-based surfactant, and a polysiloxane-based surfactant.

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

The fluorosurfactant is not particularly limited, and is, for example, perfluoroalkyl sulfonate, perfluoroalkyl carboxylate, perfluoroalkyl phosphate ester, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, per. Fluoroalkylamine oxide compounds can be mentioned. The commercially available fluorosurfactant 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 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, still more preferably 0.3 to 1% by mass, based on the total amount of the ink composition. It is 5.5% by mass.

(Defoamer)
The defoaming agent is not particularly limited, and examples thereof include a silicone-based defoaming agent, a polyether-based defoaming agent, a fatty acid ester-based defoaming agent, and an acetylene glycol-based defoaming agent. Commercially available defoaming agents include BYK-011, BYK-012, BYK-017, BYK-018, BYK-019, BYK-020, BYK-021, BYK-022, BYK-023, BYK-024, BYK. -025, BYK-028, BYK-038, BYK-044, BYK-080A, BYK-094, BYK-1610, BYK-1615, BYK-1650, BYK-1730, BYK-1770 (trade names, Big Chemie Japan) DF37, DF110D, DF58, DF75, DF220, MD-20, Envilogem AD01 (all product names, manufactured by Nissin Chemical Industry Co., Ltd.). .. The defoaming agent may be used alone or in combination of two or more.

The content of the defoaming agent is preferably 0.03 to 0.7% by mass, more preferably 0.05 to 0.5% by mass, and further preferably 0, based on the total amount of the ink composition. It is .08 to 0.3% by mass.

(Other ingredients)
The ink composition used in this embodiment is, if necessary, a solubilizing agent, a viscosity regulator, a pH regulator, an antioxidant, a preservative, a fungicide, a corrosion inhibitor, and a metal that affects dispersion. It may contain various additives such as a chelating agent for capturing ions.

(recoding media)
Examples of the recording medium include an absorbent recording medium, a low absorbency recording medium, and a non-absorbent recording medium. Among these, a low-absorbency recording medium or a non-absorbent recording medium is preferable because it can produce a recorded material useful for display and the like. By using such a recording medium, roughness, uneven density, and color difference of the obtained recorded matter are likely to occur, and the present invention is particularly useful.

The absorbent recording medium is not particularly limited, but is, for example, plain paper such as electrophotographic paper having high permeability of the ink composition, inkjet paper (an ink absorbing layer composed of silica particles or alumina particles, or polyvinyl alcohol). (PVA), polyvinylpyrrolidone (PVP), and other ink-jet paper provided with an ink-absorbing layer made of a hydrophilic polymer) and the like.

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

The non-absorbent recording medium is not particularly limited, and is, for example, a film or plate of plastics such as polyvinyl chloride, polyethylene, polypropylene, polyethylene terephthalate (PET), polycarbonate, polystyrene, polyurethane; iron, silver, copper, aluminum. Metal plates such as; or metal plates and plastic films manufactured by vapor deposition of various metals, alloy plates such as stainless steel and true cast; polyvinyl chloride, polyethylene, etc. on base materials such as paper, cloth, and film. Examples thereof include a recording medium to which a plastic film such as polypropylene, polyethylene terephthalate (PET), polycarbonate, polystyrene, or polyurethane is adhered (coated).

Here, the "low-absorbing recording medium" or "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 Technical Association of the Pulp and Paper (JAPAN TAPPI). For details of the test method, refer to the standard No. of "JAPAN TAPPI Paper and Pulp Test Method 2000 Edition". 51 "Paper and Paperboard-Liquid Absorption Test Method-Bristow Method". The low-absorbency 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 .

Further, the non-absorbent recording medium or the low-absorbency recording medium can be classified according to the wettability of the recording surface with water. For example, the recording medium is measured by dropping 0.5 μL of water droplets on the recording surface of the recording medium and measuring the reduction rate of the contact angle (comparison between the contact angle at 0.5 msec and the contact angle at 5 seconds after landing). Can be characterized. More specifically, as a property of the recording medium, the non-absorbency of the "non-absorbent recording medium" means that the above-mentioned reduction rate is less than 1%, and the low-absorbency of the "low-absorbency recording medium" is the above. It means that the rate of decrease of is 1% or more and less than 5%. Further, the absorbability means that the above-mentioned reduction rate is 5% or more. The contact angle can be measured using a portable contact angle meter PCA-1 (manufactured by Kyowa Interface Science Co., Ltd.) or the like.

[Treatment liquid adhesion process]
The treatment liquid adhesion step is a step of adhering the treatment liquid containing a flocculant that aggregates the components of the colored ink composition to the recording medium. The treatment liquid is applied to at least the region to which the colored ink composition is adhered or the region to which the colored ink composition is adhered. By providing the treatment liquid adhesion step, the components of the colored ink composition are likely to aggregate on the surface of the recording medium, and the ink components can be fixed on the recording medium at an early stage. By using the treatment liquid, the color difference caused by the bleeding of ink droplets on the recording medium and causing the density unevenness when the treatment liquid is not used can be suppressed and the color difference can be reduced. Further, by using the treatment liquid, it is possible to minimize heating the recording medium and fixing the ink at an early stage in order to reduce the density unevenness, and as a result, the color difference can be reduced.

