JP2013193338A - Recording method and recorded matter - Google Patents

Abstract

An object of the present invention is to provide a recording method capable of recording a glittering image which is excellent in glittering property and excellent in abrasion resistance, water resistance and light resistance.
A recording method according to the present invention is a recording method using an ink jet recording apparatus, in which droplets of glittering ink containing a glittering pigment are ejected onto a recording medium, and 0 on the recording medium. a first step of forming a bright image containing .10mg / inch ² or more 0.50 mg / inch ² or less of the light bright pigment, droplets of substantially free resin ink colorant containing resin A second step of discharging and forming a resin film on the glitter image, the amount of the glitter pigment contained in the glitter image [W _A (mg / inch ² )], and the resin The ratio (W _B / W _A ) to the amount [W _B (mg / inch ² )] of the resin contained in the film is 0.063 or more and 2.9 or less.
[Selection] Figure 1

Description

  The present invention relates to a recording method and a recorded matter obtained thereby.

  Conventionally, various methods for recording an image on a recording medium are known. For example, in an ink jet recording method, an image is recorded on a recording medium with fine ink droplets ejected from nozzles of an ink jet recording head.

  An image recorded on a recording medium is required to have good gloss from the viewpoints of clarity and clarity. For example, Patent Document 1 uses an ink containing a colorant and an ink not containing a colorant to print ink that does not contain a colorant only at a position where no ink containing the colorant exists on the recording medium. It is described that an image having uniform glossiness can be recorded on a recording medium.

  In recent years, among these properties of glossiness, an image having a glitter property caused by the gloss of a metal or the like has been attracting attention because it has a unique design property. For example, Patent Document 2 discloses that a glitter image is formed using a glitter ink containing a glitter pigment (for example, gold powder or silver powder prepared from brass, aluminum fine particles, or the like).

  Patent Document 3 describes that an image having a metallic luster is formed with an ink containing a bright pigment such as a metal pigment, and the image is protected with a colorless and transparent ink.

JP 2005-532924 A JP 2008-174712 A JP 2010-18651 A

  However, even if the glittering image is covered with ink that does not contain a colorant to protect the glittering image, the glittering effect of the image is reduced, or the protective effect of the image (for example, abrasion resistance, water resistance, light resistance) In some cases). Specifically, when the protective effect of the glitter image by the ink not containing the colorant is improved, the ink not containing the colorant reduces the glitter of the glitter image. On the other hand, if the use of ink that does not contain a colorant is refrained in order to maintain the glitter of the glitter image, the protective effect of the glitter image is reduced. Thus, it has been difficult to improve the protective effect of the glitter image while maintaining the glitter of the glitter image.

  One of the objects according to some embodiments of the present invention is to solve at least a part of the above-mentioned problems, thereby producing a glitter image having excellent glitter and excellent abrasion resistance, water resistance and light resistance. An object is to provide a recording method capable of recording, and a recorded matter obtained thereby.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1]
One aspect of the recording method according to the present invention is:
A recording method using an ink jet recording apparatus,
A droplet of glitter ink containing the glitter pigment is ejected onto a recording medium, and a glitter image containing the glitter pigment of 0.10 mg / inch ² or more and 0.50 mg / inch ² or less is formed on the recording medium. A first step of forming;
A second step of forming a resin film on the glitter image by discharging resin ink droplets containing a resin and substantially no colorant;
Including
The amount of the bright pigment contained in the glitter image ^{_{[W A (mg / inch 2}} )] and the amount of the resin contained in the resin film ^{_{[W B (mg / inch 2}} )] ratio of (W _B / W _A ) is 0.063 or more and 2.9 or less.

  According to the aspect described in Application Example 1, it is possible to record a glitter image having excellent glitter and excellent abrasion resistance, water resistance, and light resistance.

[Application Example 2]
In application example 1,
Ratio (D _B /%) of Duty [D _A (%)] of the glitter ink ejected in the first step and Duty [D _B (%)] of the resin ink ejected in the second step D _A ) can be 0.60 or more and 1.3 or less.

[Application Example 3]
In application example 1 or application example 2,
The horizontal diameter when the glitter ink droplets fly may be not less than 0.79 times and not more than 1.26 times the horizontal diameter when the resin ink droplets fly.

[Application Example 4]
In any one of Application Examples 1 to 3,
The ink jet recording apparatus includes a head including a nozzle row including a plurality of nozzle openings, and a carriage that scans the head in the main scanning direction.
The nozzle row includes a first nozzle row in which a plurality of nozzle openings for discharging the glitter ink droplets are arranged in a sub-scanning direction intersecting the main scanning direction, and a nozzle for discharging the resin ink. A second nozzle row in which a plurality of the nozzle openings are arranged in the sub-scanning direction,
The first nozzle row and the second nozzle row are divided and used for each group including a predetermined number of the nozzle openings in the sub-scanning direction.
The group includes a first group on the upstream side in the sub-scanning direction, and a second group on the downstream side in the sub-scanning direction with respect to the first group,
The first step is performed by discharging droplets of the glitter pigment from the first group of the first nozzle row,
The second step may be performed by discharging droplets of the resin ink from the second group of the second nozzle row.

[Application Example 5]
In any one of Application Examples 1 to 4,
The resin may be at least one selected from a urethane resin, an ester resin, and a fluorene resin.

[Application Example 6]
In any one of Application Examples 1 to 5,
Furthermore, it is possible to include a third step of discharging a colored ink containing a colorant to form a colored image on the resin film.

[Application Example 7]
In Application Example 6,
Ratio of the amount [W _A (mg / inch ² )] of the glitter pigment contained in the glitter image and the amount [W _C (mg / inch ² )] of the colorant contained in the colored image ( W _C / W _A ) can be 3.4 or less.

[Application Example 8]
In Application Example 6 or Application Example 7,
The ink jet recording apparatus includes a head including a nozzle row including a plurality of nozzle openings, and a carriage that scans the head in the main scanning direction.
The nozzle row includes a first nozzle row in which a plurality of nozzle openings for discharging the glitter ink droplets are arranged in a sub-scanning direction intersecting the main scanning direction, and a nozzle for discharging the resin ink. A second nozzle row in which a plurality of the nozzle openings are arranged in the sub-scanning direction; and a third nozzle row in which a plurality of the nozzle openings for discharging the colored ink are arranged in the sub-scanning direction;
The first nozzle row, the second nozzle row, and the third nozzle row are divided and used for each group including a predetermined number of the nozzle openings in the sub-scanning direction.
The group includes a first group on the upstream side in the sub-scanning direction, a second group on the downstream side in the sub-scanning direction with respect to the first group, and a downstream side in the sub-scanning direction with respect to the second group. A third group on the side,
The first step is performed by discharging droplets of the glitter pigment from the first group of the first nozzle row,
The second step is performed by discharging droplets of the resin ink from the second group of the second nozzle row,
The third step may be performed by discharging the colored ink droplets from the third group of the third nozzle row.

[Application Example 9]
One aspect of the recorded matter according to the present invention is:
This is obtained by the recording method described in any one of Application Examples 1 to 8.

FIG. 3 is a perspective view illustrating a configuration of a printer used in the recording method according to the embodiment of the invention. FIG. 2 is a schematic diagram illustrating a nozzle surface of a printer used in a recording method according to an embodiment of the invention.

  Hereinafter, preferred embodiments of the present invention will be described. Embodiment described below demonstrates an example of this invention. In addition, the present invention is not limited to the following embodiments, and includes various modifications that are implemented within a range that does not change the gist of the present invention. Note that not all of the configurations described in the following embodiments are indispensable constituent requirements of the present invention.

1. Recording Method A recording method according to an embodiment of the present invention is a recording method using an ink jet recording apparatus, and ejects a droplet of glitter ink containing a glitter pigment onto a recording medium. A first step of forming a glitter image containing the glitter pigment in an amount of from 0.10 mg / inch ^{2 to} 0.50 mg / inch ² and a resin ink liquid containing a resin and substantially free of a colorant A second step of discharging a droplet to form a resin film on the glitter image, and the amount of the glitter pigment contained per unit area of the glitter image [W _A (mg / inch ² )] And the amount [W _B (mg / inch ² )] of the resin contained per unit area of the resin film (W _B / W _A ) is 0.063 or more and 2.9 or less. .

