JP6229746B2 - Recording method and recording apparatus - Google Patents

Description

  The present invention relates to a recording method and a photocurable ink set used therefor.

Conventionally, in order to enhance the aesthetics of human photographs and the like, it has been demanded to use inks that are particularly excellent in curability and aesthetics, and various studies have been made.

For example, Patent Document 1 discloses a single-pass inkjet recording apparatus in which the first ink is temporarily cured after the first ink is ejected and before the second ink is ejected. Has been.

Patent Document 2 discloses an aqueous photopolymerizable composition containing an alkylphenone photoinitiator in which a plurality of alkyl groups are introduced into a phenyl group and pendant with a carboxylic acid or a sulfonic acid, or a benzyl ketal photoinitiator. Has been disclosed using a light emitting diode having a dominant wavelength of 320 nm to 380 nm.

JP 2009-285854 A JP 2009-138150 A

However, when the ink disclosed in Patent Document 1 or Patent Document 2 is used, it may be inferior in curability (LED tack-free property) or aesthetics (ink color stability and transparency of clear ink). Problems arise. Therefore, there is still a strong demand for a photocurable ink composition that forms a coating film having excellent curability and aesthetics.

Therefore, the present invention is excellent in LED tack-free properties, ink color stability, and clear ink transparency, among which, in particular, ink color stability and clear ink transparency are excellent.
An object is to provide a recording method and a photocurable ink set used therefor.

The present inventors have intensively studied to solve the above problems. As a result, when a photocurable ink set comprising a photocurable color ink composition and a photocurable clear ink composition having a predetermined composition is used, a coating film formed from the ink set is subjected to main curing by light irradiation. The recording method for setting the irradiation energy within a predetermined range has been found to be excellent in LED tack-free property, ink color stability, transparency of clear ink, and excellent in image quality (image quality), and the present invention has been completed. .

  That is, the present invention is as follows.

[1]
Photocurable ink set comprising a photocurable color ink composition containing a polymerizable compound, a photopolymerization initiator, and a coloring material, and a photocurable clear ink composition containing a polymerizable compound and a photopolymerization initiator is used. Recording method,
The photocurable color ink composition comprises (1) an acyl phosphine oxide photopolymerization initiator and 0.5 to 4% by mass of (2) thioxanthone photopolymerization based on the total mass of the color ink composition. At least one of an initiator and / or an α-aminoalkylphenone photopolymerization initiator,
The photocurable clear ink composition is used in an amount of 5 to 12 with respect to the total mass of the clear ink composition.
Containing an acyl phosphine oxide-based photopolymerization initiator in mass%,
The recording method whose irradiation energy at the time of hardening | curing the coating film formed from this ink set by light irradiation from a light source is 100-800 mJ / cm < ² >.

[2]
Forming a first coating film of the photocurable color ink composition on a recording medium, and forming a second coating film of the photocurable clear ink composition on the first coating film; [1] The recording method described in 1.

[3]
The photocurable color ink composition is 1 to 2 based on the total mass of the color ink composition.
The recording method according to [1] or [2], comprising 4% by mass of a thioxanthone photopolymerization initiator.

[4]
The recording method according to any one of [1] to [3], wherein the light source is a mercury lamp or a metal halide lamp.

[5]
Before irradiating light with the irradiation energy from the said light source with respect to the said photocurable clear ink composition, light is irradiated from the light source for temporary curing, It is any one of [1]-[4]. Recording method.

[6]
The recording method according to [5], wherein the temporary curing light source is a light emitting diode.

[7]
By curing the coating film formed by discharging the photocurable ink set from the print head and landing on the recording medium while scanning the recording medium relative to the print head by light irradiation. A recording method for forming an image, comprising:
By discharging and landing the photocurable color ink composition on the recording medium,
A first coating film forming step of forming a first coating film on the recording medium;
A first temporary curing step of temporarily curing the first coating film by first light irradiation;
By discharging the photocurable clear ink composition onto at least one of the recording medium and part or all of the first coating film, one of the first coating film and the recording medium is discharged. A second coating film forming step of forming a second coating film on at least one of the part or the whole, and
A second temporary curing step of temporarily curing the second coating film by second light irradiation;
A primary curing step of performing primary curing of the temporarily cured first coating film and the second coating film by light irradiation from the light source, according to any one of claims [1] to [6]. The recording method described in 1.

[8]
The recording method according to [7], wherein a conversion rate in the first temporary curing step is 30 to 95%.

[9]
The recording method according to [7] or [8], wherein the conversion rate in the second temporary curing step is 30 to 100%.

[10]
The recording method according to any one of [1] to [3], wherein the light source is a light emitting diode.

[11]
The recording method according to any one of [1] to [3], wherein recording is performed using a line inkjet printer.

[12]
The recording method according to any one of [1] to [3], wherein recording is performed using a serial inkjet printer.

[13]
The recording method according to [12], wherein the ink attached to the recording medium by the main scanning is irradiated by the main scanning and the main scanning after the main scanning.

[14]
The recording method according to [12] or [13], wherein the irradiation energy of the cyan ink composition and the irradiation energy of the clear ink composition are different.

[15]
A photocurable ink set comprising the photocurable color ink composition and the photocurable clear ink composition used in the recording method according to any one of [1] to [14].

[16]
[1] A recording apparatus that performs recording by the recording method according to any one of [14].

It is a block diagram which shows the structure of the line printer used in one Embodiment of this invention. FIG. 2 is a schematic view around a recording area in one embodiment of the line printer of FIG. 1. 3 is a flowchart showing a recording method according to an embodiment of the present invention. 1 is a schematic diagram illustrating a part of a configuration of a serial printer according to an embodiment of the present invention.

Hereinafter, embodiments for carrying out the present invention will be described in detail. In addition, this invention is not restrict | limited to the following embodiment, A various deformation | transformation can be implemented within the range of the summary.

In the present specification, “tack-free property” means that no rub marks are formed even when rubbed with a cotton swab. In more detail, touch the surface of the recorded material (cured film) with your finger, and the viscosity of the film surface (
Tack) refers to the property evaluated by the time until the film does not adhere to the finger, and this time is also referred to as tack free time or finger touch drying time. With excellent tack-free properties,
This time is shorter. “LED tack-free” means light-emitting diode (LE
The tack-free property after temporary curing performed using D). “Color stability” means CIE
Lab (L ^* a ^* b ^* color system) in the L ^* a ^* b ^* is, immediately after the saw be printed after printing with time L ^*
A property that hardly changes from a ^* b ^* . “Transparency” refers to a property in which discoloration such as yellowing and blueness is not noticeable in a cured film. “Curable” refers to the property of polymerizing and curing in the presence or absence of a photopolymerization initiator upon irradiation with light. “Discharge stability” refers to the property of ejecting stable ink droplets from the nozzles without clogging the nozzles.

In this specification, “color ink” is ink used for imparting color to a recording medium, and refers to any colored ink. “Clear ink” is not ink used for imparting color to a recording medium, but ink used for the purpose of imparting gloss to the recording medium, and is generally colorless and transparent or almost colorless. Transparent ink. The “conversion rate” means the rate at which the polymerizable compound contained in the ink composition is converted into a cured product, and can be translated into the degree of curing of the ink composition by light irradiation. “Temporary curing” means temporary pinning of ink (pinning), which means to cure before main curing in order to prevent dot bleeding and color mixing. It is lower than the conversion rate by the main curing performed after the step. “Main curing” refers to curing the dots formed on the recording medium to a curing state necessary for using the printed material.
In addition, “light source for main curing” means a light source used for main curing, and “light source for temporary curing” means a light source used for temporary curing.

Further, in this specification, “duty” is a value calculated by the following equation, and print duty
In other words, y or the printing rate.
duty (%) = number of actual printing dots / (vertical resolution × horizontal resolution) × 100
(In the formula, "Actual number of printed dots" is the number of actual printed dots per unit area.
And “horizontal resolution” are resolutions per unit area. Also, “duty 100%
"Means the maximum ink weight of a single color per unit pixel. )

In the present specification, “(meth) acrylate” means at least one of acrylate and methacrylate corresponding thereto, and “(meth) acryl” means at least one of acrylic and methacryl corresponding thereto. To do.

[Recording method]
One embodiment of the present invention relates to a recording method. The recording method includes a photocurable ink set (a photocurable color ink composition having a predetermined composition and a photocurable clear ink composition).
Hereinafter, it is also referred to as “specific photocurable ink set”. ) And the irradiation energy when the film formed from the ink set is fully cured by light irradiation is 200 to 800 mJ / cm.
² is a recording method.

[Recording device]
Hereinafter, the recording apparatus used in the recording method of the present embodiment will be described in detail.
FIG. 1 is a block diagram illustrating a configuration of a line printer that is an example of a recording apparatus used in the present embodiment. FIG. 2 is a schematic view around the recording area in one embodiment of the line printer of FIG.

(1. Device configuration)
As shown in FIG. 1, a printer 1 according to this embodiment includes a computer 11 that is an external device.
0 is communicably connected.

The printer 1 is an apparatus that forms an image on a recording medium by discharging a photocurable ink composition that is cured by irradiation with radiation (light).
Here, “on the recording medium” in this specification means being positioned on the surface of the recording medium and above the surface.

The printer 1 (recording apparatus) includes a transport unit 2 that transports a recording medium in the transport direction.
0 (conveyance unit), a part of the head unit 30 (first print head) for discharging the photocurable color ink composition onto the recording medium, and the color ink composition landed on the recording medium A part of the irradiation unit 40 for temporarily curing the first coating film to be cured by the first light irradiation (
A first pre-curing irradiation section) and a light curing type clear ink composition disposed at least on a part of the first coating film on the downstream side in the transport direction from the first pre-curing irradiation section. A part (second print head) of a head unit 30 that discharges an object, the temporarily cured first coating film, and at least the clear ink composition landed on the part of the first coating film. Part of the irradiation unit 40 for temporarily curing the second coating film by the second light irradiation (second temporary curing irradiation section)
And a part of the irradiation unit 40 (the main curing irradiation unit) that performs main curing of the first cured coating film and the second cured coating film by light irradiation from a main curing light source. Prepare. In addition to this, the above-described printer 1 (recording apparatus) optionally includes a detector group 50 and a controller 6.
0. In addition, said 1st light irradiation and 2nd light irradiation both mean the light irradiation from the light source for temporary hardening.

The transport unit 20 is for transporting the recording medium in the transport direction. As illustrated in FIG. 2, the transport unit 20 includes, for example, an upstream transport roller 23 </ b> A and a downstream transport roller 23 </ b> B, and a belt 24.

The head unit 30 is for discharging the photocurable ink composition toward the recording medium.

The irradiation unit 40 irradiates light toward the dots of the photocurable ink composition landed on the recording medium S. Since the irradiation unit 40 in the present embodiment can suppress bleeding and prevent color mixing, the first pre-curing irradiation unit 42e and the first in the form shown in FIG. It is preferable that the provisional curing irradiation unit 42f and the main curing irradiation unit 44 are provided.

The detector group 50 includes a rotary encoder (not shown) and a paper detection sensor (not shown) as required.