However, even when the treatment liquid is used, a color difference may occur. Since the ink droplets agglomerate on the recording medium at an early stage due to the treatment liquid, the landing order of each color differs between the main scans, which has an effect on the color difference. I presume that there is an effect of the difference in. Further, in the case of having a step of heating and drying the treatment liquid adhering to the recording medium, if there is unevenness in the heating temperature depending on the location of the recording medium, the degree of drying of the treatment liquid also becomes uneven depending on the location, and the ink aggregates. It is also speculated that it affects the degree of.

As a method of adhering the treatment liquid, in addition to the method of adhering using the inkjet method as described above, a bar coater, a roll coater, a spray or the like may be used for coating. As the inkjet method, the same method as the method for ejecting the ink composition can be exemplified.

The treatment liquid adhering step may be performed before or after the ink adhering step. When the treatment liquid adhesion step is performed before the ink adhesion step, the ink adhesion step may be performed before the treatment liquid dries, or the ink adhesion step may be performed after the treatment liquid has dried. At this time, the interval from the adhesion of the treatment liquid to the adhesion of the ink composition is preferably within 20 seconds. The recording medium may be heated to dry the adhered treatment liquid before the ink adheres. The surface temperature of the recording medium at the time of adhesion of the treatment liquid and / or from adhesion to ink adhesion may be within the range of the recording medium surface temperature at the time of ink adhesion described above.
Further, when the treatment liquid adhesion step is performed after the ink adhesion step, it is preferable to perform the treatment liquid adhesion step before the ink composition dries.

In the treatment liquid adhering step, there may be a step of drying the treatment liquid adhering to the recording medium. As the drying unit, for example, a platen heater, a hot air heater, an IR heater, etc. having a heating function, a blower having no heating function, and the like are used. The drying temperature can be 70 to 110 ° C.

The recording region to which the colored ink composition and the treatment liquid are adhered preferably has a region in which the amount of the treatment liquid adhered to the adhered amount of the colored ink composition is 5 to 50% by mass, preferably 5 to 40% by mass. It is more preferable to have a region of 5 to 30% by mass. When the amount of adhesion is equal to or more than the above range, uneven density and roughness of the image are improved, and the color difference tends to be further suppressed. Further, when the amount of adhesion is not more than the above range, it is possible to prevent the ink from agglomerating excessively and the image from becoming grainy and the color difference from increasing.
Further, it is also preferable that the adhesion amount of the treatment liquid in the region where the adhesion amount of the treatment liquid is maximum with respect to the adhesion amount of the colored ink composition in the recording region is within the above range.

(Treatment liquid)
The treatment liquid is not particularly limited as long as it contains a flocculant that aggregates the components of the ink composition. If necessary, it may contain water, an organic solvent, an antifoaming agent, and a surfactant. A water-based treatment liquid is preferable. Examples of the components that may be contained in the treatment liquid other than the coagulant include those other than the colorant among the components that may be contained in the above-mentioned colored ink composition, and their types and contents are those of the colored ink composition. Similarly, it can be done independently of the colored ink composition. The treatment liquid is not a composition used for coloring the recording medium. The content of the coloring material in the treatment liquid is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, still more preferably 0.01% by mass or less, and the lower limit is 0.00% by mass. %.

(Coagulant)
The coagulant is not particularly limited as long as it agglomerates the components of the ink composition, and examples thereof include polyvalent metal salts, organic acids or salts thereof, and cationic resins. The flocculant may be used alone or in combination of two or more.

The polyvalent metal salt is not particularly limited, and examples thereof include a polyvalent metal salt of an inorganic acid and a polyvalent metal salt of an organic acid. The polyvalent metal is not particularly limited, but for example, an alkaline earth metal of the second group of the periodic table (for example, magnesium and calcium), a transition metal of the third group of the periodic table (for example, lantern), and a periodic table. Examples include earth metals (eg, aluminum) and lanthanides (eg, neodym) from the 13th genus. Suitable salts of these polyvalent metals include carboxylates (such as formic acid, acetic acid and benzoate), sulfates, nitrates, chlorides and thiocyanates. 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. The polyvalent metal salt may be used alone or in combination of two or more.

The organic acid is not particularly limited, and examples thereof include acetic acid, phosphoric acid, oxalic acid, malonic acid, and citric acid. Of these, monovalent or divalent or higher carboxylic acids are preferable. Further, the organic acid may be in the form of a salt. The organic acid or a salt thereof may be used alone or in combination of two or more. Organic acids or salts thereof that are also polyvalent metal salts shall be included in the polyvalent metal salts.