1.1. Apparatus Configuration First, an ink jet recording apparatus (hereinafter, also simply referred to as “ink jet recording apparatus”) that can be used in the recording method according to the present embodiment will be described with reference to FIGS. In each drawing used for the following description, the scale of each member is appropriately changed to make each member a recognizable size. In the present embodiment, an inkjet printer (hereinafter simply referred to as “printer”) is illustrated as an inkjet recording apparatus. The present invention is not limited to this apparatus configuration.

  FIG. 1 is a perspective view illustrating a configuration of a printer 1 according to the present embodiment. A printer 1 shown in FIG. 1 is a serial printer. A serial printer is a printer in which a head is mounted on a carriage that moves in a predetermined direction, and droplets are ejected onto a recording medium by moving the head as the carriage moves.

  As shown in FIG. 1, the printer 1 includes a carriage 4 on which a head 2 is mounted and an ink cartridge 3 is detachably mounted, a platen 5 that is disposed below the head 2 and transports a recording medium P, and a carriage. 4 includes a carriage moving mechanism 7 that moves the recording medium P in the medium width direction of the recording medium P, and a medium feeding mechanism 8 that conveys the recording medium P in the medium feeding direction. Further, the printer 1 has a control unit CONT that controls the operation of the entire printer 1. The medium width direction is the main scanning direction (head scanning direction). The medium feeding direction is a sub-scanning direction (a direction orthogonal to the main scanning direction).

  The control unit CONT can perform execution operations such as controlling the execution timing of each operation of the carriage 4, the head 2, the carriage moving mechanism 7, the medium feeding mechanism 8, and the like, or linking them.

  The head 2 discharges ink from the nozzle opening 17 in the form of droplets having a minute particle size, and adheres the ink onto the recording medium P. The head 2 is not particularly limited as long as it has the above function, and any ink jet recording method may be used. As the ink jet recording system of the head 2, for example, a strong electric field is applied between the nozzle and the acceleration electrode placed in front of the nozzle, and droplet ink is continuously ejected from the nozzle to deflect the ink droplet. A method in which a printing information signal is applied to a polarizing electrode while flying between the electrodes and recording is performed, or a method in which ink droplets are ejected in accordance with the printing information signal without being deflected (electrostatic suction method). Pressure is applied to the liquid, and the nozzle is mechanically vibrated by a quartz oscillator or the like to forcibly eject ink droplets. The pressure and print information signal are simultaneously applied to the ink using a piezoelectric element. Examples include a method for ejecting and recording droplets (piezo method), a method for heating and foaming ink with a microelectrode in accordance with a print information signal, and a method for ejecting and recording ink droplets (thermal jet method). That.

  FIG. 2 is a schematic view showing the nozzle surface 15 of the head 2 according to the present embodiment. As shown in FIG. 2, the head 2 includes a nozzle surface 15. A plurality of nozzle rows 16 are arranged on the nozzle surface 15 which is also an ink ejection surface. The plurality of nozzle rows 16 have a plurality of nozzle openings 17 for ejecting ink for each nozzle row.

  The plurality of nozzle rows 16 can discharge, for example, inks having different compositions for each nozzle row. In the example of FIG. 2, three nozzle rows are provided corresponding to the ink composition, and each nozzle row is arranged along the main scanning direction. Specifically, it includes a nozzle row 16A capable of ejecting glitter ink described later, a nozzle row 16B capable of ejecting resin ink described later, and a nozzle row 16C capable of ejecting colored ink described later. In the example of FIG. 2, the case where there are three nozzle rows has been shown, but the present invention is not limited to this, and four or more nozzle rows may be provided.

  In the example of FIG. 2, each of the nozzle rows 16 </ b> A to 16 </ b> C extends in the sub-scanning direction intersecting the main scanning direction on the nozzle surface 15, but is not limited thereto, and the main scanning is performed in the nozzle surface 15. You may arrange | position with the angle given to the direction which cross | intersects with a direction.

  A plurality of nozzle openings 17 are arranged in a predetermined pattern to form a nozzle row. In the present embodiment, a plurality of nozzle openings 17 are arranged in the sub-scanning direction on the nozzle surface 15. However, the present invention is not limited to this, and for example, along the direction orthogonal to the main scanning direction on the nozzle surface 15. They may be arranged in a zigzag shape. The number of nozzle openings 17 constituting the nozzle row is not particularly limited.

  The plurality of nozzle rows 16 can be divided into a plurality of regions including a predetermined number of nozzle openings 17 in the sub-scanning direction. In the example of FIG. 2, the nozzle rows 16 </ b> A to 16 </ b> C include the first group on the upstream side T <b> 1 in the sub-scanning direction, the second group on the downstream side T <b> 2 in the sub-scanning direction with respect to the first group, and the second group. And a third group on the downstream side T2 in the sub-scanning direction further than the group. Note that the number of nozzle openings 17 constituting one group is not particularly limited. Further, the number of nozzle openings 17 constituting the group may be the same or different for each group. Further, the nozzle row may be divided into four or more.

  As described above, the description has focused on the serial head type printer (recording apparatus), but the present invention is not limited to this mode. Specifically, a line head type printer in which recording heads are fixed and arranged in order in the sub-scanning direction, X direction and Y direction (main scanning direction, sub-scanning direction as described in JP-A-2002-225255). It may be a lateral type printer provided with a head (carriage) provided with a mechanism after moving in the scanning direction). For example, Surepress L-4033A (manufactured by Seiko Epson Corporation) is a lateral type printer.

  Among these, it is preferable to use a recording apparatus that records an image by dividing a nozzle row of a serial head, which will be described later, or a lateral type recording apparatus. By using these, when an ink set of glitter ink and resin ink is used, after the glitter image is satisfactorily formed with the glitter ink ejected earlier, the glitter image is ejected later. It becomes easy to coat with the resin ink.

  Similarly, when an ink set of glitter ink, resin ink, and colored ink is used, after the glitter image is satisfactorily formed with the glitter ink ejected first, the glitter image is ejected later. It is possible to easily form a colored image on the glittering image coated with the resin ink by the colored ink that is coated with the resin ink and then discharged with the colored ink.

1.2. Recording Method The recording method according to the present embodiment includes a first step of forming a glitter image and a second step of forming a resin film using the above-described ink jet recording apparatus. Hereinafter, each step will be described in detail. In the present invention, “image” refers to a printing pattern formed from a group of dots (droplets), and includes text printing and solid printing.

1.2.1. First Step In the first step, a droplet of glitter ink containing a glitter pigment is ejected onto a recording medium, and a glitter of 0.10 mg / inch ² or more and 0.50 mg / inch ² or less is applied to the recording medium. This is a step of forming a glitter image containing a pigment.

  When the printer 1 of FIG. 1 is used, the first step is performed as follows. First, while moving the carriage 4 in the main scanning direction, droplets of the glitter ink are ejected from the nozzle openings 17 of the nozzle row 16A, thereby causing the droplets of the glitter ink to adhere to the recording medium. Thereby, a glitter image made of glitter ink is formed on the recording medium.

  In the present invention, the glossiness refers to a property characterized by, for example, the specular gloss of an obtained image (see Japanese Industrial Standard (JIS) Z8741). For example, the types of glitter include glitter that reflects light in a specular manner and so-called matte glitter, and can be characterized by, for example, high or low specular gloss.

The amount of the glitter pigment contained in the glitter image formed in the first step is 0.10 mg / inch ² or more and 0.50 mg / inch ² or less. When the amount of the glitter pigment contained in the glitter image is within the above range, particularly not below the lower limit, the glitter image of the glitter image is excellent. In addition, if the amount of the glitter pigment contained in the glitter image exceeds the upper limit value, the glitter is hardly improved and the equilibrium state is reached.Therefore, even if more glitter pigment is contained, the glitter can be improved. I can hardly expect it. Therefore, when the amount of the glitter pigment contained in the glitter image is 0.50 mg / inch ² or less, the amount of glitter ink used can be reduced.

The amount (mg / inch ² ) of the glitter pigment contained in the glitter image refers to the amount of the glitter pigment contained per unit area of the glitter image. For example, in order to form a glitter image. It is obtained by dividing the content (mg) of the glitter pigment in the total discharge amount of the glitter ink used by the area (inch ² ) of the glitter image.

1.2.2. Second Step The second step is a step of forming a resin film on the glitter image by discharging droplets of a resin ink (described later) that contains a resin and does not substantially contain a colorant.

  When the printer 1 of FIG. 1 is used, the second step is performed as follows. After the first step, while moving the carriage 4 in the main scanning direction, a resin film that covers the surface of the glitter image by ejecting droplets of resin ink from the nozzle openings 17 of the nozzle row 16B onto the glitter image. Form. That is, the resin film and the glitter image are in contact with each other.