The controller 60 is a control unit for controlling the printer, and the controller 60 includes an interface unit 61, a CPU 62, a memory 63, and a unit control circuit 64. The interface unit 61 is for transmitting and receiving data between the computer 110 as an external device and the printer 1. The CPU 62 is an arithmetic processing unit for controlling the entire printer. The memory 63 is for securing an area for storing a program of the CPU 62, a work area, and the like, and includes storage elements such as a RAM and an EEPROM. The unit control circuit 64 controls each unit (each unit) based on the control of the CPU 62 according to a program stored in the memory 63.

As described above, the printer 1 includes at least a photocurable color ink composition ejected first (hereinafter also simply referred to as “color ink composition”) and a photocurable clear ink composition (hereinafter also referred to as “color ink composition”). Hereinafter, it is configured to be capable of forming an image (printing can be performed).

FIG. 2 is a diagram schematically illustrating a configuration related to printing in the printer 1. FIG. 2 illustrates an embodiment in which the color ink composition is composed of a single type or a combination of two or more types. In the embodiment of FIG. 2, when the color ink composition is a combination of two or more, a print head (not shown) for the color ink composition of each color (hereinafter also simply referred to as “head”).
2 are arranged in order from the upstream side to the downstream side in the transport direction at the position of the head COLOR in FIG. As a specific example, a black ink head, a cyan ink head, a magenta ink head, and a yellow ink head are sequentially provided from the upstream side at the position of the head COLOR in FIG. As shown in FIG. 2, the color head COLOR and the clear ink head CL are provided in order from the upstream side in the transport direction.

In the aspect shown in FIG. 2, the first temporary curing irradiation section 42e is provided on the downstream side in the transport direction of the head COLOR. In addition to the first temporary curing irradiation unit 42e, a second temporary curing irradiation unit 42f is provided on the downstream side in the transport direction of the clear ink head CL. further,
The main curing irradiation unit 44 is provided on the downstream side in the transport direction of the second temporary curing irradiation unit 42f.

(2. Device operation)
The printer 1 that has received print data from the computer 110, which is an external device, is controlled by the controller 60 so that each unit (each unit), that is, the transport unit 20 and the head unit 3.
0 and the irradiation unit 40 are controlled to form an image on the recording medium in accordance with the print data. The controller 60 is based on the print data received from the computer 110.
Each part is controlled to form an image on the recording medium. The situation in the printer 1 is monitored by the detector group 50, and the detector group 50 outputs the detection result to the controller 60. The controller 60 controls each unit based on the detection result output from the detector group 50.

In the transport unit 20, when a transport motor (not shown) rotates, the upstream transport roller 23A and the downstream transport roller 23B shown in FIG. 2 rotate, and the belt 24 moves. The recording medium S fed by a paper feed roller (not shown) is conveyed by the belt 24 to a recordable area (area facing the head). Then, the recording medium S that has passed through this area is discharged to the outside by the belt 24.

At this time, the transport unit 20 (scanning unit) scans the recording medium S in the transport direction (scanning direction) relative to the head unit 30 (head), while ink (photocurable ink set described later). Is discharged from the head unit 30. Ink may be ejected while performing a scan for moving the head unit 30 relative to the recording medium S without conveying the recording medium S. Here, when the recording medium S performs scanning that moves relative to the head unit 30, the side on which the recording medium S is conveyed is downstream, and the head unit 30 is connected to the recording medium S.
When scanning is performed with respect to the head, the direction in which the head unit 30 moves is the upstream side.

Note that the recording medium S being conveyed may be electrostatically attracted or vacuum attracted to the belt 24. Further, in this specification, for convenience, the term “paper feeding” is used, but as the recording medium S in the present embodiment, a recording medium described later can be used.

The head unit 30 discharges at least a color ink composition and a clear ink composition as a photocurable ink composition for forming an image.

The head unit 30 discharges each ink to the recording medium S being conveyed, thereby forming dots on the recording medium S (landing ink), and forming a film by forming a coating film. To do. The printer 1 is a line printer, and each head of the head unit 30 can form dots corresponding to the width of the recording medium.

In the irradiation unit 40, the dots (landed ink) formed on the recording medium S are cured by receiving light irradiation from the irradiation unit 40.

The first temporary curing irradiation section 42e shown in FIG. 2 performs temporary curing of dots corresponding to the first coating film formed on the recording medium S before the clear ink composition lands on the dots. 1st light irradiation for making it do. In the first temporary curing irradiation unit, it is only necessary to be able to perform temporary curing. Therefore, at least a part of the dots (droplets), for example, the dot surface may be cured. By performing this temporary curing, it is possible to prevent ink bleeding.

Further, the second temporary curing irradiation section 42f shown in FIG. 2 can surely suppress bleeding of the color ink and the clear ink by irradiating the clear light with the second light and quickly curing it. Is. In FIG. 2, only the main curing irradiation unit 44 may be irradiated to the clear ink without providing the second temporary curing irradiation unit 42f.

The main curing irradiation section 44 shown in FIG. 2 performs main curing of the color ink composition and the clear ink composition that have landed on the recording medium by light irradiation from a main curing light source. In other words, the main curing irradiation section 44 almost completely cures the dots (the first coating film and the second coating film formed by the clear ink composition) formed on the recording medium S (main curing). Irradiate light to make it happen. Further, the length of the main curing irradiation section 44 in the width direction of the recording medium S is equal to or larger than the width of the recording medium S. The main curing irradiation unit 44 then irradiates the dots formed by the heads of the head unit 30 with light.

The main curing irradiation unit 44 includes an LED or a lamp as a main curing light source. The lamp is not particularly limited, and examples thereof include a metal halide lamp, a xenon lamp, a carbon arc lamp, a chemical lamp, a low pressure mercury lamp, and a high pressure mercury lamp.

The first provisional curing irradiation unit 42e and the second provisional curing irradiation unit 42f include a light emitting diode (LED) as a provisional curing light source. The LED can easily change the irradiation energy by controlling the magnitude of the input current.

The light irradiation energy of the main curing by the main curing irradiation unit 44 is common between the photocurable color ink composition and the photocurable clear ink composition when the main curing is performed once. On the other hand, in order to make the light irradiation energy of the main curing different between the photocurable color ink composition and the photocurable clear ink composition, the main curing is performed after each ink composition is landed on the recording medium. Must be done each time. However, if the main curing is performed twice or more, it becomes complicated and the process of the recording method becomes complicated. Therefore, the main curing is preferably performed once. Therefore, it is preferable to use the photocurable color ink composition and the photocurable clear ink composition as a set so that the main curing can be carried out once.
In this specification, the irradiation energy irradiated from the light source at the time of temporary curing (pinning) has a wavelength different from that at the time of main curing (very small). It is distinguished from

The irradiation energy at the time of the main curing, that is, the irradiation energy at the time of curing the coating film formed from the photocurable ink set described later by light irradiation from the light source for main curing is 100 to 800.
a mJ / cm ^2, preferably 200~800mJ / cm ^2, 250~750mJ / cm
² is more preferable, and 300 to 700 mJ / cm ² is particularly preferable. Details regarding the irradiation energy will be described later.

As shown in FIG. 2, the printer 1 further includes a second temporary curing irradiation unit 42 f between the clear ink head CL and the main curing irradiation unit 44. Bleed (color mixing) can be effectively suppressed.

The rotary encoder that can be provided in the detector group 50 includes an upstream side conveyance roller 23A.
And the rotation amount of the downstream side transport roller 23B is detected. The transport amount of the recording medium S can be detected based on the detection result of the rotary encoder. A paper detection sensor that can be provided in the detector group 50 detects the position of the leading end of the recording medium S being fed.
The operation of each part constituting the controller 60 is as described above.

The computer 110 is for installing a printer driver. The printer driver is a program for displaying a user interface on a display device (not shown) and converting image data output from an application program into print data (image formation data). The printer driver is recorded on a computer-readable recording medium such as a flexible disk FD or a CD-ROM. Alternatively, the printer driver can be connected to the computer 1 via the Internet.
10 can also be downloaded. In addition, this program is comprised from the code | cord | chord for implement | achieving various functions.
Then, the computer 110 outputs print data corresponding to the image to the printer 1 in order to cause the printer 1 to form an image.

The printer (recording apparatus) in the present embodiment described above includes a serial printer described later in addition to a line printer such as the printer 1. These are different printer systems. Briefly speaking, a line printer is one in which printing is performed with the head fixed without moving. On the other hand, the serial printer performs printing while the head reciprocates (shuttle movement) in a direction intersecting the conveyance direction of the recording medium.
Among these, in a line printer, an image is formed only by scanning the head once in a predetermined direction (single pass) with respect to a recording medium. When the recording medium is transported in a predetermined transport direction, the head is relatively scanned in the direction opposite to the transport direction. In other words, in the line printer, the recording medium passes under the head only once during recording. This is generally referred to as single pass printing.

(3. Modified examples)
The head unit 30 is not limited to the mode described with reference to FIG. 2 when there are two or more color ink compositions to be ejected. For example, the head unit 30 may be configured such that a plurality of heads that discharge different color ink compositions are arranged in order in the transport direction. In this modified example, the heads of the respective color ink compositions may be arranged so as to be in contact with each other or spaced apart from each other.

In addition, when the heads of the respective color ink compositions are arranged at intervals, a first temporary curing irradiation unit may be provided between the heads. That is, in the irradiation unit 40, the head of each color ink composition and the first temporary curing irradiation unit may be alternately provided.
In other words, the first temporary curing irradiation section is provided on the downstream side in the transport direction of the head of each ink color.

In the mode of FIG. 2 and the above modification, the printer 1 is a line printer, and each head of the head unit 30 can form dots corresponding to the width of the recording medium at a time.

On the other hand, the recording method of the present invention may be performed by a serial printer. In this case, for example, as disclosed in Japanese Patent Application Laid-Open No. 2003-341021, the ink composition is ejected and temporarily cured by a head and a temporary curing light source provided on the carriage, and then provided downstream in the transport direction from the carriage. The main curing may be performed with a main curing light source.

[Each step of the recording method]
Hereafter, the process which comprises the recording method of this embodiment is demonstrated in detail.
The recording method is performed using the above-described recording apparatus, and is a coating film formed by landing a photocurable ink composition on the recording medium while conveying the recording medium in the conveying direction ( The dots are cured by light irradiation to form an image. that time,
The recording method is performed by performing the following steps. FIG. 3 is a flowchart showing the recording method of the present embodiment.

As shown in FIG. 3, each of the above steps includes a first coating film forming step (S1), a first temporary curing step (S2), a second coating film forming step (S3), and a second Including a temporary curing step (S4) and a main curing step (S5). Hereinafter, each process will be described in detail.
In each step, the contents already described in the corresponding section of the recording apparatus are omitted.

(First coating film forming step)
In the first coating film forming step (S1), the first coating film is formed on the recording medium by discharging and landing the photocurable color ink composition onto the recording medium.
The first coating film forming step (S1) is performed by the head unit 30 in the printer 1 (recording apparatus). More specifically, the process is performed by a head located upstream in the transport direction. For example, in the embodiment shown in FIG. 2, the first coating film forming step (S1) is performed by the color ink head COLOR.

The weight of the color ink composition droplet is not particularly limited, but is preferably 1 ng to 20 ng, and the resolution of the color ink composition is not particularly limited, but is 720 dpi.
It is preferable that it is * 720 dpi-1440 dpi * 1440 dpi.

Furthermore, the film thickness when applying (printing) the color ink composition onto the recording medium is preferably 5 to 10 μm because good curability can be obtained.