The cationic resin is not particularly limited, and examples thereof include an amine-based resin. The amine-based resin may be any resin having an amino group in its structure. Examples of the amine-based resin include amine-based resins such as amine / epichlorohydrin condensation polymer, polyallylamine, and polyallylamine derivative. The cationic resin is preferably a resin that is soluble in the treatment liquid, or one that is dispersed in the treatment liquid in the state of a resin emulsion or the like, and the former is more preferable.

The content of the flocculant is preferably 1 to 20% by mass, more preferably 3 to 10% by mass, based on the total amount of the treatment liquid. When the content of the flocculant is within the above range, the recorded material tends to be more excellent in bleeding resistance, filling property, and rubbing resistance.

(water)
The content of water is preferably 55 to 85% by mass, more preferably 60 to 80% by mass, and further preferably 65 to 75% by mass with respect to the total amount of the treatment liquid.

(Organic solvent)
As the organic solvent contained in the treatment liquid, the same ones as those exemplified in the ink composition can be exemplified. The organic solvent may be used alone or in combination of two or more. The content of the organic solvent is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, and further preferably 20 to 30% by mass with respect to the total amount of the treatment liquid.

Further, the treatment liquid may contain a nitrogen-containing solvent as the organic solvent. The content of the nitrogen-containing solvent is preferably 3 to 25% by mass, more preferably 5 to 22% by mass, and further preferably 8 to 20% by mass with respect to the total amount of the treatment liquid. As the nitrogen-containing solvent, a nitrogen-containing solvent which may be contained in the above-mentioned colored ink composition can be used independently of those contained in the colored ink composition.

(Surfactant)
As the surfactant contained in the treatment liquid, the same ones as those exemplified in the ink composition can be exemplified. The content of the surfactant is preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, and still more preferably 0.3 to 1% by mass with respect to the total amount of the treatment liquid. It is 5% by mass. When the content of the surfactant is within the above range, the wettability of the treatment liquid tends to be further improved.

(Defoamer)
As the defoaming agent contained in the treatment liquid, the same ones as those exemplified in the ink composition can be exemplified. The content of the defoaming agent is preferably 0.03 to 0.7% by mass, more preferably 0.05 to 0.5% by mass, and further preferably 0. It is 08 to 0.3% by mass.

[Recording device]
The recording apparatus used in the present embodiment records by the above-mentioned recording method, and may have an inkjet head having a nozzle for ejecting an ink composition to a recording medium and a mechanism for adhering a treatment liquid. There is no particular limitation. A schematic cross-sectional view of the recording device is shown in FIG. As shown in FIG. 1, the recording device 1 includes a recording head 2, an IR heater 3, a platen heater 4, a drying heater 5, a cooling fan 6, a preheater 7, and a fan 8. There is.

The recording head 2 ejects the ink composition to the recording medium. As the recording head 2, a conventionally known method can be used, and a head that ejects droplets by utilizing the vibration of the piezoelectric element, that is, a head that forms ink droplets by mechanical deformation of the electrolytic strain element can be mentioned. The IR heater 3 and the platen heater 4 mainly heat the recording medium 10, but the recording head can also be heated. The IR heater 3 can heat the recording medium from the recording head 2 side. Thereby, if the platen heater 4 is used, the recording medium can be heated from the side opposite to the recording head 2 side. The platen heater 4 may be configured by arranging a plurality of heater elements in the main scanning direction. This is preferable because the platen heater is easily available and easy to manufacture. On the other hand, temperature unevenness in heating in the main scanning direction tends to occur. The drying heater 5 dries the recording medium to which the ink composition is attached. By heating the recording medium on which the image is recorded, the water content contained in the ink composition evaporates and scatters more quickly, and a film is formed by the resin contained in the ink composition. In this way, the dried ink is firmly fixed (adhered) on the recording medium, and a high-quality image having excellent scratch resistance can be obtained in a short time. During recording, the recording medium 10 is conveyed from right to left in the figure.

The recording device 1 may have a cooling fan 6. After drying, the ink composition on the recording medium is cooled by the cooling fan 6, so that a film with good adhesion tends to be formed on the recording medium.

Further, the recording device 1 may include a preheater 7 that preheats (preheats) the recording medium before the ink composition is ejected to the recording medium. By preheating the recording medium before ejecting the ink composition, it tends to be possible to form a high-quality image with less bleeding on the recording medium, particularly the non-absorbent and low-absorbent recording medium.

The recording head 2 is mounted on the carriage 9. The carriage 9 performs scanning (main scanning) in which the ink composition is ejected from the head while moving in the front-back direction of the figure and adhered to the recording medium on which the head faces. Recording is performed by alternately and repeatedly scanning and transporting (sub-scanning) the recording medium 10. That is, a serial recording method is performed in which recording is performed by performing scanning a plurality of times.