  Further, the resin film may cover the entire glittering image or a part thereof. The resin film may form a continuous film on the glitter image, or may form two or more independent films. Further, the resin film may be formed in a region on the recording medium where the glitter image is not formed as long as it covers at least a part of the surface of the glitter image.

  In the recording method according to the present embodiment, the resin ink is preferably ejected at a timing that does not mix with the droplets of the glitter ink on the recording medium. That is, after the surface of the glitter image is sufficiently dried, the resin ink droplets may be attached to the surface of the glitter image. By doing so, it is possible to reduce the disorder of the arrangement of the glitter pigment in the glitter image, so that a glitter image having further excellent glitter can be obtained.

Here, the amount [W _A (mg / inch ² )] of the glitter pigment contained in the glitter image formed in the first step and the amount [W of resin contained in the resin film formed in the second step] _B (mg / inch ² )] (W _B / W _A ) is 0.063 or more and 2.9 or less, preferably 0.070 or more and 2.0 or less, more preferably 0.15. It is not less than 0.50 and particularly preferably not less than 0.20 and not more than 0.30. When the quantity ratio (W _B / W _A ) is within the above range, a glitter image having excellent glitter, water resistance and light resistance can be obtained while being excellent in glitter. On the other hand, when the quantity ratio (W _B / W _A ) exceeds the above range, the rubbing resistance, water resistance, and light resistance of the glittering image are improved, but the light irregular reflection effect due to the resin film is increased. The glitter of the glitter image is lowered. On the other hand, when the quantity ratio (W _B / W _A ) is below the above range, the brightness of the glittering image is improved, but the effect of protecting the glittering image of the resin film is reduced, and the image is rub-resistant. , Water resistance and light resistance are reduced.

The amount of resin [W _B (mg / inch ² )] contained in the resin film formed in the second step is the solid content of the resin contained per unit area of the resin film covering the glitter image. For example, it can be obtained by dividing the total amount (mg) of resin solids in the resin ink deposited on the glitter image by the area (inch ² ) of the resin film on the glitter image.

Further, the ratio (D _B / D) between the Duty [D _A (%)] of the glitter ink ejected in the first step and the Duty [D _B (%)] of the resin ink ejected in the second step. _A ) is preferably 0.60 or more and 1.3 or less, more preferably 0.70 or more and 1.3 or less. When the duty ratio (D _B / D _A ) is within the above range, and particularly does not exceed the upper limit, the glitter of the glitter image tends to be sufficiently secured. In addition, since the duty ratio (D _B / D _A ) is within the above range, particularly not lower than the lower limit, the surface of the glitter image can be sufficiently filled with droplets (dots) made of resin ink. In some cases, the rubbing resistance, water resistance and light resistance of the color image can be further improved.

  In the present invention, the “Duty value” is a value calculated by the following equation (1).

Duty (%) = number of actual ejection dots / (vertical resolution × horizontal resolution) × 100 (1)
(In the formula, “number of actual ejection dots” is the number of actual ejection dots per unit area, and “vertical resolution” and “horizontal resolution” are resolutions per unit area.)

  The horizontal diameter of the glitter ink ejected in the first step is preferably 0.79 times or more the horizontal diameter of the resin ink ejected in the second step. 26 times or less, more preferably 0.84 times or more and 1.14 times or less. If it is within the above range, the dots (droplets) made of resin ink can sufficiently cover the dots (droplets) made of the glitter pigment constituting the glitter image. In some cases, water resistance and light resistance can be further improved.

  The diameter of the droplet in flight is determined by measuring the longest portion in the horizontal direction with an inkjet droplet automatic measuring device (trade name “JetMeasure”, manufactured by Microjet Co., Ltd.). When the droplets that should have been ejected from the nozzle are divided into a plurality of droplets, the droplet having the largest diameter among the divided droplets is used as a reference.

  The film thickness of the resin film formed on the glitter image is preferably 0.1 μm or more and 0.2 μm or less. When the film thickness of the resin film is within the above range, the abrasion resistance, water resistance, and light resistance may be improved while maintaining the glitter of the glitter image.

1.2.3. Third Step The recording method according to the present embodiment may include a third step of forming a colored image on the glitter image by discharging a colored ink (described later) containing a colorant.

  When the printer 1 of FIG. 1 is used, the third step is performed as follows. After the second step, colored ink droplets are ejected from the nozzle openings 17 of the nozzle row 16C while moving the carriage 4 in the main scanning direction to form a colored image on the glitter image.

  The colored image is not particularly limited as long as it is provided on the glitter image. In other words, the colored image may be provided in contact with the resin film on the glitter image, or provided in a region where the resin film is not formed on the glitter image (that is, in contact with the glitter image). Also good.

  When a colored image is formed on a glitter image, an image having a hue derived from a colorant while having a glitter derived from the glitter pigment is formed.

  In this specification, an image obtained by forming a colored image on a glitter image is also referred to as a “color glitter image”. Further, the colored glitter means a state having a glitter derived from the glitter pigment while having a hue derived from the colorant.

  In the recording method according to the present embodiment, the colored ink is preferably ejected at a timing that does not mix with the glitter ink and the resin ink droplets on the recording medium. That is, after the surface of the glitter image and the resin ink is sufficiently dried, droplets of the colored ink may be attached on the glitter image. By doing so, the disorder of the arrangement of the glitter pigment in the glitter image can be suppressed, and the occurrence of bleeding of the colored image can be suppressed, so that a colored glitter image having excellent colored glitter can be obtained.

Here, the amount [W _A (mg / inch ² )] of the glitter pigment contained in the glitter image formed in the first step and the amount of the colorant contained in the colored image formed in the third step [ The ratio (W _C / W _A ) to W _C (mg / inch ² )] is preferably 3.4 or less, more preferably 2.0 or less, and particularly preferably 0.50 or less. When the quantity ratio (W _C / W _A ) is 3.4 or less, a colored glitter image having excellent colored glitter tends to be obtained.

The amount of colorant contained in the colored image formed in the third step [W _C (mg / inch ² )] is the amount of colorant contained per unit area of the colored image formed on the glitter image. For example, it can be obtained by dividing the total amount (mg) of the colorant contained in the colored ink deposited on the glitter image by the area (inch ² ) of the color image on the glitter image.

1.2.4. Nozzle Division Use In the recording method according to the present embodiment, a mode in which the nozzle row is divided into groups each including a predetermined number of nozzle openings can be preferably used. Hereinafter, a recording method when the nozzle row is divided and used will be described with reference to FIG.

  As shown in FIG. 2, the nozzle rows 16A to 16C include a first group on the upstream side T1 in the sub-scanning direction, a second group on the downstream side T2 in the sub-scanning direction with respect to the first group, and the first group It is divided into three parts for use in the third group on the downstream side T3 in the sub-scanning direction from the second group. In addition, when not using the coloring ink mentioned above, a nozzle row can also be divided into two and used.

  First, while moving the carriage 4 in the main scanning direction, droplets of the glitter ink are ejected from the first group of the first nozzle row 16A, and the droplets of the glitter ink are deposited on the recording medium P. As a result, a first glitter image made of glitter ink is obtained on the recording medium P.

  Next, the recording medium P is moved by the length of the first group in the sub-scanning direction in the downstream T2 direction in the sub-scanning direction. Then, while moving the carriage 4 in the main scanning direction, resin ink droplets are ejected from the second group of the second nozzle row 16B, and the resin ink liquid is formed on the first glittering image formed on the recording medium P. Let the drops adhere. Thereby, the 1st glittering image coat | covered with the 1st resin film is obtained. At this time, the surface of the first glitter image is sufficiently dried while the recording medium P is moved by the length of the first group. Thereby, since mixing of the glitter ink and the resin ink can be satisfactorily suppressed, the first glitter image covered with the first resin film is excellent in the glitter, water resistance and light resistance. It will be excellent.

  Thereafter, the recording medium P is moved by the length of the second group in the sub-scanning direction in the downstream T2 direction in the sub-scanning direction. Then, while moving the carriage 4 in the main scanning direction, the colored ink droplets are ejected from the third group of the third nozzle row 16C, and the colored ink is applied onto the first glittering image covered with the first resin film. Of droplets. As a result, a first colored glitter image in which the first colored image is formed on the first glitter image (on the first resin film) is obtained. At this time, the surface of the first glitter image covered with the first resin film is sufficiently dried while the recording medium P is moved by the length of the second group. As a result, the mixing of the colored ink with the resin ink and the glitter ink can be satisfactorily suppressed, so that the first colored glitter image is excellent in the abrasion resistance, water resistance and light resistance while being excellent in the color glitter. It will be.