(First temporary curing step)
In the first temporary curing step (S2), the first coating film is temporarily cured by first light irradiation.
This first temporary curing step (S2) is performed by the first temporary curing irradiation section 42e (FIG. 2) of the irradiation unit 40 in the printer 1 (recording apparatus).

As the conversion rate in this specification, a value measured by infrared spectroscopy (IR) spectroscopy is used. That is, when the amount of double bonds in the ink composition is measured by IR spectroscopy, the higher the conversion rate, the more the polymerization reaction proceeds, so the amount of double bonds decreases. It is represented by

The conversion rate in the first temporary curing step (S2) is preferably 30% or more and more preferably 40% or more in order to suppress the mixing of the color ink and the clear ink. On the other hand, regarding the upper limit of the conversion rate, the first temporary curing step is for preventing the color ink and the clear ink from being mixed, but if the conversion rate of the color ink is too high, When clear ink is ejected, clear ink repelling may occur. Therefore, the conversion rate of the color ink by temporary curing is preferably 95% or less.

In the first temporary curing step (S2), a light emitting diode (LED: Li) is used as a light source for the first light irradiation.
ght Emitting Diode). As described above, the LED can easily change the irradiation energy by controlling the magnitude of the input current.

The LED in the first temporary curing step (S2) preferably has a peak wavelength in the range of 350 nm to 450 nm, more preferably in the range of 380 nm to 450 nm. When the LED has a peak wavelength within the above range, an advantageous effect of cost reduction is obtained.

Although there is no restriction | limiting in the light irradiation energy of temporary hardening and it changes also with ink compositions, Preferably it is 300 mJ / cm < ² > or less as ultraviolet irradiation energy, More preferably, it is 5-200.
mJ / cm ² . When the ultraviolet irradiation energy is within the above range, bleeding is suppressed, and repelling of the applied ink is suppressed when further ink is applied onto the color ink after irradiation.

(Second coating film forming step)
In the second coating film forming step (S3), the photocurable clear ink composition is discharged and landed on at least one of the recording medium and part or all of the first coating film. Thus, the second coating film is formed on at least one of the recording medium and a part or all of the first coating film. That is, when the second coating film is formed on a part or all of the first coating film, an image in which the color ink and the clear ink constituting the photocurable ink set are (substantially) overlapped is formed. be able to. Further, when the second coating film is formed on the recording medium, it is possible to form separate images in which the color ink and the clear ink constituting the photocurable ink set do not overlap. Further, when the second coating film is formed on the recording medium and on a part or all of the first coating film, a pattern in which the color ink and the clear ink constituting the photocurable ink set overlap each other. And separate patterns that do not overlap can be formed.

The second coating film forming step (S3) is performed by the head unit 30 in the printer 1 (recording apparatus). More specifically, in the embodiment shown in FIG.
This is performed by the clear ink head CL located on the downstream side in the transport direction.
Here, the duty of the clear ink composition is not particularly limited.

The film thickness when applying (printing) the clear ink composition on the recording medium is preferably 3 to 15 μm because good curability can be obtained.

(Second temporary curing step)
In the second temporary curing step (S4), the second coating film is temporarily cured by second light irradiation. It is preferable to irradiate light from the temporary curing light source in the second temporary curing step before the clear ink composition is irradiated with light with irradiation energy from the main curing light source in the main curing step described later. . This mixes color ink and clear ink (
(Bleeding) can be suppressed.

The second temporary curing step (S4) is performed by the second temporary curing irradiation unit 42f (FIG. 2) of the irradiation unit 40 in the printer 1 (recording apparatus).

The conversion rate in the second temporary curing step (S4) is preferably 30% or more, and more preferably 40% or more in order to suppress the mixture of the color ink and the clear ink.

In the second temporary curing step (S4), LE is used as a light source for second light irradiation, that is, a light source for temporary curing.
It is preferable to use D. As described above, the LED can easily change the irradiation energy by controlling the magnitude of the input current.

The LED in the second temporary curing step (S4) preferably has a peak wavelength in the range of 350 nm to 450 nm, more preferably in the range of 380 nm to 450 nm. When the LED has a peak wavelength within the above range, an advantageous effect of cost reduction is obtained.

Although there is no restriction | limiting in the light irradiation energy of temporary hardening and it changes also with ink compositions, Preferably it is 300 mJ / cm < ² > or less as ultraviolet irradiation energy, More preferably, it is 5-200.
mJ / cm ² . When the ultraviolet irradiation energy is within the above range, bleeding is suppressed.

(Main curing process)
In the main curing step (S5), the temporarily cured first coating film and the second coating film are cured by light irradiation from a main curing light source to form an image.
This main curing step (S5) is performed by the irradiation unit 4 in the printer 1 (recording apparatus).
This is performed by the zero main curing irradiation unit 44. As described above, the light source for light irradiation from the main curing light source that can be used in the main curing irradiation unit 44 includes an LED or a lamp. Examples of the lamp include, but are not particularly limited to, for example, metal halide lamps, xenon lamps, carbon arc lamps, chemical lamps, and mercury lamps such as low-pressure mercury lamps and high-pressure mercury lamps. Mercury lamps or metal halide lamps are preferred.

The irradiation energy in the main curing step, that is, the irradiation energy when curing the coating film formed from the photocurable ink set described later by light irradiation from the light source for main curing is 200 to 800 mJ / cm ^{2 as} described above. 250-750 mJ / cm ² is preferable, 300-
700 mJ / cm ² is more preferable. When the irradiation energy is 200 mJ / cm ² or more, the transparency of the cured film of the clear ink is good. On the other hand, the irradiation energy is 8
Good color stability is acquired as it is 00 mJ / cm ² or less.
Note that when the clear ink main curing step and the color ink main curing step are performed simultaneously, the irradiation energy of the clear ink and the irradiation energy of the color ink can be the same irradiation energy. When the main curing step and the color ink main curing step are performed separately, it is possible to make the irradiation energy of the clear ink different from the irradiation energy of the color ink. However, even in this case, the recording device and the recording method should be simplified, assuming that the type of the main curing light source used in the clear ink main curing step and the color ink main curing step and the time required for the main curing step are close. Therefore, the irradiation energy of the clear ink main curing step and the irradiation energy of the color ink main curing step are each in the above-described range.
Moreover, the irradiation energy in this specification means the irradiation energy when evaluating by setting the film thickness after hardening of a coating film to 10 micrometers.
Here, the irradiation energy in the present embodiment is the irradiation energy from the main curing light source, and does not consider the irradiation energy from the temporary curing light source at all. The reason is,
There is a difference in wavelength due to the difference in the type of light source.

In the present embodiment, the main curing step may be performed without performing the first temporary curing step and the second temporary curing step described above. That is, when the second coating film is formed in the second coating film forming step on the first coating film formed in the first coating film process, the first coating film is The first temporary curing step may be performed or may not be performed.
When not performing the first temporary curing step and the second temporary curing step, the first coating film forming step and the second
Bleed (by performing the main curing process at an early stage after the coating film forming process of
It is possible to reduce bleeding. For example, the main curing step may be performed within 1 second, preferably within 0.1 second after completion of the coating film forming step.
In addition, in the case of performing the first temporary curing and the second temporary curing, and in the case of performing the main curing without performing the first temporary curing and the second temporary curing, after completion of the coating film forming step, It is preferable to perform the first curing step within 1 second, preferably within 0.1 second.
Alternatively, this embodiment may be used for applications where bleeding is not a problem.

When the main curing step is performed without performing the first temporary curing step and the second temporary curing step, recording is performed with the temporary curing irradiation portions 42e and 42f being OFF in the inkjet printer of FIG. Recording may be performed without providing the irradiation unit. In this embodiment, when the first temporary curing step and the second temporary curing step are performed or not performed, “main curing” is simply “curing”, “main curing light source” is “light source”, “main”. The “curing irradiation part” is also referred to as “irradiation part”, and the “main curing process” is also referred to as “curing process”.
Further, when the present embodiment is performed with the above-described serial printer, when performing the main curing step without performing the first temporary curing step and the second temporary curing step, for example, a head that ejects ink in a carriage Curing (main curing) may be performed in the same main scanning as the main scanning for ejecting ink with a light source provided downstream in the main scanning direction.

(Irradiation intensity of each irradiation part)
The irradiation energy by each irradiation unit can be obtained as the irradiation intensity of the irradiation unit multiplied by the irradiation duration. In irradiation, the irradiation intensity of the irradiation unit is constant, and it is preferable to adjust the irradiation energy by adjusting the irradiation duration. The adjustment of the irradiation duration time can be performed by adjusting the irradiation speed and the irradiation area when the irradiation unit performs relative scanning with respect to the recording medium. The irradiation intensity of the pre-curing irradiation part is 100 to 2000 mW / c.
m ² is preferable, 100 to 1000 mW / cm ² is more preferable, and 1
It is especially preferable to set it as 00-500 mW / cm < ² >. On the other hand, the irradiation intensity of the curing light source is preferably in a 100~2000mW / cm ^2, more preferably to 500~2000mW / cm ^2, and particularly preferably to 800~2000mW / cm ^2. In addition to the mercury lamp or metal halide lamp, a light emitting diode can also be used as the main curing light source.

[Photocurable ink set]
One embodiment of the present invention relates to a photocurable ink set used in the recording method of the above embodiment. The photocurable ink set (specific photocurable ink set) includes a photocurable color ink composition and a photocurable clear ink composition having a predetermined composition.

[Photocurable color ink composition]
The photocurable color ink composition constituting the photocurable ink set contains a polymerizable compound, a photopolymerization initiator, and a coloring material, and (1) acylphosphine oxide photopolymerization is used as the photopolymerization initiator. An initiator and (2) at least one of a thioxanthone photopolymerization initiator and / or an α-aminoalkylphenone photopolymerization initiator. In addition, the content of at least one of the thioxanthone photopolymerization initiator and / or the α-aminoalkylphenone photopolymerization initiator contained in the color ink composition is the total mass of the color ink composition ( 100% by mass), a predetermined amount is included.

[Photocurable clear ink composition]
On the other hand, the photocurable clear ink composition constituting the photocurable ink set contains a polymerizable compound and a photopolymerization initiator, and contains an acylphosphine oxide photopolymerization initiator as the photopolymerization initiator. In addition, the content of the acylphosphine oxide photopolymerization initiator contained in the clear ink composition is a predetermined amount with respect to the total mass of the clear ink composition.

Hereinafter, an additive (or an additive that may be included in the photocurable color ink composition and the photocurable clear ink composition (hereinafter, collectively referred to as “ink composition”) in this embodiment) Component).

(Photopolymerization initiator)
The photopolymerization initiator contained in the ink composition in the present embodiment is used to form a print by curing the ink present on the surface of the recording medium by photopolymerization by ultraviolet irradiation. By using ultraviolet rays (UV) among the radiation, the safety is excellent and the cost of the light source lamp can be suppressed.

(Acylphosphine oxide photopolymerization initiator)
The color ink composition and clear ink composition of this embodiment contain an acyl phosphine oxide photopolymerization initiator. Thereby, it is excellent in LED tack-free property.

The acylphosphine oxide compound constituting the acylphosphine oxide photopolymerization initiator is not particularly limited, and examples thereof include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,4,6-triethylbenzoyldiphenylphosphine. Fin oxide, 2,4,6-triphenylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis- (2,6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide is mentioned.