FIG. 3 is a perspective view showing an example of the configuration around the carriage of the recording device of FIG. The configuration 11 around the carriage includes a carriage 9, an inkjet head 2 mounted on the carriage 9, a member 12 that is a part of the inkjet head 2 and includes a nozzle for ejecting ink, an ink container (not shown), and an ink container (not shown). It has an ink supply path (not shown) such as an ink supply tube that supplies ink from the ink container to the inkjet head 2. The ink container may be provided in a place other than the carriage 9 or may be provided in the carriage. Further, the platen 4 which is arranged below the carriage 9 and conveys the recording medium 10, the carriage moving mechanism 13 which moves the carriage 9 relative to the recording medium 10, and the recording medium 10 in the sub-scanning direction (conveyance). A transport means 14 which is a roller for transporting in the direction) and a control unit CONT for controlling the operation of the carriage 9 and the like are provided. The direction of S1-S2 is the main scanning direction, and the direction of T1 → T2 is the sub-scanning direction. Note that scanning is performed in either one of the main scanning directions (left-right direction of the device) in one scan.

Further, the recording device 1 of FIG. 1 includes a fan 8 for sending wind to the surface of the recording medium from the viewpoint of efficient drying of the ink composition and the viewpoint of adjusting the temperature of the recording medium and the nozzle surface. In order to explain the fan 8 in more detail, it will be described with reference to FIG. Also in FIG. 2, the recording head 2 is mounted on the carriage, and the ink composition is ejected from the head while moving in the main scanning direction, which is the front-back direction in the figure, to perform the main scanning. 2A and 2B show a state in which wind is flowing through a recording medium in a place where there is no carriage in the main scanning direction (front-back direction in the figure) in the main scanning of the carriage, and FIG. 2A and a place where the carriage is present. FIG. 2B shows a state in which the wind does not flow directly to the recording medium.

A plurality of fans 8 are provided side by side in the width direction (main scanning direction) of the recording medium 10, and are provided so that the wind can always be sent in a band shape from one end to the other of the width of the recording medium 10. ing. In FIG. 2A, the wind hits the surface of the recording medium 10. Since the hit angle is tilted to the left in the figure with respect to the surface of the recording medium, the direction of the wind changes to the left in the figure after hitting, and the wind blows to the recording medium in the region where the ink of the recording medium adheres. It is sent to the downstream side in the recording medium transport direction in parallel with the surface of the recording medium. By doing so, it is possible to accelerate the drying of the ink in the region to which the ink of the recording medium is attached.

FIG. 4 is a view of the fan 8 of FIG. 2 as viewed from the front of the fan. As shown in the figure, a plurality of fans 8 are provided side by side in the width direction of the recording medium.

On the other hand, in FIG. 2B, the wind hits the windbreak member provided on the upper part of the carriage, separates in the left-right direction in the figure and changes its direction, and does not directly hit the surface of the recording medium. By doing so, it is possible to reduce the influence of clogging and landing position shift caused by the wind from the nozzle and the ink droplets in flight in the place where the carriage is located.

However, in FIG. 2A, the direction of the wind sent parallel to the surface of the recording medium may fluctuate slightly, and even in the place where the carriage is located, the wind blows from the side to the recording head 2 to the landing position. There is an influence of. Further, in FIG. 2B, the wind that hits the windbreak member and has its direction changed may flow in an unintended direction, and the same effect may occur to some extent.

It should be noted that the fan 8 in FIG. 2 shows one aspect of the sending means for sending wind on the recording medium, and the blowing means is not limited to this as long as the wind can be sent to the recording medium. do not have. As another aspect, a mode in which the air blower is directed sideways on the upper layer of the recording medium and a mode in which the wind is blown from above to the ink adhesion region on the surface of the recording medium can be considered.

(Number of scans)
The number of scans is also called the number of passes. The number of scans in which the nozzle group used for recording a certain ink composition passes against a certain position to be recorded on the recording medium is referred to as the number of scans of the ink composition. The nozzle group is a group of nozzles such as a row of nozzles arranged in the sub-scanning direction of the inkjet head, and ejects the ink composition at the time of recording. The number of main scans can be increased by shortening the distance of one sub-scan, and can be reduced by increasing the distance. For example, the number of scans can be set to 8 (pass) by setting the distance of one sub-scan to 1/8 of the length of the nozzle group in the sub-scan direction. The number of scans is 1 or more, preferably 2 to 20, more preferably 4 to 10. It is preferable that the number of main scans is large because the total amount of the ink composition to be adhered can be increased and the ink composition can be adhered separately by a plurality of scans. On the other hand, when the number of scans is small, the recording speed is high, which is preferable.