  Note that, when the first glitter image is covered with the first resin film (during the same scanning of the carriage 4), droplets of glitter ink are again ejected from the first group of the first nozzle row 16A, and the recording medium A droplet of glitter ink can be deposited on P. As a result, a second glitter image is formed in a portion where the first glitter image is not recorded (upstream side of the first glitter image in the sub-scanning direction). Then, when the first colored glitter image is formed (during the same scanning of the carriage 4), the resin ink droplets are again ejected from the second group of the second nozzle row 16B, and the resin is applied to the second glitter image. By attaching ink droplets, a second glitter image covered with the second resin film is obtained. Thereafter (that is, after the formation of the first colored glitter image), the recording medium P is moved by the length of the third group in the sub-scanning direction in the downstream T2 direction in the sub-scanning direction, and the third nozzle row 16C. The colored ink droplets are ejected from the third group, and the colored ink droplets are adhered onto the second glittering image coated with the second resin film, thereby forming the second glittering image on the second glittering image. A second colored glitter image having a second colored image formed on the resin film is obtained.

  By repeating such an operation, a colored glitter image can be formed on the recording medium.

  In the present embodiment, a method for recording a colored glitter image has been described. However, the present invention is not limited to this, and only a glitter image covered with a resin film can be formed without using a colored ink. The same can be done when the nozzle row is divided into four or more.

  The recording method according to the present embodiment can increase the recording speed by dividing and using the nozzle rows. Further, when the nozzle row is divided and used, the recording medium is not back-fed or the number of back-feeds of the recording medium can be reduced. Accordingly, it is possible to reduce the shift of the printing position that is likely to occur due to the back feed of the recording medium.

1.3. Ink Next, components included in each ink used in the recording method according to the present embodiment will be described in detail.

1.3.1. Bright ink (1) Bright pigment The bright ink used in the recording method according to this embodiment contains a bright pigment. The glitter pigment is not particularly limited as long as it can exhibit glitter when attached to a medium. For example, aluminum, silver, gold, platinum, nickel, chromium, tin, zinc, indium, titanium, and Examples thereof include one or two or more alloys selected from the group consisting of copper (also referred to as metal pigments) and pearl pigments having pearly luster. Representative examples of pearl pigments include pigments having pearly luster and interference gloss such as titanium dioxide-coated mica, fish scale foil, and bismuth oxychloride. Further, the glitter pigment may be subjected to a surface treatment for suppressing reaction with water. By including a glitter pigment in the ink, an image having excellent glitter can be formed.

  The content of the glitter pigment is preferably 0.5% by mass or more and 30% by mass or less, and more preferably 1% by mass or more and 15% by mass or less with respect to the total mass of the glitter ink. When the content of the glitter pigment is within the above range, the ejection stability from the nozzle of the ink jet recording apparatus and the storage stability of the glitter ink can be improved.

  The glitter ink according to the present embodiment is preferably a metal pigment among the glitter pigments. This is because the metallic pigment can impart excellent metallic gloss to the recorded image.

  Hereinafter, silver particles as an example of a preferable embodiment of the glitter pigment will be described. When the glitter ink of this embodiment contains silver particles as a glitter pigment, the silver particles are supplied, for example, as the following silver particle aqueous dispersion. The silver particles do not necessarily have to be supplied in the form of an aqueous dispersion, and may be supplied in the form of powder as long as dispersibility can be ensured.

  The silver particle aqueous dispersion contains silver particles and water. The silver particles contained in the silver particle aqueous dispersion of the present embodiment are particles mainly composed of silver. For example, the silver particles may contain other metals, oxygen, carbon, and the like as subcomponents. The purity of silver in the silver particles can be, for example, 50% or more. The silver particles may be an alloy of silver and another metal. The silver particles in the silver particle aqueous dispersion may be present in a colloid (particle colloid) state. When the silver particles are dispersed in a colloidal state, the dispersibility is further improved. For example, it is possible to contribute to improvement in storage stability when the silver particle aqueous dispersion is mixed with ink.

  An example of a method for producing an aqueous silver particle dispersion is described below. The following production method is an example of a method for producing a silver colloid particle dispersion, but silver particles that can be used in the present embodiment are not limited to this.

  The silver particle production method exemplified below includes a first solution preparation step of preparing a first solution containing at least a polymer of vinylpyrrolidone and a polyhydric alcohol, and a silver precursor that can be reduced to metallic silver as a solvent. A second solution preparing step of preparing a second solution dissolved in the solution, a first solution heating step of heating the first solution to a predetermined temperature, and mixing the heated first solution and the second solution to obtain a mixed solution A mixing step, a reaction advancing step for holding the mixture at a predetermined temperature for a predetermined time, and a dispersion step for taking out silver particles (silver colloidal particles) from the mixture that has undergone the reaction and dispersing the particles in an aqueous dispersion medium. Yes.

  First, a first solution containing a vinylpyrrolidone polymer and a polyhydric alcohol is prepared. One of the functions of the vinylpyrrolidone polymer contained in the first solution is to prevent the aggregation of silver particles and form silver colloidal particles by adsorbing on the surface of the silver particles produced by the production method of this example. To do.

  The vinyl pyrrolidone polymer used may include a vinyl pyrrolidone homopolymer (polyvinyl pyrrolidone) and a vinyl pyrrolidone copolymer. As the copolymer of vinyl pyrrolidone, for example, a copolymer of vinyl pyrrolidone and α-olefin, a copolymer of vinyl pyrrolidone and vinyl acetate, a copolymer of vinyl pyrrolidone and dimethylaminoethyl (meth) acrylate, Copolymer of vinylpyrrolidone and (meth) acrylamidopropyltrimethylammonium chloride, copolymer of vinylpyrrolidone and vinylcaprolactam dimethylaminoethyl (meth) acrylate, copolymer of vinylpyrrolidone and styrene, vinylpyrrolidone and (meta ) A copolymer with acrylic acid. When polyvinyl pyrrolidone is used as the polymer of vinyl pyrrolidone, the weight average molecular weight of polyvinyl pyrrolidone is preferably 3000 or more and 60,000 or less.

  The silver particle aqueous dispersion may contain substances other than those described above. For example, compounds remaining after production, that is, alcohols, dispersants, reducing agents, salts, phenols, amines, various polymers, and the like may be included. These components may be referred to as solid components as components other than water.

  The silver particle aqueous dispersions exemplified above can be suitably used as a raw material when selecting silver particles as the glitter pigment blended in the glitter ink of the present embodiment. Further, the silver particle aqueous dispersion exemplified above can be easily applied to ink because the base as a solvent is water. In addition, a plurality of types of glitter pigments may be blended in the glitter ink according to the present embodiment.

(2) Other ingredients (Alkanediols)
The glitter ink according to this embodiment may contain alkanediols. One of the functions of alkanediols is to reduce nozzle clogging when the glitter ink is ejected from the nozzles of the ink jet recording apparatus.

  Examples of alkanediols include ethylene glycol, propylene glycol, butylene glycol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 2-ethyl-1,3-hexanediol, 1 In addition to 1,2-heptanediol, 1,2-octanediol, hexylene glycol, and the like, alkanediols represented by the following general formula (2) are exemplified. These alkanedirs may be used alone or in combination of two or more.

HO— (CH ₂ ) _n —OH (2)
In the general formula (2), n represents an integer of 3 or more and 20 or less.

  Among the alkanediols, it is preferable to use an alkanediol represented by the general formula (2). The alkanediol represented by the general formula (2) has a function of bringing a glitter image closer to an achromatic color. As a result, for example, when a glitter image is used as a base layer of a color image, an image having good color gloss with little influence of the color of the base layer can be obtained. In the formula, a preferable range of n is an integer of 4 to 8, more preferably an integer of 4 to 6.

  Examples of the compound represented by the general formula (2) include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, and the like. Are preferable. Among these, when silver particles are used as the glitter pigment, it is preferable to use 1,5-pentanediol or 1,6-hexanediol.

  When the alkanediol is contained, its content is preferably 1% by mass or more and 30% by mass or less, and preferably 1% by mass or more and 15% by mass or less with respect to the total mass of the glitter ink. Is more preferable. When the content of alkanediol is within the above range, the above-described function may further enhance the function of alkanediol.