Examples of commercially available acylphosphine oxide photopolymerization initiators include DAROC.
UR TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide), IRGACURE 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide), and CGI403 (bis- (2,6- Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide).

(Thioxanthone photopolymerization initiator)
The color ink composition of this embodiment may contain a thioxanthone photopolymerization initiator together with the acylphosphine oxide photopolymerization initiator. Thereby, it is excellent in LED tack-free property.

The thioxanthone compound constituting the thioxanthone photopolymerization initiator is not particularly limited, and examples thereof include thioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-
Examples include chlorothioxanthone and 2,4-diethylthioxanthone.

As a commercial item of a thioxanthone compound, for example, KAYACURE DETX-S (
2,4-diethylthioxanthone) (trade name manufactured by Nippon Kayaku Co., Ltd.), KAYACURE ITX (2- / 4-isopropylthioxanthone), and the like. Particularly preferred.

(Α-aminoalkylphenone photopolymerization initiator)
The color ink composition of this embodiment may contain an α-aminoalkylphenone photopolymerization initiator together with the acylphosphine oxide photopolymerization initiator. Thereby, it is excellent in LED tack-free property.

The α-aminoalkylphenone compound constituting the α-aminoalkylphenone photopolymerization initiator is preferably a 1,3-α-aminoalkylphenone compound. Specific examples thereof include 2
-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,
2- (Dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- (4-methylthiophenyl)
-2-morpholinopropan-1-one.

Examples of commercially available α-aminoalkylphenone photopolymerization initiators include IRGACUR.
E 369 (2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl)-
Butanone-1), IRGACURE 379 (2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone)
IRGACURE 907 (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one).

(Other photopolymerization initiators)
Other photopolymerization initiators are not limited as long as they generate active species such as radicals and cations by the energy of light (ultraviolet rays) and initiate polymerization of the polymerizable compound. An agent or a cationic photopolymerization initiator can be used, and among these, it is preferable to use a radical photopolymerization initiator.

Examples of the radical photopolymerization initiator include aromatic ketones, aromatic onium salt compounds, organic peroxides, thio compounds other than thioxanthone compounds (thiophenyl group-containing compounds, etc.), hexaarylbiimidazole compounds, ketoximes. Examples include ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds other than α-aminoalkylphenone compounds.

Specific examples of the photo radical polymerization initiator include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl)- 2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (me Lucio) phenyl] -2-morpholino - propan-1
ON, triethanolamine, methyldiethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylamino Isoamyl benzoate, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, 4
-2-ethylhexyl dimethylaminobenzoate is mentioned.

Examples of commercially available radical photopolymerization initiators include IRGACURE 651 (2, 2
-Dimethoxy-1,2-diphenylethane-1-one), IRGACURE 184 (1
-Hydroxy-cyclohexyl-phenyl-ketone), DAROCUR 1173 (2-
Hydroxy-2-methyl-1-phenyl-propan-1-one), IRGACURE 2
959 (1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one), IRGACURE 127 (2-hydroxy-1- {
4- [4- (2-Hydroxy-2-methyl-propionyl) -benzyl] phenyl] -2
-Methyl-propan-1-one}, IRGACURE 907 (2-methyl-1- (4-
Methylthiophenyl) -2-morpholinopropan-1-one), IRGACURE 7
84 (bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium), IRGACURE
OXE 01 (1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]), IRGACURE OXE 02 (ethanone, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime)), IRGACURE 754 (oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid, 2- (2
-Hydroxyethoxy) ethyl ester mixture), Lucirin TPO, LR88
93, LR8970 (above, product name manufactured by BASF), Ubekrill P36 (product name manufactured by UCB), and the like.

The said photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type.

The photopolymerization initiator has a sufficiently high ultraviolet curing rate, and since there is almost no coloring due to the undissolved residue of the photopolymerization initiator or the photopolymerization initiator, the total weight (100% by mass) of the ink composition is It is preferable that it is 5-12 mass%.

In particular, (2) a thioxanthone photopolymerization initiator contained in the color ink composition and / or
Alternatively, the content of at least one of the α-aminoalkylphenone photopolymerization initiator is 0.5 to 4% by mass, preferably 1 to 4% by mass, based on the total mass of the color ink composition. 1.5-2.5 mass% is more preferable. When the content is 0.5% by mass or more, L
Excellent ED tack free. On the other hand, when the content is 4% by mass or less, the color stability of the ink is excellent. Among the thioxanthone photopolymerization initiators and α-aminoalkylphenone photopolymerization initiators, adhesion is excellent particularly when a thioxanthone photopolymerization initiator is included.
Moreover, it is preferable that a clear ink composition does not contain a thioxanthone photopolymerization initiator and an α-aminoalkylphenone photopolymerization initiator. This is because when the clear ink composition contains a thioxanthone photopolymerization initiator and an α-aminoalkylphenone photopolymerization initiator, it is transparent as well as the acylphosphine oxide photopolymerization initiator after color stabilization. This is because the property may be inferior.

Further, the content of the (1) acylphosphine oxide photopolymerization initiator contained in the color ink composition is preferably 4 to 12% by mass relative to the total mass of the color ink composition. The mass% is more preferable. When the content is within the above range, good LED tack-free properties can be obtained when combined with a thioxanthone-based initiator or an α-alkylphenone-based initiator.

Moreover, content of the acyl phosphine oxide type photoinitiator contained in the said clear ink composition is 5-12 mass% with respect to the total mass of this clear ink composition, and 6.5.
-9.5 mass% is preferable, and 7-9 mass% is more preferable. When the content is 5% by mass or more, the LED tack-free property is excellent. On the other hand, when the content is 12% by mass or less,
Excellent transparency of clear ink.

In addition, it is possible to omit the addition of a photopolymerization initiator by using a photopolymerizable compound as the polymerizable compound described above, but it is easier to start polymerization by using a photopolymerization initiator. It can be adjusted and is preferred.

(Polymerizable compound)
The polymerizable compound contained in the ink composition in the present embodiment is not particularly limited as long as it is a compound that is polymerized and solidified upon irradiation with light such as ultraviolet rays by the action of the above-described photopolymerization initiator. Various monomers and oligomers having a bifunctional group and a polyfunctional group having three or more functional groups can be used.

Examples of the monomer include unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid, salts or esters thereof, urethane,
Amides and their anhydrides, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes. Examples of the oligomer include oligomers formed from the above monomers such as linear acrylic oligomers, epoxy (meth) acrylates, aliphatic urethane (meth) acrylates, aromatic urethane (meth) acrylates, and polyesters (meth). An acrylate is mentioned.

Moreover, an N-vinyl compound may be included as another monofunctional monomer or polyfunctional monomer. Examples of the N-vinyl compound include N-vinylformamide, N-vinylcarbazole, N-vinylacetamide, N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine, and derivatives thereof. Among these, N-vinylcaprolactam is preferable because adhesion to the base material can be improved.

Among those listed above, esters of (meth) acrylic acid, that is, (meth) acrylates are preferred.

Among the (meth) acrylates, monofunctional (meth) acrylates include, for example, isoamyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, iso Myristyl (meth) acrylate, isostearyl (meth) acrylate, 2-ethylhexyl-diglycol (meth) acrylate, 2-hydroxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydiethylene glycol ( (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, lactone-modifiable Flexible (meth) acrylate, t-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, (
Examples include 2- (2-vinyloxyethoxyethyl) ethyl methacrylate and isobornyl (meth) acrylate and acryloylmorpholine.

Among the (meth) acrylates, examples of the bifunctional (meth) acrylate include triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and tripropylene glycol di ( (Meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4
-Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (
(Meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, EO (ethylene oxide) adduct di (meth) acrylate of bisphenol A, PO (propylene oxide) adduct di (meth) acrylate of bisphenol A, hydroxypivalic acid Examples include neopentyl glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate.

Among the (meth) acrylates, the trifunctional or higher polyfunctional (meth) acrylates include, for example, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate. ,
Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerin propoxytri (meth) acrylate, cowprolactone modified trimethylolpropane tri (meth) acrylate, pentaerythritol ethoxy Tetra (meth) acrylate,
And caprolactam-modified dipentaerythritol hexa (meth) acrylate.

Among these, a monofunctional (meth) acrylate is included as a polymerizable compound from the viewpoint of easy injection stability at the time of ink jet recording because the coating film has a high elongation at curing and low viscosity. It is preferable. Further, from the viewpoint of increasing the hardness of the coating film, it is more preferable to use a monofunctional (meth) acrylate and a bifunctional (meth) acrylate in combination. Said polymeric compound may be used individually by 1 type, and may use 2 or more types together.

Furthermore, the monofunctional (meth) acrylate preferably has one or more skeletons selected from the group consisting of an aromatic ring skeleton, a saturated alicyclic skeleton, and an unsaturated alicyclic skeleton. When the polymerizable compound is a monofunctional (meth) acrylate having the skeleton, the viscosity of the ink composition can be reduced, and the epoxy group-containing polymer can be effectively dissolved in the ink composition. it can.

As a monofunctional (meth) acrylate having an aromatic ring skeleton, for example, phenoxyethyl (
And (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate. Examples of the monofunctional (meth) acrylate having a saturated alicyclic skeleton include isobornyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. Examples of the monofunctional (meth) acrylate having an unsaturated alicyclic skeleton include dicyclopentenyloxyethyl (meth) acrylate. In the above, (meth) acrylate is exemplified, but simple acrylate is also useful.

  Said polymeric compound may be used individually by 1 type, and may use 2 or more types together.

As for content of a polymeric compound, 20 mass% or more is preferable with respect to the total mass of a color ink composition or a clear ink composition, More preferably, it is 60-90 mass%. When the content is within the above range, storage stability and curability are improved.
The color ink composition and / or clear ink composition particularly preferably contains a monofunctional monomer and a polyfunctional monomer. As the monofunctional monomer, N-vinylcaprolactam, phenoxyethyl (meth) acrylate, isobornyl (meta ) Acrylate, dicyclopentenyl (meth) acrylate, and (meth) acrylic acid 2- (2-vinyloxyethoxyethyl) ethyl are preferably contained. As a polyfunctional monomer, tripropylene glycol di (meth) It is preferable to contain any of acrylate, dipropylene glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate.

[Color material]
The ink composition in the present embodiment may further include a color material. Coloring materials are pigments and / or
Alternatively, at least one of the dyes can be used. Here, as described above, the color ink in the present specification refers to any colored ink except a colorless and transparent clear ink.
Therefore, unlike the color ink composition, the clear ink composition in the present embodiment does not contain a color material.

(Pigment)
In this embodiment, the light resistance of the ink composition can be improved by using a pigment as the color material. As the pigment, both inorganic pigments and organic pigments can be used.

As the inorganic pigment, carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black and channel black, iron oxide, and titanium oxide can be used.

Organic pigments include insoluble azo pigments, condensed azo pigments, azo lakes and chelate azo pigments, phthalocyanine pigments, perylene and perinone pigments, anthraquinone pigments, quinacridone pigments, dioxane pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc. Polycyclic pigments, dye chelates (eg basic dye chelates, acid dye chelates, etc.), dye rakes (basic dye rakes, acid dye rakes), nitro pigments, nitroso pigments, aniline black, daylight A fluorescent pigment is mentioned.