(Other embodiments)
Other embodiments of the present invention are as follows.
A colored ink composition containing a cyan ink composition, a magenta ink composition, a yellow ink composition, and a special color ink composition having a hue angle different from that of each of the ink compositions is ejected from an inkjet head and recorded. Ink adhesion process to adhere to the medium and
A treatment liquid adhering step of adhering a treatment liquid containing a flocculant that agglomerates the components of the colored ink composition to the recording medium is provided.
The ink adhesion step is performed by performing scanning for ejecting the colored ink composition a plurality of times while changing the position of the inkjet head relative to the recording medium in the scanning direction.
A recording method in which the difference in surface temperature of the recording medium when the colored ink is adhered in the ink adhesion step is 1 to 10 ° C.

The other embodiment does not necessarily have a maximum distance of 50 cm or more in one scan in the ink adhering step of the above-described embodiment, and instead, a recording medium for adhering colored ink in the ink adhering step. It is provided that the difference in surface temperature is 1 to 10 ° C. In the other embodiment, it is noted that the difference in the surface temperature of the recording medium occurs as one of the causes of the color difference of the recorded matter in the ink adhesion step as described above. According to the embodiment, even when the difference in surface temperature of the recording medium is within a predetermined range, reduction of density unevenness, reduction of color difference, and the like are excellent and preferable. The difference in surface temperature of the recording medium is more preferably in the above range. The other embodiment may be the same as the above-described embodiment except for the above-mentioned configuration, and may further include the other configuration of the above-mentioned embodiment.

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.
[Material for ink composition]
The main materials of the ink composition and the treatment liquid used in the following Examples, Comparative Examples, and Reference Examples are as follows.
[Pigment dispersion]
See Production Example 1 below.
〔Organic solvent〕
Dipropylene Glycol Dimethyl Ether Propylene Glycol 2-Pyrrolidone [Coagulant]
Calcium acetate monohydrate Acetic acid Catiomaster PD-7 (manufactured by Yokkaichi Synthetic Co., Ltd., cationic resin: amine / epichlorohydrin condensed polymer)
〔resin〕
St-Ac resin emulsion (see Production Example 2 below)
〔wax〕
AQUACER515 (Wax emulsion manufactured by Big Chemie Japan)
[Surfactant]
Dynol 607 (Acetylene diol-based surfactant manufactured by Air Products Japan Co., Ltd.)
BYK348 (Silicone-based surfactant manufactured by Big Chemie Japan)
[Defoamer]
Surfinol DF110D (manufactured by Nissin Chemical Industry Co., Ltd., acetylene diol type)

[Production Example 1: Preparation of Pigment Dispersion Liquid]
St-Ac acid copolymer (copolymerized at a mass ratio of methacrylic acid / butyl acrylate / styrene / hydroxyethyl acrylate = 25/50/15/10. Weight average molecular weight 7000, acid value 150 mgKOH / g) 40 parts by mass Was put into a mixed solution of 7 parts by mass of potassium hydroxide, 23 parts by mass of water, and 30 parts by mass of triethylene glycol-mono-n-butyl ether, and heated at 80 ° C. with stirring to prepare a resin aqueous solution.

20 parts by mass of the pigment, 10 parts by mass of the aqueous resin solution, 10 parts by mass of diethylene glycol, and 60 parts by mass of the ion-exchanged water were mixed and dispersed using a zirconium bead mill to obtain a pigment dispersion liquid of each color. The pigments used are as follows.
Cyan pigment dispersion; C.I. I. PigmentB1ue15: 3
Magenta pigment dispersion; C.I. I. PR122
Yellow pigment dispersion; C.I. I. PY74
Orange pigment dispersion; C.I. I. PO43
Red pigment dispersion; C.I. I. PR178
Green pigment dispersion; C.I. I. PG7
Blue pigment dispersion; C.I. I. PB60
Black pigment dispersion C. I. PBk7

[Production Example 2: Preparation of St-Ac resin emulsion]
An St-Ac resin emulsion was obtained by emulsifying and copolymerizing 75 parts by mass of styrene, 0.5 parts by mass of acrylic acid, 14.5 parts by mass of methyl methacrylate, and 10 parts by mass of cyclohexyl methacrylate. As the emulsion polymerization surfactant, Neucol NT-30 (manufactured by Nippon Emulsifying Co., Ltd.) was used, and the amount used was 2 parts by mass with the total amount of the monomers being 100 parts by mass.

[Preparation of ink composition and treatment liquid]
Each material was mixed with the composition shown in Tables 1 and 2 below and sufficiently stirred to obtain each ink composition and treatment liquid. In Tables 1 and 2 below, the unit of the numerical value is mass%, and the total is 100.0 mass%. The pigment and the resin in the table are the mass% of the solid content of the pigment and the resin in the ink.