(Polyvinylpyrrolidone)
The glitter ink according to the present embodiment may contain polyvinyl pyrrolidone. As a function of polyvinylpyrrolidone, it is possible to reduce the hygroscopicity of the recorded image while reducing the disorder of the arrangement of the glitter pigment adhering to the recording medium. In addition, when adding polyvinylpyrrolidone, you may use as a dispersing agent and may use it as an additive of a glossy ink manufacturing process.

  The weight average molecular weight of polyvinylpyrrolidone is preferably 5,000 or more, more preferably 5,000 or more and 500,000 or less. When the weight average molecular weight of polyvinyl pyrrolidone is 5,000 or more, the function of the polyvinyl pyrrolidone described above may be further improved.

  In the case of containing polyvinylpyrrolidone, the content thereof can be appropriately set in consideration of the viscosity of the glitter ink, etc., for example, preferably 0.1% by mass with respect to the total mass of the glitter ink. It is 20 mass% or less, More preferably, it is 1 mass% or more and 10 mass% or less.

(Polyhydric alcohols)
The glitter ink according to this embodiment may contain polyhydric alcohols. Examples of polyhydric alcohols include diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, dipropylene glycol, 1,2,6-hexanetriol, thioglycol, glycerin, trimethylolethane, trimethylolpropane, and the like. One of the functions of these polyhydric alcohols is to reduce nozzle clogging when the glitter ink is ejected from the nozzles of the ink jet recording apparatus.

  When polyhydric alcohols are contained, the content thereof is preferably 1% by mass or more and 30% by mass or less with respect to the total mass of the glitter ink.

(Surfactant)
The glitter ink according to this embodiment may contain a surfactant. The surfactant can appropriately maintain the surface tension of the glitter ink and the interface tension with a printer member such as a nozzle in contact with the glitter ink. Thereby, the ejection stability of the glitter ink can be enhanced. Further, it has the effect of spreading uniformly on the recording medium.

  The surfactant having such an effect is preferably a nonionic surfactant. Among the nonionic surfactants, it is more preferable to use at least one of a silicone surfactant and an acetylene glycol surfactant.

  As the silicone surfactant, a polysiloxane compound or the like is preferably used, and examples thereof include polyether-modified organosiloxane. More specifically, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-348 (above trade names, 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 (above trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. When the silicone-based surfactant is contained, the content thereof is preferably 0.1% by mass or more and 2% by mass or less with respect to the total mass of the glitter ink.

  As acetylene glycol surfactants, for example, Surfinol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, 504, 61, DF37 , CT111, CT121, CT131, CT136, TG, GA, DF110D (all trade names, manufactured by Air Products and Chemicals Inc.), Olfin B, Y, P, A, STG, SPC, E1004, E1010, PD- 001, PD-002W, PD-003, PD-004, EXP. 4001, EXP. 4036, EXP. 4051, AF-103, AF-104, AK-02, SK-14, AE-3 (all trade names, manufactured by Nissin Chemical Industry Co., Ltd.), acetylenol E00, E00P, E40, E100 (all trade names, Kawaken Fine Chemical Co., Ltd.). When the acetylene glycol surfactant is contained, the content thereof is preferably 0.1% by mass or more and 2% by mass or less with respect to the total mass of the glitter ink.

  In addition, you may further add anionic surfactant, a nonionic surfactant, an amphoteric surfactant etc. as surfactants other than the above.

(water)
The glitter ink according to the present embodiment may contain water. It is preferable to use pure water or ultrapure water such as ion exchange water, ultrafiltration water, reverse osmosis water, or distilled water. In particular, water obtained by sterilizing these waters by ultraviolet irradiation or addition of hydrogen peroxide is preferable because generation of mold and bacteria is prevented for a long period of time.

(Other ingredients)
The glittering ink according to the present embodiment can further contain a resin, a penetrating solvent, a pyrrolidone derivative, a pH adjuster, an antiseptic / antifungal agent, a rust inhibitor, a chelating agent, and the like. When the glitter ink contains these compounds, the characteristics may be further improved.

  Examples of the resin include acrylic resins, styrene acrylic resins, fluorene resins, urethane resins, polyolefin resins, rosin modified resins, terpene resins, polyester resins, polyamide resins, epoxy resins, vinyl chloride resins. Known resins such as resins, vinyl chloride-vinyl acetate copolymers, ethylene vinyl acetate resins, polyolefin waxes and the like can be mentioned. These resins can be used singly or in combination of two or more. These resins can improve the fixability and abrasion resistance of the glitter ink to the recording medium, and can improve the dispersibility of the glitter pigment in the glitter ink.

  The penetrating solvent has a function of further improving the wettability of the glitter ink with respect to the recording medium and applying it uniformly. Examples of the penetrating solvent include glycol ethers and monohydric alcohols.

  Examples of glycol ethers include ethylene glycol monobutyl ether, 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 mono-n-butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono -T-butyl ether, propylene glycol mono-n-propyl ether, prop Propylene glycol monomethyl -iso- propyl ether, propylene glycol mono -n- butyl ether, dipropylene glycol mono -n- butyl ether, dipropylene glycol mono -n- propyl ether, dipropylene glycol monomethyl -iso- propyl ether.

  Examples of monohydric alcohols include methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, 2,2-dimethyl-1-propanol, n-butanol, 2-butanol, tert-butanol, iso-butanol, 2 -Water-soluble ones such as methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, n-pentanol, 2-pentanol, 3-pentanol, tert-pentanol It is done.

  Examples of the pyrrolidone derivative include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-pyrrolidone, 5-methyl-2-pyrrolidone and the like.

  Examples of the pH adjuster include potassium dihydrogen phosphate, disodium hydrogen phosphate, sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia, diethanolamine, triethanolamine, triisopropanolamine, potassium carbonate, sodium carbonate, Examples thereof include sodium hydrogen carbonate.

  Examples of antiseptics and fungicides include sodium benzoate, sodium pentachlorophenol, 2-pyridinethiol-1-oxide sodium, sodium sorbate, sodium dehydroacetate, 1,2-dibenzisothiazoline-3-one Etc. Examples of commercially available products include Proxel XL2, Proxel GXL (above trade name, manufactured by Avicia), Denside CSA, NS-500W (above trade name, manufactured by Nagase ChemteX Corporation), and the like.

  Examples of the rust inhibitor include benzotriazole.

  Examples of the chelating agent include ethylenediaminetetraacetic acid and salts thereof (such as ethylenediaminetetraacetic acid dihydrogen disodium salt).

1.3.2. Resin Ink The resin ink according to the present embodiment contains a resin and does not substantially contain a colorant (for example, pigment, dye, etc.). Therefore, when the volatile component contained in the resin ink volatilizes, a transparent or translucent film (resin film) is formed.

  In the present invention, “substantially free of A” means that it is not added in excess of an amount that sufficiently achieves the significance of adding A. Specific examples of “substantially free” include, for example, 1.0% by mass or more, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and still more preferably 0% by mass. 0.05% by mass or less, particularly preferably 0.01% by mass or less, more preferably 0.001% by mass or less.

  Hereinafter, components contained in the resin ink will be described.

(1) Resin The resin ink according to the present embodiment contains a resin. The function of the resin includes forming a film to protect the glitter image.

  Examples of the resin include acrylic resins, styrene acrylic resins, fluorene resins, urethane resins, olefin resins, rosin modified resins, terpene resins, ester resins, amide resins, epoxy resins, vinyl chloride resins. Examples thereof include known resins such as resins, vinyl chloride-vinyl acetate copolymers, and ethylene vinyl acetate resins.

  Among these resins, urethane resins, ester resins and fluorene resins are used from the viewpoint of excellent functions capable of improving abrasion resistance, water resistance and light resistance while maintaining the glitter of the glitter image. It is preferable to use at least one selected resin.

  Urethane resin is a polymer synthesized by reacting polyisocyanate and polyol. The synthesis of the urethane resin can be carried out by a known method. Commercially available products can be used as the urethane resin, and examples thereof include SF210 (trade name, manufactured by Daiichi Kogyo Co., Ltd.), WBR-2018 (trade name, manufactured by Taisei Fine Chemical Co., Ltd.), and the like.

  The ester resin is a polymer obtained by polycondensation of a polyol and a polycarboxylic acid. The ester resin can be synthesized by a known method. As the ester-based resin, commercially available products can be used. For example, Eastek 1100, 1300 (above trade name, manufactured by Eastman Chemical Japan), Elitel KZA-1449, KZA-3556 (above trade name, manufactured by Unitika Ltd.) Etc.