More specifically, as carbon black used as black ink, No. 2
300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52
, MA7, MA8, MA100, No. 2200B, etc. (Mitsubishi Chemical Corporation (Mitsubishi C
product name), Raven 5750, Raven 5250, R
aven 5000, Raven 3500, Raven 1255, Raven 70
0 etc. (above, product name manufactured by Carbon Columbia), Rega 1 40
0R, Rega1 330R, Rega1 660R, Mogul L, Monarch
700, Monarch 800, Monarch 880, Monarch 900
, Monarch 1000, Monarch 1100, Monarch 1300,
Monarch 1400, etc. (trade name manufactured by CABOT JAPAN K.K.), Col
or Black FW1, Color Black FW2, Color Black
FW2V, Color Black FW18, Color Black FW200
, Color B1ack S150, Color Black S160, Color
Black S170, Printex 35, Printex U, Printex
V, Printex 140U, Special Black 6, Special
Black 5, Special Black 4A, Special Black 4
Etc. (the above-mentioned product name manufactured by Degussa).

Examples of pigments used in white ink include C.I. I. Pigment White 6, 18,
21.

Examples of pigments used in yellow ink include 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, 9
8, 99, 108, 109, 110, 113, 114, 117, 120, 124, 128
129, 133, 138, 139, 147, 151, 153, 154, 167, 172
, 180.

Examples of pigments used in magenta ink include C.I. I. Pigment Red 1, 2, 3
4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19,
21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48 (Ca),
48 (Mn), 57 (Ca), 57: 1, 88, 112, 114, 122, 123, 14
4, 146, 149, 150, 166, 168, 170, 171, 175, 176, 17
7, 178, 179, 184, 185, 187, 202, 209, 219, 224, 24
5, and C.I. I. Pigment violet 19, 23, 32, 33, 36, 38,
43, 50.

Examples of pigments used for cyan ink include C.I. I. Pigment Blue 1, 2, 3,
15, 15: 1, 15: 2, 15: 3, 15:34, 15: 4, 16, 18, 22, 25
, 60, 65, 66, and C.I. I. Bat Blue 4, 60.

Examples of pigments other than magenta, cyan and yellow include C.I. I. Pigment green 7, 10, and C.I. I. Pigment brown 3, 5, 25, 26, and C.I. I. Pigment Orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34
36, 38, 40, 43, 63.

  The said pigment may be used individually by 1 type, and may use 2 or more types together.

(dye)
In the present embodiment, a dye can be used as the color material. The dye is not particularly limited, and acid dyes, direct dyes, reactive dyes, and basic dyes can be used.
Examples of the dye include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 1
42, C.I. I. Acid Red 52, 80, 82, 249, 254, 289, C.I. I. Acid Blue 9, 45, 249, C.I. I. Acid Black 1, 2, 24, 94, C.I. I
. Food Black 1, 2, C.I. I. Direct yellow 1, 12, 24, 33, 50, 5
5, 58, 86, 132, 142, 144, 173, C.I. I. Direct red 1, 4,
9, 80, 81, 225, 227, C.I. I. Direct blue 1, 2, 15, 71, 86
87, 98, 165, 199, 202, C.I. I. Directed Black 19, 38, 51
71, 154, 168, 171, 195, C.I. I. Reactive Red 14, 32, 5
5, 79, 249, C.I. I. Reactive black 3, 4, and 35 are mentioned.

  The said dye may be used individually by 1 type, and may use 2 or more types together.

The content of the color material is preferably 2 to 25% by mass with respect to the total mass of the color ink composition.
When the content is 2% by mass or more, the color developability is good, and when the content is 25% by mass or less, the effect of ultraviolet absorption of the coloring material on the curability is small so that the curability is good. It can be. That is, when the content is within the above range, both color developability and curability can be improved.

[Surfactant]
Since the ink composition in the present embodiment can prevent repellency to the substrate, it may further contain a surfactant. The surfactant is not particularly limited. For example, polyester-modified silicone or polyether-modified silicone can be used as the silicone-based surfactant, and polyether-modified polydimethylsiloxane or polyester-modified polydimethylsiloxane can be used. Particularly preferred. As a specific example, BYK-347
, BYK-348, BYK-UV3500, 3510, 3530, 3570 (trade names manufactured by BYK Japan KK).

(Polymerization inhibitor)
The ink composition in the present embodiment may further contain a polymerization initiator because of its good storage stability. The polymerization inhibitor that can be contained in the photocurable clear ink composition is not particularly limited. For example, IRGASTAB UV10 and UV22 (trade name, manufactured by BASF), hydroquinone monomethyl ether (KANTO CHEMICAL CO., INC)
Product name) etc. can be used.

[Other additives]
The ink composition in the present embodiment may contain additives (components) other than the additives listed above. Such components are not particularly limited, and may include, for example, conventionally known polymerization accelerators, penetration enhancers, wetting agents (humectants), and other additives. Examples of the other additives include conventionally known pigment dispersants, fixing agents, antifungal agents, preservatives, antioxidants, ultraviolet absorbers, chelating agents, pH adjusting agents, and thickeners.

[Recording medium]
A recorded matter is obtained by discharging the ink composition of the present embodiment onto a recording medium using the above-described recording method. Examples of the recording medium include an absorptive or non-absorbable recording medium. The recording method of the above embodiment has various absorption performances ranging from a non-absorbable recording medium in which the water-soluble ink composition is difficult to penetrate to an absorbent recording medium in which the water-soluble ink composition is easily penetrated. Widely applicable to recording media. However, when the ink composition is applied to a non-absorbable recording medium, it may be necessary to provide a drying step after being cured by irradiation with ultraviolet rays.

The absorbent recording medium is not particularly limited. For example, plain paper such as electrophotographic paper having high water-based ink permeability, ink jet paper (an ink absorbing layer composed of silica particles or alumina particles, or polyvinyl alcohol). Art paper and coats used for general offset printing with relatively low permeability of water-based ink from (PVA) and inkjet pyrrole (PVP) and other ink-absorbing layers composed of hydrophilic polymers such as polyvinylpyrrolidone (PVP). Examples thereof include paper and cast paper.

The non-absorbable recording medium is not particularly limited. For example, films and plates of plastics such as polyvinyl chloride, polyethylene, polypropylene, and polyethylene terephthalate (PET), and metals such as iron, silver, copper, and aluminum are used. Examples thereof include a plate, a metal plate produced by vapor deposition of these various metals, a plastic film, a plate made of an alloy such as stainless steel or brass.

As described above, according to this embodiment, it is possible to provide a recording method and a photocurable ink set used therefor, which are excellent in LED tack-free property, ink color stability, and clear ink transparency. . In particular, in high-speed other color printing in the single pass method, by adjusting the type and content of the photopolymerization initiator contained in the color ink composition and the clear ink composition, respectively, and the irradiation energy at the time of main curing, A printed matter with excellent color stability can be obtained.

Hereinafter, the embodiments of the present invention will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to only these examples.

[Use ingredients]
The components used in the following examples and comparative examples are as follows.

(Pigment dispersion)
IRGALITE BLUE GLO (CI Pigment Blue) as a pigment
15: 3, manufactured by BASF), Solspers 36000 (Noveon (No
veon Inc. ) Product name) (1% by mass with respect to the pigment dispersion). And the dispersion medium (T
A pigment dispersion having a pigment concentration of 15% by mass was prepared by dispersing the pigment in (PGDA).

(Photopolymerization initiator)
KAYACURE DETX-S (thioxanthone type, trade name of Nippon Kayaku Co., Ltd., abbreviated as “DETX-S” in Tables 1 and 2)
IRGACURE 369 (1,3-α aminoalkylphenone type, trade name, manufactured by BASF, abbreviated as “369” in Tables 1 and 2)
IRGACURE 819 (acylphosphine oxide type, trade name, manufactured by BASF, abbreviated as “819” in Tables 1 and 2)
DAROCURE TPO (acylphosphine oxide type, trade name, manufactured by BASF, abbreviated as “TPO” in Tables 1 and 2)

(Polymerizable compound)
Tripropylene glycol diacrylate (V # 310HP (trade name), manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), In Tables 1 and 2, “TPGDA
". )
N-vinylcaprolactam (Vinylcaprolactam (trade name), manufactured by BASF, abbreviated as “NVC” in Tables 1 and 2)

(Polymerization inhibitor)
Irgastab UV22 (trade name, manufactured by BASF, abbreviated as “UV22” in Tables 1 and 2)

[Surfactant]
Silicone surface conditioner BYK-UV3500 (trade name, manufactured by BYK, abbreviated as “UV3500” in Tables 1 and 2)

[Preparation of Photocurable Cyan Ink Composition]
The components described in Table 1 below were added so as to have the composition (unit: mass%) described in Table 1, and this was stirred with a high-speed water-cooled stirrer to obtain a photocurable cyan ink composition (hereinafter referred to as “the composition”). ,
It is also simply called “cyan”. ) Was prepared.

[Preparation of Photocurable Clear Ink Composition]
The components described in Table 2 below were added so as to have the composition (unit: mass%) described in Table 2, and this was stirred with a high-speed water-cooled stirrer to obtain a photocurable clear ink composition (hereinafter, Simply referred to as “clear”).

[Examples 1-6, Comparative Examples 1-6]
Evaluation 1 was performed using a photocurable ink set. The evaluation items are as follows. The results are shown in Tables 3 and 4 below.

[1. (Image quality evaluation on color stability)
Evaluation was performed using the inkjet printer (inkjet printer 1) shown in FIG. First, under the conditions of an ink discharge weight of 15 ng and a resolution of 720 × 720 dpi, 1
An inch × 1 inch cyan solid pattern was printed. Next, the first temporary curing irradiation unit 4
2e LED Firefly (Phoseon, peak wavelength 395 nm, irradiation intensity 100
mW / cm ² ) was irradiated with ultraviolet rays having an irradiation energy of 10 mJ / cm ² to perform temporary curing.
Subsequently, under the conditions of an ink discharge weight of 15 ng and a resolution of 720 × 720 dpi, 1 inch ×
A 2-inch clear solid pattern was overcoated. At this time, in order to perform this evaluation by observing the occurrence of bleeding at the boundary between the cyan solid pattern and the clear solid pattern, the cyan solid pattern and the clear solid pattern were aligned at the center. Next, the LED Firefly (trade name, manufactured by Phoseon, peak wavelength: 395 nm, irradiation intensity: 100 mW / cm ² ) of the second temporary curing irradiation section 42f is irradiated with ultraviolet rays having an irradiation energy of 10 mJ / cm ^{2 to} perform temporary curing. went.
And a metal halide lamp (main body irradiation device name: UVAPRINT 300HPLK)
The ink is irradiated with light from the main curing light source so as to have a predetermined integrated energy (irradiation energy at the time of main curing) using Honle Co., Ltd. A test pattern in which a cured film (image) was formed on # 125-E20 (trade name, manufactured by Toray Industries, Inc.) was obtained. In addition, the value of irradiation energy is the ultraviolet illuminance meter UM-10, light-receiving part UM-400.
(Trade name manufactured by KONICA MINOLTA SENSING, INC.).

L ^* , a ^* , b ^* of this cured film was measured, and the color difference (ΔE) based on the hue after one week
The change with time after the cured film was formed was plotted, and the time until ΔE became less than 2 was derived. The test pattern was produced using the printing apparatus described in FIGS.