A recording pattern was recorded with an adhesion amount of 10 mg / inch ² with one ink for each ink 1 to 8, the pattern was measured, and the hue angle was obtained from the color measurement value. The formula for calculating the hue angle is as follows. Inks 1 to 8 had different hue angles from each other. Further, it was within the range of the preferable hue angle for each of the above-mentioned color inks.
∠H ° = tan-1 (b ^* / a ^* ) +180 (when a ^* <0)
∠H ° = tan-1 (b ^* / a ^* ) +360 (when a ^* > 0)

[Recording method]
A modified machine of SC-S80650 (manufactured by Seiko Epson Corporation) having a platen heater in which heater elements are arranged side by side in the width direction of the media and a fan arranged in the width direction of the recording medium on the head (hereinafter, "SC-S80650 modified machine"). ".) Was prepared. The inkjet head is a serial type as shown in FIG. 1, and ink and the like can be recorded in order from the inkjet head. In addition, a normal temperature (25 ° C.) wind was blown from above toward the recording medium by a fan.

The above treatment liquid was filled in a nozzle row (360 nozzles) upstream in the recording medium transport direction of the inkjet head, and each ink composition was filled in the nozzle row downstream in the recording medium transport direction of the inkjet head. Then, by the inkjet method, the treatment liquid was ejected from the inkjet head and adhered to a recording medium (JetFlex FL 80 manufactured by Ultraflex), and then the ink composition was ejected and adhered to the recording medium.

The amount of the reaction solution adhered in the table was set to mass% with respect to the total amount of the ink composition adhered. Further, the mass of the treated droplet and the mass of the ink droplet were set to 20 ng / dot each, the basic resolution was set to 720 × 720 dpi, and the dot density was adjusted so that each adhered amount could be adjusted. The number of scans for each composition was set to 8 passes. Finally, the recorded material was heated at 95 ° C. for 30 seconds with a secondary heater located downstream of the inkjet head to dry it.

Under the above recording conditions, a solid pattern for color difference evaluation is recorded.
First, the amount of adhesion of the basic color and the special color ink for recording the solid pattern of any of the recording colors to be recorded for each example is adjusted and determined. The following are the target colors for each color solid pattern.
Red solid pattern (L ^* 50, a ^* = 40, b ^* = 10, ∠H ° = 14)
Orange solid pattern (L ^* 50, a ^* = 30, b ^* = 30, ∠H ° = 45)
Blue solid pattern (L ^* 50, a ^* = 40, b ^* = -40, ∠H ° = 315)
Green solid pattern (L ^* 50, a ^* = -40, b ^* = 10, ∠H ° = 166)

When determining the amount of ink adhered, a solid test pattern is recorded on the above recording medium and the color is measured. For color measurement, Spectrolino manufactured by GretagMacbeth was used. The color measurement is based on the CIELAB color system. The amount of ink adhered is adjusted and determined so that the hue angle (∠H °) of the color measurement value becomes the value of the above target color.
In this way, the amount of adhesion of each ink used for recording each color solid pattern was determined for each example.
Reference Example 3 is a cyan-colored pattern obtained by recording with cyan ink alone, and the adhesion amount was 10 mg / inch ² .

A solid pattern for color difference evaluation was continuously recorded under the above-mentioned recording conditions with the above-determined ink adhesion amount to prepare a recorded matter. The solid pattern was recorded in the entire recordable range in the width direction of the medium and with a length of 1500 mm in the media feed direction. The width of the recording medium was adjusted by cutting or pasting the recording medium, and the maximum distance of one scan was adjusted to the values in Tables 3 to 4.
The types of ink compositions used are as shown in Tables 3-4.

In the above recording method, the platen heater was controlled so that the surface temperature of the recording medium in the platen region facing the head during recording was the heating temperature in Tables 3 to 4. Specifically, when the surface temperature is 35 ° C or higher, the platen heater is turned on for adjustment, and when the surface temperature is 25 ° C or lower, the room temperature is adjusted without using the platen heater and recording is performed. The surface temperature of the medium was adjusted.

The surface temperature of the recording medium is the highest during recording on the surface of the recording medium in the area where the temperature is measured at 1 cm square intervals over the entire area that can be opposed during the main scan of the head of the recording medium supported by the platen. The temperature was set. The measurement was performed with a non-contact thermometer. The temperature was continuously recorded for 1 hour under the above-mentioned conditions, and the measurement was started 1 minute after the start of recording and measured every 1 minute during recording.