  The fluorene-based resin is not particularly limited as long as it has a fluorene skeleton in its structure. For example, a polyol containing a first diol containing a fluorene skeleton and a second diol having a hydrophilic group It can be obtained by reacting the component with a polyisocyanate component containing a polyisocyanate compound. The fluorene resin can be used in the form of either a water-insoluble resin (emulsion) or a water-soluble resin, but is preferably used in the form of a water-soluble resin. Moreover, it is preferable that the weight average molecular weights of a fluorene-type resin are the range of 3000-20000, More preferably, it is 5000-15000, More preferably, it is 6000-12000. Furthermore, the Tg (glass transition temperature) of the fluorene resin is preferably 0 ° C. or higher, more preferably 0 ° C. or higher and 250 ° C. or lower, still more preferably 40 ° C. or higher and 250 ° C. or lower, and even more preferably 80 ° C. or higher and 250 ° C. It is 120 degrees C or less, Most preferably, it is 120 degrees C or less and 250 degrees C or less.

  The content of the resin is preferably 0.4% by mass or more and 10% by mass or less, and preferably 0.5% by mass or more and 5.0% by mass or less in terms of solid content with respect to the total mass of the resin ink. It is more preferable. When the resin content is within the above range, particularly not lower than the lower limit, the resin is sufficiently formed into a film, so that the abrasion resistance, water resistance and light resistance of the glitter image may be further improved. . Moreover, since the film | membrane formed with resin becomes flat because content of resin exists in the said range, and does not exceed an upper limit especially, the glitter of a glitter image may become still better.

(2) Other components (polyolefin wax)
The resin ink according to the present embodiment may contain a polyolefin wax. One of the functions of the polyolefin wax is to increase the slipperiness of the resin film. Thereby, the abrasion resistance of the glitter image formed under the resin film can be further improved.

  The polyolefin wax is not particularly limited. For example, a wax produced from an olefin such as ethylene, propylene, butylene or a derivative thereof, and a copolymer thereof, specifically, a polyethylene wax, a polypropylene wax, a polybutylene series. Examples thereof include wax and paraffin wax. Among these polyolefin waxes, paraffin waxes are preferably used because the above functions may be further improved.

  When the polyolefin wax is contained, the content thereof is preferably 0.05% by mass or more and 2% by mass or less in terms of solid content with respect to the total mass of the resin ink, and 0.1% by mass or more. More preferably, it is 1 mass% or less. When the content of the polyolefin wax is within the above range, the abrasion resistance of the glitter image may be further improved while maintaining the metallic gloss of the glitter image.

(Alkanediols)
The resin ink according to the present embodiment may contain alkanediols. Specific examples and functions of alkanediol are the same as those described for the glittering ink, and thus description thereof is omitted. When the alkanediol is contained, the content thereof is preferably 1% by mass or more and 30% by mass or less, and preferably 1% by mass or more and 15% by mass or less with respect to the total mass of the resin ink. More preferred.

(Surfactant)
The resin ink according to the present embodiment may contain a surfactant. Specific examples and functions of the surfactant are the same as those described for the glitter ink, and thus the description thereof is omitted. When the surfactant is contained, the content thereof is preferably 0.1% by mass or more and 2% by mass or less with respect to the total mass of the resin ink.

(Polyhydric alcohols)
The resin ink according to the present embodiment may contain a polyhydric alcohol. Specific examples of polyhydric alcohols and their functions are the same as those described with respect to the glitter ink, and thus description thereof is omitted. When the surfactant is contained, the content thereof is preferably 0.1% by mass or more and 2% by mass or less with respect to the total mass of the resin ink.

(water)
The resin ink according to the present embodiment may contain water. Since the water contained in the resin ink is the same as that described for the glitter ink, the description thereof is omitted.

(Other ingredients)
For the purpose of further improving the performance of the resin ink, the resin ink according to this embodiment is a penetrating solvent, a pyrrolidone derivative, a pH adjuster, an antiseptic / antifungal agent, a rust inhibitor, a chelating agent, silica particles, isoprene, etc. You may contain resin which has frame | skeleton, a ultraviolet absorber, etc. Since the components other than the silica particles, the resin having an isoprene skeleton, and the ultraviolet absorber are the same as those described in the glitter ink, the description thereof is omitted.

Since silica (SiO ₂ ) particles have a high absorption coefficient with respect to ultraviolet rays, when the resin ink contains silica particles, the light resistance of the glitter image can be improved.

  The silica particles are preferably added as a colloidal solution in which silica particles are dispersed in water or an organic solvent (colloidal silica). Thereby, the silica particles can be easily dispersed in the resin ink. As such colloidal silica, commercially available products may be used, and examples thereof include Snowtex series such as Snowtex XS, OXS, NXS, CXS-9 manufactured by Nissan Chemical Co., Ltd.

  When silica particles are contained, the content thereof is preferably 0.1% by mass or more and 5% by mass or less, and 0.5% by mass or more and 2% by mass or less with respect to the total mass of the resin ink. More preferably.

  The resin having an isoprene skeleton can suppress a decrease in glitter caused by components contained in the recording medium.

  The resin having an isoprene skeleton has an isoprene group as a unit skeleton, and more preferably has an isoprene sulfonic acid skeleton. Commercially available products can be used as the resin having an isoprene skeleton, and examples thereof include DK201, DK202A, and DK106 (above, trade names, manufactured by JSR Corporation).

  When the resin having an isoprene skeleton is contained, the content thereof is preferably 0.1% by mass or more and 5% by mass or less, and 0.5% by mass or more and 2% by mass with respect to the total mass of the resin ink. % Or less is more preferable.

  The ultraviolet absorber has a function of absorbing light such as ultraviolet rays and converting it into vibration energy and heat energy. Thereby, the light resistance of a glitter image can be improved.

  Examples of the ultraviolet absorber include organic ultraviolet absorbers (for example, triazine compounds, benzotriazole compounds, benzophenone compounds), and inorganic ultraviolet absorbers (for example, cerium oxide particles, zirconium oxide particles, iron oxide particles, And titanium oxide particles and zinc oxide particles). Among the ultraviolet absorbers, it is preferable to use an organic ultraviolet absorber (for example, a triazine compound, a benzotriazole compound, etc.) from the viewpoint of excellent transparency.

  When the ultraviolet absorber is contained, the content thereof is preferably 0.1% by mass or more and 5% by mass or less, and 0.5% by mass or more and 2% by mass or less with respect to the total mass of the resin ink. It is more preferable that

1.3.3. Colored ink In the recording method according to the present embodiment, as described above, a colored ink containing a colorant may be used. Hereinafter, the components contained in the colorant will be described.

(1) Colorant The color ink according to the present embodiment contains a colorant. Although it does not specifically limit as a coloring agent, For example, dye, a pigment, a white color material, etc. are mentioned.

  As the dye and the pigment, those described in US Patent Application Publication No. 2010/0086690, US Patent Application Publication No. 2005/0235870, International Publication No. 2011/027842, and the like can be suitably used. Of the dyes and pigments, it is more preferable to include a pigment. The pigment is preferably an organic pigment from the viewpoint of storage stability such as light resistance, weather resistance, and gas resistance.

  Specifically, the pigment is an insoluble azo pigment, condensed azo pigment, azo lake, chelate azo pigment or other azo pigment, phthalocyanine pigment, perylene and perinone pigment, anthraquinone pigment, quinacridone pigment, dioxane pigment, thioindigo pigment, isoindolinone pigment, Polycyclic pigments such as quinophthalone pigments, dye chelates, dye lakes, nitro pigments, nitroso pigments, aniline black, daylight fluorescent pigments and the like are used. The above pigments can be used alone or in combination of two or more.

  Examples of the dye include various dyes used for normal inkjet recording such as direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, disperse dyes, vat dyes, soluble vat dyes, and reactive disperse dyes. Can be used.

  Examples of white color materials include metal oxides, barium sulfate, calcium carbonate, and the like. Examples of the metal oxide include titanium dioxide, zinc oxide, silica, alumina, and magnesium oxide. The white color material includes particles having a hollow structure, and the particles having a hollow structure are not particularly limited, and known ones can be used. As the particles having a hollow structure, for example, particles described in specifications such as US Pat. No. 4,880,465 can be preferably used.

  The content of the colorant is preferably 1% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 15% by mass or less with respect to the total mass of the colored ink.