The evaluation criteria are as follows. Of the evaluation criteria, 1, 2, and 3 are practically acceptable criteria.
3: Less than 1 hour,
2: 1 hour or more and less than 2 hours,
1: 2 hours to less than 24 hours,
0: More than 24 hours.

[2. (Image quality evaluation on bleeding)
A test pattern was obtained in the same manner as in “1. Image quality evaluation related to color stability”.
Evaluation was performed by visually observing the test pattern. The evaluation criteria are as follows.
A: There was no blur at the boundary between the cyan solid pattern and the clear solid pattern.
B: There was blurring at the boundary between the cyan solid pattern and the clear solid pattern.

From Table 3 and Table 4 above, in the test pattern image in which clear was overlaid on cyan, an image having poor color stability or a blur was observed. Therefore, in order to understand more clearly the relationship between the recording method of the photocurable ink set and the image quality, next, evaluate with images of separate test patterns that do not overlap cyan and clear (evaluation 2 by ink set). went.

[Examples 7 to 12, Comparative Examples 7 to 12]
Evaluation 2 with an ink set was performed. The evaluation items are as follows. The results are shown in Table 5 below.
And in Table 6.

Here, the following LED tack-free property is an evaluation of tack-free property after provisional curing (pinning) performed using an LED. On the other hand, the integrated energy shown in the table is the total amount of energy irradiated during the main curing performed using a metal halide lamp, and the light irradiation during the temporary curing performed using the LED (first and second). ) Is not included. In addition, the irradiation apparatus used in the main curing is UVAPRINT 300HPLK (trade name) manufactured by Honle.

[Evaluation items common to cyan ink and clear ink]
(1. LED tack free)
Photocurable ink was applied to Lumirror # 125-E20 (trade name, PET film manufactured by Toray Industries Inc.) with a bar coater so as to have a film thickness of 10 μm. Next, LED “Firefly (trade name, manufactured by Phoseon) having a peak at a wavelength of 395 nm” and ultraviolet light with an illuminance of 70 mW / cm ² were irradiated to the coated ink for a predetermined time. After the irradiation, the surface of the coating film was rubbed with a cotton swab and the irradiation time until the scratch marks were not measured was measured.
The evaluation criteria are as follows.
2: 0 seconds to less than 30 seconds,
1:30 to less than 60 seconds,
0: More than 60 seconds.

(2. Color stability)
Evaluation was performed using the ink jet printer shown in FIG. First, a cyan solid pattern of 1 inch × 1 inch was printed under the conditions of an ink discharge weight of 15 ng and a resolution of 720 × 720 dpi. Next, LED Firefly (
(Manufactured by Phoseon) was irradiated with ultraviolet rays having an irradiation energy of 10 mJ / cm ² to perform temporary curing.
And a metal halide lamp (main body irradiation device name: UVAPRINT 300HPLK)
The ink is irradiated with light from the main curing light source so as to have a predetermined integrated energy (irradiation energy at the time of main curing) using Honle Co., Ltd. A test pattern in which a cured film (image) was formed on 125-E20 (trade name, manufactured by Toray Industries, Inc.) was obtained. The L ^* , a ^* , b ^* of the cured film was measured, and the color difference (ΔE based on the hue after one week)
), The change over time after the cured film was formed was plotted, and the time until ΔE was less than 2 was derived.
The evaluation criteria are as follows. Of the evaluation criteria, 1, 2, and 3 are practically acceptable criteria.
3: Less than 1 hour,
2: 1 hour or more and less than 2 hours,
1: 2 hours to less than 24 hours,
0: More than 24 hours.

(3. Image quality evaluation on bleeding)
Evaluation was performed using the ink jet printer shown in FIG. First, a cyan solid pattern of 1 inch × 1 inch was printed under the conditions of an ink discharge weight of 15 ng and a resolution of 720 × 720 dpi. Next, LED Firefly (
(Manufactured by Phoseon) was irradiated with ultraviolet rays having an irradiation energy of 10 mJ / cm ² to perform temporary curing.
Subsequently, under the conditions of an ink discharge weight of 15 ng and a resolution of 720 × 720 dpi, 1 inch ×
A 2-inch clear solid pattern was overcoated. At this time, in order to perform this evaluation by observing the occurrence of bleeding at the boundary between the cyan solid pattern and the clear solid pattern, the cyan solid pattern and the clear solid pattern were aligned at the center. Next, the LED Firefly (trade name, manufactured by Phoseon Co., Ltd.) of the second temporary curing irradiation section 42f was irradiated with ultraviolet rays having an irradiation energy of 10 mJ / cm ² to perform temporary curing.
And a metal halide lamp (main body irradiation device name: UVAPRINT 300HPLK)
The ink is irradiated with light from the main curing light source so as to have a predetermined integrated energy (irradiation energy at the time of main curing) using Honle Co., Ltd. A test pattern in which a cured film (image) was formed on # 125-E20 (trade name, manufactured by Toray Industries, Inc.) was obtained. In addition, the value of irradiation energy is the ultraviolet illuminance meter UM-10, light-receiving part UM-400.
(Trade name manufactured by KONICA MINOLTA SENSING, INC.).
Evaluation was performed by visually observing the above test pattern. The evaluation criteria are as follows.
A: There was no blur at the boundary between the cyan solid pattern and the clear solid pattern.
B: There was blurring at the boundary between the cyan solid pattern and the clear solid pattern.

[Clear ink evaluation items] (4. Clear ink transparency)
Evaluation was performed using the ink jet printer shown in FIG. First, solid printing was performed on an area of 1 inch × 1 inch using clear ink under the conditions of an ink discharge weight of 15 ng and a resolution of 720 dpi × 720 dpi. Next, the LED Fi of the second temporary curing irradiation section 42f.
Refly (trade name, manufactured by Phoseon) was irradiated with ultraviolet rays having an irradiation energy of 10 mJ / cm ² to perform temporary curing. And metal halide lamp (main body irradiation device name: UVAPRINT)
The photocurable ink was cured by irradiating light from the light source for main curing so as to obtain a predetermined integrated energy (irradiation energy at the time of main curing) using 300 HPLK, manufactured by Honle. As a result, a test pattern in which a cured film (image) was formed on a recording medium (# 125-E20 [trade name], manufactured by Toray Industries, Inc.) was obtained. Measure the color of the cured film and the substrate, and the color difference between them (Δ
E) was calculated.
The evaluation criteria are as follows. Of the evaluation criteria, 1, 2, and 3 are practically acceptable criteria.
3: Less than 2,
2: 2 or more and less than 3,
1: 3 to less than 4,
0: 4 or more.

From Table 5 and Table 6 above, in the test pattern image in which cyan ink and clear ink are applied to different locations on the recording medium and cured, the cyan image has inferior color stability or blurring It was observed. As for clear images, it was newly found out that although there was no problem in color stability in all examples and comparative examples, there was an inferior transparency, that is, there was an initial coloration.

From the results of Table 5 and Table 6 above, when the tack-free properties of cyan ink and clear ink are evaluated separately, there is a correlation between the cyan ink bleeding and the tack-free property evaluation results of each ink. I understood that. Note that Comparative Example 8 and Comparative Example 11 will be described later.

Here, the significance of using ink as a set will be described. As described above, the test pattern was produced using the printing apparatus shown in FIG. 2, and in FIG. 2, the irradiation energy by the main curing irradiation unit 44 is the accumulated energy. Then, this accumulated energy becomes common between the color ink and the clear ink. In order to separate the integrated energy of the color ink and the clear ink, the main curing irradiation unit 44 is required for each ink color. However, when the main curing irradiation section 44 is provided in this way, it becomes complicated and the process of the recording method becomes complicated.
It is preferable that the color ink and the clear ink are fully cured at once by the main curing irradiation unit 44. Therefore, it is preferable to use the color ink and the clear ink as a set so that the main curing can be performed at one time. In this case, it is necessary to select each ink composition and accumulated energy so that all evaluations are other than 0 with a common accumulated energy.

Note that the irradiation energy of the first temporary curing irradiation unit 42e and the second temporary curing irradiation unit 42f in FIG. 2 is not included in the accumulated energy. Main curing irradiation section 44 (metal halide lamp)
The first temporary curing irradiation unit 42e and the second preliminary curing irradiation unit 42f (LED) have different wavelengths, but the integrated energy of the metal halide lamp affects the color stability and transparency.
On the other hand, the first temporary curing irradiation unit 42e and the second temporary curing irradiation unit 42f may be irradiated in consideration of bleeding or the like for each ink. In the case where the first temporary curing irradiation unit 42e and the second temporary curing irradiation unit 42f irradiate light with a sufficient amount of energy at the recording medium conveyance speed,
The curability of the ink composition is required. Tack free evaluation was performed as the standard.

[Reference Examples 1 to 23]
Next, as a reference, in order to examine what conditions are suitable as cyan ink and clear ink constituting the ink set used in the recording method of the present invention, it is used in the above examples and comparative examples. The ink was individually evaluated (Evaluation 3) using the ink composition prepared and the ink composition newly prepared. The evaluation items are as follows. The results are shown in Table 7, Table 8, and Table 9 below ("-" in Table 8 indicates that no evaluation was performed). In addition, except that the test was performed with each ink composition alone without performing the test with the ink composition set,
Test patterns were created and evaluated in the same procedure as in Examples 7-12 and Comparative Examples 7-12.

Here, the following LED tack-free property is an evaluation of temporary curing (pinning) property by the LED. On the other hand, the integrated energy described in the table is for the main curing by the metal halide lamp and does not include the pinning (temporary curing) by the LED. In addition, the irradiation apparatus used in the main curing is UVAPRINT 300HPLK (trade name) manufactured by Honle.

[1. (LED tack-free)
This evaluation was performed in the same manner as the LED tack-free evaluation performed in Examples 7-12 and Comparative Examples 7-12.
The evaluation criteria are as follows.
2: 0 seconds to less than 30 seconds,
1:30 to less than 60 seconds,
0: More than 60 seconds.

[2. (Color stability)
This evaluation was performed in the same manner as the color stability evaluation performed in Examples 7 to 12 and Comparative Examples 7 to 12 described above.
The evaluation criteria are as follows. Of the evaluation criteria, 1, 2, and 3 are practically acceptable criteria.
3: Less than 1 hour,
2: 1 hour or more and less than 2 hours,
1: 2 hours to less than 24 hours,
0: More than 24 hours.

[3. (Transparency of clear ink)
This evaluation was performed in the same manner as the transparency evaluation of the clear ink performed in Examples 7 to 12 and Comparative Examples 7 to 12 described above.
The evaluation criteria are as follows. Of the evaluation criteria, 1, 2, and 3 are practically acceptable criteria.
3: Less than 2,
2: 2 or more and less than 3,
1: 3 to less than 4,
0: 4 or more.

From Tables 7, 8 and 9, the following was found. From Reference Example 9, it was found that when neither the thioxanthone photopolymerization initiator nor the 1,3-α aminoalkylphenone photopolymerization initiator was contained, the tack-free property was poor. Further, from Reference Example 23, it was found that when the content of the acylphosphine oxide photopolymerization initiator was as small as 4% by mass, the tack-free property was poor (Reference Example 20 having a content of 6% by mass). The tack-free property of is good.)