[Color difference evaluation]
The solid pattern of the obtained recorded material was divided into 2 × 2 cm square regions, and the colors were measured for each region to obtain the largest color difference (ΔE00) between the regions. The occurrence of color difference was evaluated according to the following evaluation criteria. The maximum color difference between regions.
A: The maximum color difference between regions is ΔE ≦ 1.0
B: Maximum color difference between regions is 1.0 <ΔE ≦ 1.5
C: Maximum color difference between regions is 1.5 <ΔE ≦ 2.0
D: Maximum color difference between regions is 2.0 <ΔE

[Abrasion resistance]
The recording area of the obtained recorded material is cut into a rectangle of 30 x 150 mm, and a plain weave cloth is attached to the Gakushin type friction fastness tester AB-301 (trade name manufactured by Tester Sangyo Co., Ltd.) with a load of 500 g. And rubbed 10 times. Then, the peeling of the recording pattern portion of the recording medium was visually observed and evaluated according to the following evaluation criteria.
A: No peeling occurs and no transfer to cloth.
B: No peeling occurs, but there is transfer to the cloth.
C: Peeling occurs, and the peeled area is less than 10% of the evaluated area.
D: Peeling occurs, and the peeled area is 10% or more of the evaluated area.

[Water resistance]
The recording area of the obtained recorded material was cut into a rectangle of 30 x 150 mm, and the friction fastness tester AB-301 (trade name manufactured by Tester Sangyo Co., Ltd.) was attached with a plain weave cloth soaked in water. The child rubbed 10 times with a load of 200 g. Then, the peeling of the recording pattern portion of the recording medium was visually observed and evaluated according to the following evaluation criteria.
A: No peeling occurs and no transfer to cloth.
B: No peeling occurs, but there is transfer to the cloth.
C: Peeling occurs, and the peeled area is less than 10% of the evaluated area.
D: Peeling occurs, and the peeled area is 10% or more of the evaluated area.

[Evaluation of image quality roughness]
The recording area of the obtained recorded material was visually confirmed and evaluated according to the following evaluation criteria.
A: No roughness at all B: I'm worried about the roughness, but there is no problem C: There is a roughness

[Concentration unevenness (bleed)]
The recording area of the obtained recorded material was visually confirmed and evaluated according to the following evaluation criteria.
A: There is no unevenness of light and shade in the solid pattern surface.
B: There is some fine unevenness in the solid pattern surface.
C: Large unevenness of light and shade is conspicuous in the solid pattern surface.

From the above results, all of the examples in which the maximum distance of one scan is 50 cm or more using cyan ink, magenta ink, yellow ink, special color ink, and processing liquid are excellent in suppressing the color difference of the obtained recorded matter. I understood.
On the other hand, the color difference suppression was inferior in all of the comparative examples that did not. It will be described in detail below.

From the comparison of Examples 7 to 10 and 4, when the surface temperature of the recording medium at the time of ink adhesion is low, the friction resistance and water friction resistance of the obtained recorded material, and the suppression of roughness and density unevenness are relatively lowered. I understand. In addition, it is presumed that the suppression of color difference also decreased slightly probably because the suppression of density unevenness decreased.
On the other hand, it can be seen that the higher the surface temperature of the recording medium, the better the abrasion resistance and the water friction resistance, the roughness and the density unevenness of the obtained recorded matter, but the color difference is relatively reduced. From this, when the heating temperature of the recording medium at the time of adhesion is optimized, it is possible to further suppress the density unevenness and the color difference.

From the comparison of Examples 11 to 13, 17 and 4, it can be seen that the longer the maximum distance of one scan, the more likely the color difference is to occur, and the shorter the maximum distance of one scan, the less likely it is to occur. From this, the present embodiment is particularly useful in that excellent color difference suppression can be achieved even when a recorded material having a long distance and useful for display or the like can be obtained.

From the comparison of Examples 15, 16 and 4, the color difference suppression was slightly inferior regardless of whether the amount of the treatment liquid adhered was large or small. It is presumed that when the amount of the treatment liquid adhered was small, the suppression of density unevenness was slightly inferior, and the suppression of color difference was slightly reduced due to the density unevenness. On the other hand, when the amount of the treatment liquid adhered is large, the aggregation of the ink components is promoted, so that the scratch resistance tends to be slightly lowered and the image quality tends to be slightly increased. It is presumed that the color difference tends to increase due to the roughness of the image quality. It was found that there was a more preferable amount of adhesion of the treatment liquid.

From the comparison of Examples 14 and 4, it was found that the larger the content of the nitrogen-containing solvent in the ink, the better the color difference suppression.

On the other hand, in Comparative Examples 1 to 8, the color difference suppression was inferior because the special color ink was not used.
Further, in Reference Examples 1 and 2, since the problem of color difference does not occur when the maximum distance of one scan is short, the problem of color difference is a problem peculiar to the case where the maximum distance of one scan is long. It can be seen that it is. However, it could not be used as a useful record for display.
From Reference Example 3, it was found that the occurrence of color difference does not matter if the primary color is recorded.
In Reference Example 4, the image quality (concentration unevenness) was inferior because the treatment liquid was not used. The components of the ink were aggregated by the treatment liquid and could not be fixed at an early stage, and the ink bleeded, causing uneven density. The image looked grainy due to uneven shading. It is presumed that the recorded color to be recorded could not be reproduced stably due to the uneven density, and the color difference suppression was also reduced.
In Reference Example 5, the suppression of density unevenness was improved by raising the temperature of the recording medium at the time of ink adhesion, but the heating temperature at the time of ink adhesion was high, the temperature unevenness was large, and the color difference was deteriorated.
Although not described in the table, it was found that ink 9 (black ink with lower brightness and lower saturation can be recorded by adding black ink) to the ink set of each example.