(2) Others For the purpose of further improving the performance of the colored ink, the colored ink according to this embodiment is water, alkanediols, polyhydric alcohols, surfactants, resins, penetrating solvents, pyrrolidone derivatives, pH adjusters. Further, it may contain preservatives / fungicides, rust preventives, chelating agents and the like. Since these components are the same as those described for the glitter ink, the description thereof is omitted.

1.3.4. Ink physical properties Each of the above inks (glossy ink, resin ink and colored ink) has a surface tension at 20 ° C. of 20 mN / m or more and 50 mN / m from the viewpoint of the balance between the recording quality and the reliability as an ink for inkjet recording. m is preferable, and 25 mN / m or more and 40 mN / m or less is more preferable. The surface tension is measured by using an automatic surface tension meter CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.) by confirming the surface tension when the platinum plate is wetted with ink in an environment of 20 ° C. be able to.

  From the same viewpoint, the viscosity of each ink described above at 20 ° C. is preferably 2 mPa · s or more and 15 mPa · s or less, and more preferably 2 mPa · s or more and 10 mPa · s or less. The viscosity is measured by using a viscoelasticity tester MCR-300 (manufactured by Pysica), increasing the Shear Rate to 10 to 1000 in an environment of 20 ° C., and reading the viscosity at Shear Rate 200. Can be measured.

1.4. Recording medium The recording medium used in the recording method according to the present embodiment is not particularly limited, and examples thereof include paper, cardboard, textiles, leather, sheets or films, plastics, glass, ceramics, metals, and the like. .

2. EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

2.1. Preparation of ink 2.1.1. Brilliant ink First, polyvinylpyrrolidone (PVP, weight average molecular weight 10,000) was heated at 70 ° C. for 15 hours, and then cooled at room temperature. The PVP 1000g was added to the ethylene glycol solution 500ml, and the PVP solution was adjusted. In another container, 500 ml of ethylene glycol was added, 128 g of silver nitrate was added, and the mixture was sufficiently stirred with a magnetic stirrer to prepare a silver nitrate solution. While stirring the PVP solution using an overhead mixer at 120 ° C., the silver nitrate solution was added and the reaction was allowed to proceed by heating for about 80 minutes. And it was made to cool at room temperature after that. The obtained solution was centrifuged for 10 minutes with a centrifuge at 2200 rpm. Thereafter, the separated silver colloid was taken out and added to 500 ml of an ethanol solution to remove excess PVP. Then, further centrifugation was performed to take out silver colloid. Furthermore, the taken-out silver colloid was dried on 35 degreeC and 1.3 Pa conditions with the vacuum dryer.

  Using the silver colloid (silver particles) produced in this way, the components shown in Table 1 are mixed and stirred, and filtered through a membrane filter with a pore size of 5 μm to remove impurities such as dust and coarse particles. Thus, glitter inks 1 to 3 were prepared.

  In Table 1, the components described by trade names are as follows. Moreover, the unit of the numerical value in Table 1 is the mass%.

・ Orphine E1010 (trade name, manufactured by Nissin Chemical Industry Co., Ltd., acetylene glycol surfactant)
· PVP K15 (trade name, ISP JAPAN Co., Ltd., weight average molecular weight _M W: 10,000)

2.1.2. Resin Inks Resin inks 1 to 3 were prepared by mixing and stirring the components shown in Table 2 and filtering impurities through a membrane filter having a pore size of 5 μm to remove impurities such as dust and coarse particles. Each component described in Table 2 is as follows. In addition, resin and the content of wax of Table 2 are the values converted into solid content.

  In Table 2, the components indicated by abbreviations are as follows.

Urethane resin (trade name “W-615”, manufactured by Mitsui Chemicals, polycarbonate anionic polyurethane, Tg: 85 ° C.)
Fluorene-based resin (obtained by the production method described later. Water-soluble resin, weight average molecular weight: 3300)
Paraffin wax (trade name “AQUACER 539”, manufactured by Big Chemie Japan, paraffin wax emulsion, average particle size: 54 nm)

  In addition, what was synthesize | combined as follows was used as a fluorene-type resin. The fluorene resin is composed of 30 parts by mass of isophorone diisocyanate, 50 parts by mass of 4,4 ′-(9-fluorenylidene) bis [2- (phenoxy) ethanol], 3-hydroxy-2- (hydroxymethyl) -2-methylpropionic acid. 100 parts by mass and 30 parts by mass of triethylamine were weighed and mixed well, and then synthesized by stirring at 120 ° C. for 5 hours in the presence of a catalyst. The obtained fluorene-based resin was a resin having a molecular weight of 3300, containing 4,4 '-(9-fluorenylidene) bis [2- (phenoxy) ethanol] having a monomer composition ratio of about 50% by mass.

2.1.3. Colored ink Magenta ink ICM37 manufactured by Seiko Epson Corporation was used as the colored ink. Hereinafter, the magenta ink ICM 37 is also referred to as “colored ink 1”.

2.2. Evaluation 1 (Evaluation of glitter image)
In Evaluation 1, an ink jet printer PX-G930 (trade name, manufactured by Seiko Epson Corp.) equipped with the ink set using the cartridge filled with the glitter ink and the resin ink was used.

2.2.1. Creation of Evaluation Samples Evaluation samples of Examples 1 to 5 and Comparative Examples 2 and 3 were produced as follows. First, glitter ink droplets were ejected from the nozzle opening of the printer, and a glitter image was formed on a recording medium (trade name “photo paper gloss”, manufactured by Seiko Epson Corporation).

  Next, resin ink was ejected from the nozzle opening of the printer and adhered onto the glitter image, thereby forming a resin film covering the glitter image. In this way, evaluation samples of Examples 1 to 5 and Comparative Examples 2 and 3 were obtained.

  The evaluation sample of Comparative Example 1 was prepared in the same manner except that no resin film was formed on the glitter image.

The glitter image and the resin film were recorded at an image resolution of 1440 dpi × 1440 dpi. Also shown Duty value at the time of recording, the amount of the bright pigment contained in the bright image ^{_{W A (mg / inch 2)}} , the amount of resin contained in the resin film _W B a (mg / inch ²⁾ in Table 3.

2.2.2. Evaluation Test (1) Glossiness (Brightness)
The 60 ° specular glossiness of the glitter image of the obtained evaluation sample was measured according to JIS Z8741: 1997 using a gloss meter (trade name “GlossMeter model number VGP5000” manufactured by Nippon Denshoku Industries Co., Ltd.). Based on the obtained 60 ° specular gloss, the glitter of the glitter image was evaluated. The classification of evaluation criteria is as follows.
A: 60 ° specular gloss is 325 or more B: 60 ° specular gloss is 290 or more and less than 325 C: 60 ° specular gloss is less than 290 (2) Friction resistance Gakushin type friction fastness tester AB-301 (tester The surface condition of the glitter image is obtained by rubbing the glitter image with the friction element attached with the white cotton cloth for friction (Kanakin No. 3) under the conditions of no load and 50 times of friction. Was visually observed. The evaluation criteria are as follows.
A: No scratches are observed in the glitter image B: Slight scratches are observed in the glitter image C: Clear scratches are observed in the glitter image D: Clear scratches are observed in the glitter image Part of the image is peeled off

(3) Water resistance The glitter image of the obtained evaluation sample was wiped 10 times with a water-soaked Bencot (trade name, manufactured by Asahi Kasei Fibers Co., Ltd.), and the glitter image and Bencott were visually observed. The evaluation criteria are as follows.
A: No change in the appearance of the glitter image, and no deposits are observed in the bencott B: Slight unevenness is observed in the glitter image, but no deposits are observed in the bencott C: Clear unevenness in the glitter image And deposits are observed on Bencott

(4) Light resistance The light resistance of the glitter image of the obtained evaluation sample was evaluated. Specifically, in accordance with the “Digital Color Photo Print Image Preservation Test Method” (JEITA CP-3901) issued by the Japan Electronics and Information Technology Industries Association (JEITA), an accelerated test that reproduces image degradation equivalent to 20 years is performed. went. Thereafter, the 60 ° specular glossiness of the glitter image was measured by the same method as the glossiness evaluation method described above, and this was compared with the 60 ° specular glossiness before the light resistance test. The evaluation criteria are as follows.
A: The decrease in 60 ° specular gloss is less than 7% B: The decrease in 60 ° specular gloss is 7% or more and less than 15% C: The decrease in 60 ° specular gloss is 15% or more

2.2.3. Evaluation result of evaluation 1 Table 3 shows the result of each evaluation test of evaluation 1.

  Each of the evaluation samples according to Examples 1 to 5 was provided with a glitter image excellent in glitter and excellent in abrasion resistance, water resistance and light resistance.