From Reference Example 10, since the cyan pigment has an absorption wavelength even when the acylphosphine oxide photopolymerization initiator is added up to the maximum amount (12% by mass) that is acceptable for clear ink, tack-free properties are different from those for clear ink. Was found to be insufficient. When compared with Reference Example 9 in which the content of the acylphosphine oxide photopolymerization initiator was reduced to 5% by mass, the effect of improving the curability was not observed. Moreover, from Reference Example 11, it was found that tack-free properties can be secured by containing a predetermined amount of DETX-S (thioxanthone photopolymerization initiator). The thioxanthone photopolymerization initiator has a larger light absorption on the shorter wavelength side than the acylphosphine oxide photopolymerization initiator, and the overlap with the absorption wavelength of the pigment is less than that of the acylphosphine oxide photopolymerization initiator. It was found that a tack-free state can be secured. Further, from Reference Example 12, when the cyan ink does not contain an acylphosphine oxide photopolymerization initiator, the curability is inferior, and it is difficult to improve the curability with only the thioxanthone photopolymerization initiator. I understood. Moreover, from Reference Example 13, it was found that the 1,3-α aminoalkylphenone photopolymerization initiator produced the same results as the thioxanthone photopolymerization initiator.

In addition, the following has been confirmed or expected: It was confirmed that the content of the acylphosphine oxide photopolymerization initiator in the cyan ink was preferably 2 to 10% by mass. Specifically, each evaluation result was good in the reference examples within this range. On the other hand, from Reference Example 12, it is expected that the tack-free property is inferior when the content is less than 2% by mass. About the upper limit of the said content, it was confirmed from Reference Example 11 that it can add to 10 mass%. If the content exceeds 10% by mass, the clear ink may be yellowed from the result of the transparency evaluation. However, unlike the clear ink, the cyan ink is not noticeably colored (yellowing). It is unclear whether the content exceeding 10% by mass is in a practically acceptable range. However, even if the content is 10% by mass, Reference Example 1
From the result of 0, the photopolymerization initiator is inferior in curability when the acyl phosphine oxide is used alone.
Therefore, even if the content is 11% by mass, there is a high possibility that the content is not practically acceptable. Further, if the content of the acylphosphine oxide photopolymerization initiator is further increased, the risk of yellowing increases. It was not tested at a content higher than.

From the results of the examples, comparative examples, and reference examples described above, the color stability evaluation result of cyan ink and the transparency evaluation result of clear ink are independent and do not interact with each other. I understand. Therefore, not limited to the above-described examples and comparative examples, as long as the accumulated energy amount is within a predetermined range, Reference Examples 1 to 14 related to cyan and Reference Examples 15 to 23 related to clear
Can be combined as appropriate to produce a desired ink set.

[Examples 12 to 20, Comparative Examples 13 to 19]
Evaluation 4 with an ink set was performed. The ink composition and evaluation items are as follows. The results are shown in Tables 10 and 11 below.
[Ink composition]
The ink compositions other than the cyan ink composition 11 and the cyan ink composition 12 were the same as those described above, and the cyan ink composition 11 and the cyan ink composition 12 were newly prepared.
Cyan ink composition 11: 3% by mass of DETX-S in cyan ink composition 1
Cyan ink composition 11 was prepared in the same manner except that 3% of isopropylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., 2-isopropylthioxanthone, 4-isopropylthioxanthone mixed product) was used instead of 3%.
Cyan ink composition 12: 3% by mass of DETX-S in cyan ink composition 1
The cyan ink composition 12 was used in the same manner except that 4 mass% was used instead of 5 and 54.9 mass% was used instead of 55.9 mass% of tripropylene glycol diacrylate.
It was created.

[1. (Image quality evaluation on color stability)
The evaluation was performed in the same manner as the image quality evaluation related to the color stability of evaluation 1 described above.
[2. (Image quality evaluation on bleeding)
The evaluation was performed in the same manner as the image quality evaluation related to the blur of evaluation 1 described above.
[3. Image quality evaluation for adhesion)
A test pattern was obtained by the same method as the image quality evaluation related to the color stability of Evaluation 1 described above.
Adhesiveness evaluation was performed by the following method about the location where the solid pattern by the cyan ink and the solid pattern by the clear ink of the obtained test pattern overlapped.
JIS K5600-5-6 (Coating General Test Method-Part 5: Mechanical Properties of Coating Film-Section 6:
The adhesion between the film and the cured film was evaluated according to adhesion (cross-cut method). The classification of evaluation criteria is as follows.
A: The edge of the cut is completely smooth, and there is no peeling in the eyes of any lattice.
B: Small peeling of the coating film at the intersection of cuts is observed.
C: The coating film is peeled along the edge of the cut and / or at the intersection.
D: The coating film is partially or completely peeled along the edges of the cut, and / or various parts of the eyes are partially or completely peeled off.

[About Example 17]
For Example 17, when creating a test pattern in each of the image quality evaluations described above, the first temporary curing irradiation unit 42e and the second temporary curing irradiation unit 42 of the inkjet printer 1 were used.
f was turned OFF, and the main curing with the light source for main curing was performed without performing temporary curing of the solid pattern with cyan ink and the solid pattern with clear ink.

[Comparative Example 20]
In Comparative Example 20, in the inkjet printer 1, the cyan ink head on the upstream side in the transport direction is filled with clear ink, the clear ink head on the downstream side is filled with cyan ink,
The configuration is the same as that of Example 13 except that the clear ink is first ejected onto the recording medium to form a clear pattern and a cyan pattern is formed on a part of the clear pattern.

From Tables 10 and 11, all examples were excellent in image quality evaluation regarding color stability and image quality evaluation regarding adhesion. In Example 17, in which the cyan ink composition and the clear ink composition were not temporarily cured, the image quality evaluation related to bleeding was evaluation B. However, the image quality evaluation related to color stability and the image quality evaluation related to adhesion were evaluated temporarily. The evaluation was the same as that of the cured example. In addition, for Example 17, the above-described Evaluation 2 of 4. When a test pattern was created by the same method as the transparency evaluation of the clear ink and the transparency evaluation of the clear ink was performed, the evaluation was 1. On the other hand, all the comparative examples were inferior in image quality evaluation regarding adhesion. Note that Comparative Example 18 has the same configuration as Comparative Example 8 and Comparative Example 19 have the same configuration as Comparative Example 11 described above, but the image quality evaluation related to adhesion was poor. Comparative Example 20 was inferior in adhesion.

[Examples 21 to 29, Comparative Examples 21 to 28]
Evaluation 5 with an ink set was performed. The ink composition and evaluation items are as follows. The contents and results are shown in Tables 12 to 14 below.

[Ink composition]
A cyan ink composition (compositions 13 to 17) and a clear ink composition (composition 6) were prepared in the same procedure as the ink composition used in the above-described evaluation except that the compositions were changed to those shown in Tables 12 and 13. To 10).

[Use ingredients]
・ 2- (2-vinyloxyethoxyethyl) ethyl acrylate (Nippon Shokubai Co., Ltd., described as VEEA in the table)
・ Phenoxyethyl acrylate (Osaka Organic Chemical Co., Ltd., described as PEA in the table)
Dicyclopentenyl acrylate (FA-511AS, manufactured by Hitachi Chemical Co., Ltd., described as FA511 in the table)

[Image quality evaluation method]
Each image quality evaluation was performed in the same manner as the above evaluation.

[Recording method]
In Examples 21 to 27 and Comparative Examples 21 to 26 of Evaluation 5, the main curing irradiation unit 44 in the inkjet printer (inkjet printer 1) of FIG.
A pattern for image quality evaluation was prepared in the same manner as in Evaluation 1 except that it was replaced with ED (peak wavelength: 395 nm, irradiation intensity: 1000 mW / cm ² ) (inkjet printer 2). On the other hand, in Examples 28 to 29 and Comparative Examples 27 and 28, an image quality evaluation pattern was created using the inkjet printer 3 which is a serial printer shown in FIG.

The inkjet printer 3 has the configuration shown in FIG. 4 with respect to the periphery of the carriage including the head and the irradiation unit and the recording medium transport mechanism, and the configuration of the entire printer other than these is the same as that of the inkjet printer 1.
In FIG. 4, 6 is a carriage, 8 is each color ink head including a cyan ink head, 10 is a clear ink head, 11 is an irradiation unit, 5 is a guide rail, and 2 is a platen. 4 is a conveyance roller, A and B are main scanning directions, and X
Is the sub-scanning direction. Ink is ejected from the ink head to the ink recording medium (recording medium) by main scanning in the main scanning direction (either direction A or direction B) of the carriage,
In addition, the ink that has adhered to the recording medium is irradiated from the irradiation unit behind the ink head in the main scanning direction of the two irradiation units 11. Main scanning and sub-scanning (conveyance of the recording medium) are alternately performed, and the main scanning direction is alternately switched between the A direction and the B direction at each main scanning.

In each color ink head 8 and clear ink head 10, the length (distance H) in the sub-scanning direction of the nozzle row used for ejecting one ink is the same. When the distance (distance S) in one sub-scanning direction is the same as the distance H, a serial 1-pass recording method is performed in which printing is performed in one main scan (pass) for one ink, and the distance S is the distance. If shorter than H,
A serial multi-pass printing method is performed in which printing is performed in two or more main scans (passes) for one ink. When the serial multi-pass recording method is performed, the number of passes can be increased as the distance S is shorter, and the number of passes can be 2 or more. When the serial multi-pass printing method is performed, the ink ejected to the recording medium in the first pass is 1 in the first pass.
After one irradiation from each irradiation unit 11, two irradiations are further performed from two irradiation units 11 per pass in the second and subsequent passes. Each irradiation part 11 is LE.
D (peak wavelength: 395 nm, irradiation intensity: 1000 mW / cm ² ), and from the irradiation unit 11 only from the portion aligned with the ink head 8 or the clear ink head 10 in the main scanning direction (the portion where the position in the sub-scanning direction matches). The recording medium can be irradiated by emitting UV light. For details of the ink jet printer 3, reference can be made, for example, to JP-A-2006-289722.

Examples 21 to 25, Comparative Examples 21 to 24: As in Evaluation 1, this is a recording method in which the recording medium is scanned (passed) only once with respect to the print head by the line printer (line 1 pass). The cyan pattern is the first temporary curing (irradiation energy 1) by the first temporary curing irradiation unit 44e.
0 mJ / cm ²⁾ and, curing the second temporary curing (irradiation energy 10 mJ / cm ²⁾ and further the subsequent main curing radiation section by a subsequent second temporary curing irradiation section 44f (irradiation energy 200 mJ / cm ² ), The ink was cured by being irradiated with a total of 220 mJ / cm ² . The clear pattern is obtained by performing second temporary curing (irradiation energy 10 mJ / cm ² ) by the second temporary curing irradiation unit 44 f and subsequent main curing (irradiation energy 20 by the main curing irradiation unit).
0 mJ / cm ² ), and the ink was cured by irradiation of a total of 210 mJ / cm ² . The irradiation energy of each irradiation part for temporary curing and the irradiation part for main curing was performed by adjusting the irradiation continuation time irradiated to the recording medium from each irradiation part.

Examples 26 and 27, Comparative Examples 25 and 26: An image quality evaluation pattern was prepared in the same manner as in Example 21 except that the irradiation energy for main curing was changed to that shown in the table.