In Example 12, the temperature difference between the maximum temperature (temperature in the table) and the minimum temperature of the surface temperature of the platen region that can face the head by the main scanning of the head during recording was confirmed. ° C., Example 13 was 6 ° C., Example 11 was 1 ° C., Example 17 was 2 ° C., Example 10 was 10 ° C., and Reference Example 1 was less than 1 ° C. .. From this, it was found that the larger the maximum distance of one scan, the larger the temperature difference is likely to be. Further, the higher the surface temperature of the recording medium, the larger the temperature difference tended to be.

Although not described in the table, in Example 12, the heating temperature of the platen heater was raised, the wind force of the wind blown from the fan was raised from 1 m / s to 2 m / s, and the platen heater was used for heating. When the surface temperature of the recording medium at the time of recording was controlled to 35 ° C., which is the same as in Example 12, by utilizing the fact that the temperature of the recording medium is lowered by the wind, it is difficult to reduce the temperature difference between the maximum temperature and the minimum temperature. The temperature difference was 6 ° C., and the color difference evaluation was C. From this, it was found that a large temperature difference in the recording medium is at least one of the causes of the color difference.

In the above-mentioned other embodiments, the above-mentioned embodiment may be a comparative example or the comparative example may be a comparative example.

1 ... Recording device, 2 ... Recording head, 3 ... IR heater, 4 ... Platen heater, 5 ... Drying heater, 6 ... Cooling fan, 7 ... Preheater, 8 ... Fan, 9 ... Carriage, 10 ... Recording medium, 11 ... Configuration around the carriage, 12 ... Members including nozzles, 13 ... Carriage moving mechanism, 14 ... Transport means

Claims (14)

A heating process that heats the recording medium with a heating mechanism,
A colored ink composition containing a cyan ink composition, a magenta ink composition, a yellow ink composition, and a special color ink composition having a hue angle different from that of each ink composition is ejected from an inkjet head to obtain the above -mentioned ink composition. An ink adhesion step of adhering to the recording medium heated by the heating step, and
A treatment liquid adhering step of adhering a treatment liquid containing a flocculant that agglomerates the components of the colored ink composition to the recording medium is provided.
The ink adhesion step is performed by performing scanning for ejecting the colored ink composition a plurality of times while changing the position of the inkjet head relative to the recording medium in the scanning direction.
The maximum distance of one scan in the ink adhesion step is 50 cm or more .
The recording medium is a low-absorbency recording medium or a non-absorbent recording medium.
The flocculant contains a polyvalent metal salt and contains
The colored ink composition is a water-based ink composition .
Recording method. The spot color ink composition comprises at least one of an orange ink composition, a red ink composition, a green ink composition, and a blue ink composition.
The recording method according to claim 1. The colored ink composition further comprises a black ink composition.
The recording method according to claim 1 or 2. The low-absorbency recording medium is coated paper.
The non-absorbent recording medium is either a plastic film or plate, or a metal plate .
The recording method according to any one of claims 1 to 3. The ink adhering step comprises a blowing step of blowing air to a region to which the colored ink composition is adhered.
The recording method according to any one of claims 1 to 4. In the heating step, the surface temperature of the recording medium heated by the heating mechanism is 30 to 45 ° C.
The recording method according to any one of claims 1 to 5. The maximum time of one scan in the ink adhesion step is 0.8 seconds or more.
The recording method according to any one of claims 1 to 6. The polyvalent metal salt is at least one of a calcium salt and a magnesium salt .
The recording method according to any one of claims 1 to 7. The maximum distance of one scan in the ink adhesion step is 50 to 500 cm.
The recording method according to any one of claims 1 to 8. The recording region to which the colored ink composition and the treatment liquid are adhered has a region in which the adhesion amount of the treatment liquid is 5 to 30% by mass with respect to the adhesion amount of the colored ink composition.
The recording method according to any one of claims 1 to 9. The temperature difference between the maximum temperature and the minimum temperature of the total surface temperature of the regions that can face each other during the main scanning of the head of the recording medium in the ink adhesion step is 1 to 10 ° C.
The recording method according to any one of claims 1 to 10. In the colored ink composition, the content of the organic solvent having a standard boiling point of more than 280 ° C. is 1% by mass or less.
The recording method according to any one of claims 1 to 11. In the ventilation step, the temperature of the ventilation is 30 ° C. or lower.
The recording method according to claim 5. A recording device for recording by the recording method according to any one of claims 1 to 13 .

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