  On the other hand, in the evaluation sample according to Comparative Example 1, the glitter image is not covered with the resin film. Therefore, the recorded glitter image was excellent in glitter, but was not excellent in abrasion resistance, water resistance and light resistance.

The evaluation sample according to Comparative Example 2 includes the amount of the glitter pigment contained in the glitter image [W _A (mg / inch ² )] and the amount of the resin contained in the resin film [W _B (mg / inch ² )]. (W _B / W _A ) was less than 0.063. Therefore, the recorded glitter image was excellent in glitter, but was not excellent in abrasion resistance, water resistance and light resistance.

The evaluation sample according to Comparative Example 3 includes the amount of the glitter pigment contained in the glitter image [W _A (mg / inch ² )] and the amount of the resin contained in the resin film [W _B (mg / inch ² )]. The ratio (W _B / W _A ) exceeds 2.9. Therefore, the recorded glitter image was excellent in abrasion resistance, water resistance and light resistance, but not in glitter.

2.3. Evaluation 2 (Evaluation of colored glitter image)
In the evaluation 2, an ink jet printer PX-G930 (trade name, manufactured by Seiko Epson Corporation) equipped with the inks each including the above-described glitter ink, resin ink, and colored ink was used.

2.3.1. Preparation of Evaluation Sample Evaluation samples of Experimental Examples 1 to 4 were manufactured as follows. First, glitter ink droplets were ejected from the nozzle opening of the printer, and a glitter image was formed on a recording medium (trade name “photo paper gloss”, manufactured by Seiko Epson Corporation).

  Next, resin ink was ejected from the nozzle opening of the printer and adhered onto the glitter image, thereby forming a resin film covering the glitter image.

  Thereafter, colored ink was ejected from the nozzle opening of the printer to form a colored image on the glitter image (resin film). In this way, evaluation samples of Experimental Examples 1 to 4 in which colored glitter images were formed were obtained.

Recording of the glitter image, the resin film, and the colored image was performed at an image resolution of 1440 dpi × 1440 dpi. Further, Duty value at the time of recording, the amount _W A bright pigment contained in the bright image (mg / inch ^2), the amount _W B of the resin contained in the resin film (mg / inch ^2), contained in the colored image The amount of colorant W _C (mg / inch ² ) is shown in Table 4.

W _A , W _B , and W _C are the mass percentages of the glitter pigment, resin, and color pigment contained in each ink, the ejection weight per dot ejected for each ink, and the It can be calculated from the number of discharges per inch ² .

2.3.2. Evaluation test (1) Color metallic feeling (colored glitter)
Each of the obtained evaluation samples was visually observed to evaluate the color metallic feeling (that is, colored glitter). The evaluation criteria are as follows.
A: Vivid color metallic feel B: Color is felt but metallic feel is low C: Magenta without metallic feel or colored ink overflows and unevenness occurs

(2) Scratch resistance, water resistance, light resistance Evaluation of the scratch resistance, water resistance, and light resistance was performed by the same evaluation method and evaluation criteria as in Evaluation 1.

2.3.3. Evaluation results of evaluation 2 Table 4 shows the results of the evaluation tests of evaluation 2.

  All of the evaluation samples according to Experimental Examples 1 to 3 were provided with colored glitter images excellent in colored glitter and excellent in abrasion resistance, water resistance and light resistance.

On the other hand, the evaluation sample according to Experimental Example 4 includes the amount of glitter pigment contained in the glitter image [W _A (mg / inch ² )] and the amount of colorant contained in the colored image [W _C (mg / inch). ² )] and the ratio (W _C / W _A ) exceeds 3.4. For this reason, the recorded glitter image was excellent in abrasion resistance and water resistance, but was not excellent in light resistance and colored glitter. The reason why the light resistance is lowered is that the resin film made of the protective resin ink is partially redissolved due to the large amount of the colored ink applied. As a result, the bright pigment of the resin film made of the resin ink is removed. Although it thinks that the effect | action to protect fell, it is not necessarily limited to the said principle.

  The present invention is not limited to the embodiments described above, and various modifications are possible. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

DESCRIPTION OF SYMBOLS 1 ... Printer, 2 ... Head, 3 ... Ink cartridge, 4 ... Carriage, 5 ... Platen, 7 ... Carriage moving mechanism, 8 ... Medium feed mechanism, 15 ... Nozzle surface, 16 ... Multiple nozzle row, 17 ... Nozzle opening

Claims (9)

A recording method using an ink jet recording apparatus,
A droplet of glitter ink containing the glitter pigment is ejected onto a recording medium, and a glitter image containing the glitter pigment of 0.10 mg / inch ² or more and 0.50 mg / inch ² or less is formed on the recording medium. A first step of forming;
A second step of forming a resin film on the glitter image by discharging resin ink droplets containing a resin and substantially no colorant;
Including
The amount of the bright pigment contained in the glitter image ^{_{[W A (mg / inch 2}} )] and the amount of the resin contained in the resin film ^{_{[W B (mg / inch 2}} )] ratio of (W _B / W _A ) is a recording method of 0.063 or more and 2.9 or less. In claim 1,
Ratio (D _B /%) of Duty [D _A (%)] of the glitter ink ejected in the first step and Duty [D _B (%)] of the resin ink ejected in the second step _A recording method in which D _A ) is 0.60 or more and 1.3 or less. In claim 1 or claim 2,
The recording method, wherein a diameter in the horizontal direction when the glitter ink droplets fly is not less than 0.79 times and not more than 1.26 times a diameter in the horizontal direction when the resin ink droplets fly. In any one of Claims 1 thru | or 3,
The ink jet recording apparatus includes a head including a nozzle row including a plurality of nozzle openings, and a carriage that scans the head in the main scanning direction.
The nozzle row includes a first nozzle row in which a plurality of nozzle openings for discharging the glitter ink droplets are arranged in a sub-scanning direction intersecting the main scanning direction, and a nozzle for discharging the resin ink. A second nozzle row in which a plurality of the nozzle openings are arranged in the sub-scanning direction,
The first nozzle row and the second nozzle row are divided and used for each group including a predetermined number of the nozzle openings in the sub-scanning direction.
The group includes a first group on the upstream side in the sub-scanning direction, and a second group on the downstream side in the sub-scanning direction with respect to the first group,
The first step is performed by discharging droplets of the glitter pigment from the first group of the first nozzle row,
The recording method, wherein the second step is performed by discharging droplets of the resin ink from the second group of the second nozzle row. In any one of Claims 1 thru | or 4,
The recording method, wherein the resin is at least one selected from a urethane resin, a fluorene resin, and an ester resin. In any one of Claims 1 thru | or 5,
The recording method further includes a third step of discharging a colored ink containing a colorant to form a colored image on the resin film. In claim 6,
Ratio of the amount [W _A (mg / inch ² )] of the glitter pigment contained in the glitter image and the amount [W _C (mg / inch ² )] of the colorant contained in the colored image ( The recording method wherein W _C / W _A ) is 3.4 or less. In claim 6 or claim 7,
The ink jet recording apparatus includes a head including a nozzle row including a plurality of nozzle openings, and a carriage that scans the head in the main scanning direction.
The nozzle row includes a first nozzle row in which a plurality of nozzle openings for discharging the glitter ink droplets are arranged in a sub-scanning direction intersecting the main scanning direction, and a nozzle for discharging the resin ink. A second nozzle row in which a plurality of the nozzle openings are arranged in the sub-scanning direction; and a third nozzle row in which a plurality of the nozzle openings for discharging the colored ink are arranged in the sub-scanning direction;
The first nozzle row, the second nozzle row, and the third nozzle row are divided and used for each group including a predetermined number of the nozzle openings in the sub-scanning direction.
The group includes a first group on the upstream side in the sub-scanning direction, a second group on the downstream side in the sub-scanning direction with respect to the first group, and a downstream side in the sub-scanning direction with respect to the second group. A third group on the side,
The first step is performed by discharging droplets of the glitter pigment from the first group of the first nozzle row,
The second step is performed by discharging droplets of the resin ink from the second group of the second nozzle row,
The recording method according to claim 3, wherein the third step is performed by discharging droplets of the colored ink from the third group of the third nozzle row.   A recorded matter obtained by the recording method according to any one of claims 1 to 8.

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