Example 28: Using a serial printer (inkjet printer 3), cyan pattern formation is completed by two passes of a cyan ink head arranged upstream of the recording medium in the sub-scanning direction of the ink head. Among them, there are dots attached to the recording medium by the first pass scanning and dots attached to the recording medium by the second pass scanning. Subsequently, a clear pattern is formed so as to overlap with a part of the cyan pattern by two passes by the clear ink head arranged in the downstream direction of the sub-scanning direction of the recording medium in the print head. In the clear pattern, there are dots attached to the recording medium by the first pass scanning and dots attached to the recording medium by the second pass scanning. The irradiation duration in one main scanning was adjusted so that the irradiation energy of one irradiation by the irradiation unit 11 was 100 mJ / cm ² .
The cyan pattern (A) is attached to the recording medium in the first pass of the cyan ink head,
Irradiated once by one irradiation unit 11 in a pass to which dots are attached, and then irradiated six times by two irradiation units 11 in each of the second pass of the cyan head and three passes by two passes of the clear head, Cyan dots irradiated with a total of 100 × 7 = 700 mJ / cm ² and (B
) Attached to the second pass of the cyan head, one irradiation unit 1 in the pass where the dots are attached
1 is irradiated once, and then two irradiation units 11 are respectively provided by two passes of the clear head.
A cyan dot irradiated four times with a total of 100 × 5 = 500 mJ / cm ² ,
Exists. In the clear pattern, (A) the first pass of the clear ink head is attached to the recording medium, and the irradiation unit 11 irradiates once in the pass where the dots are attached, and then the second pass of the clear head. Irradiated twice by the irradiation unit 11, a total of 100 × 3 = 300
Clear dots irradiated with mJ / cm ² and (B) attached to the second pass of the clear ink head, and irradiated once by the irradiation unit 11 in the pass where the dots were attached, and 100 × 1 = 10
And cyan dots irradiated with 0 mJ / cm ² .

Example 29: The irradiation duration in one main scan was adjusted so that the energy of one irradiation with respect to the recording medium by each irradiation unit of the serial printer (inkjet printer 3) was 200 mJ / cm ² . Cyan pattern formation was completed in one pass by a cyan ink head arranged upstream of the recording medium in the sub-scanning direction of the ink head, and the cyan pattern was attached to the recording medium by scanning in one pass. There are dots. Subsequently, a clear pattern is formed so as to overlap with a part of the cyan pattern by one pass by the clear ink head arranged in the downstream direction of the sub-scanning direction of the recording medium in the print head. In the clear pattern, there are dots attached to the recording medium by one-pass scanning. The irradiation energy of cyan dots is 200 + 200 mJ / cm ² , and the irradiation energy of clear dots is 200 mJ / cm ² .

Comparative Example 27: The irradiation duration in one main scanning was adjusted so that the energy of one irradiation of the recording medium by each irradiation unit of the serial printer (inkjet printer 3) was 50 mJ / cm ² . The cyan pattern formation is completed by two passes by the cyan ink head arranged upstream of the recording medium in the sub-scanning direction of the ink head, and the cyan pattern is attached to the recording medium by the first pass scanning. Dots and dots attached to the recording medium by the second pass scanning exist. Subsequently, a clear pattern is formed so as to overlap with a part of the cyan pattern by one pass by the clear ink head arranged in the downstream direction of the sub-scanning direction of the recording medium in the print head. 1 in clear pattern
There are dots attached to the recording medium by the second pass scanning and dots attached to the recording medium by the second pass scanning. In the cyan pattern, the irradiation energy is 50 × 1 + 50 ×
4 mJ / cm ² of present and cyan dots cyan dots and 50 × 3 + 50 × 4mJ / cm 2, the cyan dots and 50 of the irradiation energy in the clear pattern 50 × 1 mJ / cm ²
× 3 mJ / cm ² cyan dots exist.

Comparative Example 28: The irradiation duration in one main scan was adjusted so that the energy of one irradiation with respect to the recording medium by each irradiation unit of the serial printer (inkjet printer 3) was 150 mJ / cm ² . The cyan pattern formation is completed by two passes by the cyan ink head arranged upstream of the recording medium in the sub-scanning direction of the ink head, and the cyan pattern is attached to the recording medium by the first pass scanning. Dots and dots attached to the recording medium by the second pass scanning exist. Subsequently, a clear pattern is formed so as to overlap with a part of the cyan pattern by one pass by the clear ink head arranged in the downstream direction of the sub-scanning direction of the recording medium in the print head. In the clear pattern, there are dots attached to the recording medium by the first pass scanning and dots attached to the recording medium by the second pass scanning. Irradiation energy is 150 × 1 + 1 in the cyan pattern
There are 50 × 4 mJ / cm ² cyan dots and 150 × 3 + 150 × 4 mJ / cm ² cyan dots. In the clear pattern, the irradiation energy is 150 × 1 mJ / cm ² cyan dots and 150 × 3 mJ / cm ^2. Cyan dots.

From Tables 13 and 14 above, all the examples had excellent image quality evaluation results, while the comparative examples were
At least one of the image quality evaluations was inferior. Accordingly, a cyan ink containing an acylphosphine oxide photopolymerization initiator and at least one of 0.5 to 4% by mass of a thioxanthone photopolymerization initiator and / or an α-aminoalkylphenone photopolymerization initiator. A coating film formed from the ink set is cured by light irradiation from a light source using an ink set comprising the composition and a clear ink composition containing 5 to 12% by mass of an acylphosphine oxide photopolymerization initiator. It has been found that when the irradiation energy at the time is 100 to 800 mJ / cm ² , the image quality can be excellent, and in particular, both transparency and color stability can be achieved. In this evaluation 5, it is understood that each irradiating part at the time of irradiation is the same type of light source, and when performing a plurality of times of irradiation, the total irradiation energy should be within the predetermined range described above. . Further, it can be seen that the irradiation energies of the cyan ink and the clear ink do not have to be the same, and each may be within a predetermined range.

When using a serial printer, the following can also be said. The serial printer can be configured so that the irradiation is performed by the main scanning after the main scanning in which the ink is ejected. Therefore, even if the irradiation energy is small in one irradiation, the irradiation by the subsequent main scanning is performed. Thus, the total irradiation energy can be increased. Although not shown in FIG. 4, at least one of the irradiation units 11 extends to the downstream side of the clear ink head in the sub-scanning direction, and the extending portion also emits light for printing by the clear ink head. Irradiation may be performed after the main scanning by the extended portion of the irradiation unit. In this case, the total irradiation energy including irradiation by the extended part of the irradiation part may be within the above range. In this case, it is preferable in that the difference in irradiation energy between the cyan ink and the clear ink can be reduced while using a serial ink jet printer, and that the irradiation energy can be supplemented by irradiation from the extended portion when the irradiation energy of the clear ink is insufficient. .

DESCRIPTION OF SYMBOLS 1 ... Printer, 20 ... Conveyance unit, 23A ... Upstream conveyance roller, 23B ... Downstream conveyance roller, 24 ... Belt, 30 ... Head unit, 40 ... Irradiation unit, 42e ... First temporary curing irradiation part, 42f ... Second pre-curing irradiation unit, 44 ... main curing irradiation unit, 50 ... detector group, 60 ... controller, 110 ... computer, CL ... clear ink head,
COLOR ... Color head, S ... Recording medium, S1 ... First coating film forming step, S2 ... First temporary curing step, S3 ... Second coating film forming step, S4 ... Second temporary curing step, S5 ... Main curing process.

Claims (16)

Photocurable ink set comprising a photocurable color ink composition containing a polymerizable compound, a photopolymerization initiator, and a coloring material, and a photocurable clear ink composition containing a polymerizable compound and a photopolymerization initiator is used. Recording method,
The photocurable color ink composition comprises (1) an acyl phosphine oxide photopolymerization initiator and 0.5 to 4% by mass of (2) thioxanthone photopolymerization based on the total mass of the color ink composition. At least one of an initiator and / or an α-aminoalkylphenone photopolymerization initiator,
The photocurable clear ink composition contains 5 to 12% by mass of acylphosphine oxide photopolymerization initiator based on the total mass of the clear ink composition,
Forming a first coating film on the recording medium from the photocurable color ink composition;
Irradiating the first coating film with light from a light emitting diode to temporarily cure;
Forming a second coating film by the photocurable clear ink composition on the first coating film that has been temporarily cured;
Curing a coating film formed from the photocurable color ink composition and the photocurable clear ink composition by light irradiation from a light source,
Irradiation energy at the time of curing the coating film formed from said photocurable color ink composition and the light-curable clear ink composition by irradiation with light from a light source is 100 to 800 mJ / cm ^2, the light source emitting A recording method, which is a diode. Irradiation energy at the time of curing the coating film formed from said photocurable color ink composition and the light-curable clear ink composition by irradiation with light from a light source is 200~800mJ / cm ^2, to claim 1 The recording method described.   The said photocurable color ink composition of Claim 1 or 2 containing 0.5-4 mass% (alpha) amino alkyl phenone type photoinitiator with respect to the total mass of this color ink composition. Recording method.   The coating film formed from the ink set is formed by discharging the photocurable color ink composition and the photocurable clear ink composition from a print head, respectively. The recording method according to any one of the above.   The recording method according to claim 1, wherein the light emitting diode has a peak wavelength in a range of 350 to 450 nm. The photocurable color ink composition comprises 0.5 to 3% by mass of (2) a thioxanthone photopolymerization initiator and / or an α-aminoalkylphenone photopolymerization initiator based on the total mass of the color ink composition. 6. The recording method according to claim 1 , comprising at least one of the above. By curing the coating film formed by discharging the photocurable ink set from the print head and landing on the recording medium while scanning the recording medium relative to the print head by light irradiation. A recording method for forming an image, comprising:
A first coating film forming step of forming a first coating film on the recording medium by discharging and landing the photocurable color ink composition on the recording medium;
A first temporary curing step of temporarily curing the first coating film by first light irradiation;
By discharging the photocurable clear ink composition onto at least one of the recording medium and part or all of the first coating film, one of the first coating film and the recording medium is discharged. A second coating film forming step of forming a second coating film on at least one of the part or the whole, and
A second temporary curing step of temporarily curing the second coating film by second light irradiation;
7. The recording according to claim 1, comprising: a main curing step in which the temporarily cured first coating film and the second coating film are cured by light irradiation from the light source. Method.   The recording method according to claim 7, wherein a conversion rate in the first temporary curing step is 30 to 95%.   The recording method according to claim 7 or 8, wherein a conversion rate in the second temporary curing step is 30 to 100%. The recording method according to claim 1, wherein the light source has an irradiation intensity of 500 to 2000 mW / cm ² .   The recording method according to claim 1, wherein recording is performed using a line inkjet printer.   The recording method according to claim 1, wherein recording is performed using a serial ink jet printer.   The recording method according to claim 12, wherein the ink attached to the recording medium by the main scanning is irradiated by the main scanning and the main scanning after the main scanning.   The recording method according to claim 12 or 13, wherein the irradiation energy of the photocurable color ink composition is different from the irradiation energy of the photocurable clear ink composition. The said photocurable color ink composition contains 5-12 mass% (1) acyl phosphine oxide type photoinitiator with respect to the gross mass of this color ink composition. 2. The recording method according to item 1. Recording apparatus for recording by the recording method according to any one of claims 1 to 15.

Images