JP5132382B2 - Inkjet recording device - Google Patents

Description

  The present invention relates to a high-quality on-demand foil transfer printing apparatus, and more particularly to an ink jet recording apparatus capable of multicolor foil transfer and printing on a foil.

  In the printing field, a metal layer or hologram can be attached to a substrate (paper, film) ("foil stamping" or "foil transfer") in order to enhance the decorativeness of printed materials such as packages and catalogs and to prevent counterfeiting. It is used.

Two types of foil transfer devices are known.
(1) Hot stamping: a transfer film with a heated die using a transfer film provided with a wax layer as a separating layer, usually a thin metal layer spread on it and further coated with a heat sensitive adhesive. Is bonded to the substrate, whereby the die-shaped foil is bonded to the substrate. With this device, it is necessary to produce a dedicated press die for each image. Since a stationary time is required in a state where the die is pressed, printing and foil pressing are performed in separate processes, and productivity is poor.
(2) Cold foil method: An image of a dedicated adhesive is formed on a substrate in place of ink in a printing machine that prints process colors other than foil. A special foil transfer film (with a separation layer on the film and a metal layer spread on top of it) is niped at room temperature in the printing machine, and the foil is formed like an adhesive image. Transfer onto the substrate. The adhesive used for this is a pressure-sensitive UV curable adhesive. When the foil is transferred, it remains sticky and acts as a pressure-sensitive adhesive. It is polymerized and cured by UV light transmitted through the film to strongly bond the substrate and the foil. This cold foil method is becoming mainstream because it does not require a die that is expensive and has a long production lead time, can be stamped on a printing press, and has high productivity.

  On the other hand, in the printing field, digital (on-demand) printing presses that do not use printing plates have increased the share of digital printing presses using various methods (electrophotographic / inkjet) from the viewpoint of low cost and short lead time when small lots are used. ing. However, printing using foil stamping is frequently used in catalogs and packages that require high decorativeness, but digital printing has not been easily applied because there is no device that can perform foil stamping as needed without plate. For this reason, as in the case of digital printing of color images, there has been a demand for an apparatus that can perform stamping as needed without using a plate based on digital images.

(1) Problems of conventional digital on-demand foil stamping apparatus.
In Patent Document 1, i) a liquid is applied to a desired pattern by ink jet, ii) "a means for irradiating UV light of this adhesive and curing", "a means for transferring a pattern from a foil to a substrate", and a dry process An apparatus for continuously performing image forming and foil pressing, in which an image forming unit is continuously formed by an electrophotographic and inkjet digital printing apparatus, is disclosed. However, in this document, foil transfer is performed after image formation. For example, in the case of a job for transferring a gold foil and a job for transferring a silver foil, it is necessary to exchange the foil for each job. The digital on-demand printing method has the advantage of good efficiency with short jobs, but with this method, it is necessary to change the foil each time the foil color changes, and the number of short jobs increases and the foil type can be switched. As the number of times increases, the efficiency decreases significantly. Moreover, it is necessary to stock many types of foils, and this is also inefficient.

  Patent Document 2 discloses a printing apparatus in which a digital image is formed by a radiation curable ink jet method and then continuously pressed by hot stamping. Foil stamping after image formation. Foil transfer is not on-demand using a die and again the foil type must be changed each time the foil color is changed. , I) A method is disclosed in which a liquid is applied to a desired pattern by inkjet, and ii) “curing the UV light of this adhesive by curing” and “transferring the pattern from the foil to the substrate” simultaneously. . According to this method, the cured liquid can be a crosslinked polymer rather than a pressure-sensitive adhesive, so that sufficient adhesion between the foil and the substrate can be obtained. However, since the liquid before curing has a low viscosity, the liquid moves and spreads when it is pressure-bonded to the foil transfer film, so that the shape of the transferred foil is disturbed and the quality of the transferred foil is poor. There is.

JP 2005-501761 A JP 2007-283732 A

  The present invention is an ink jet recording apparatus that solves the above-described problems of the prior art in that high-quality on-demand foil transfer printing apparatus cannot perform multicolor foil transfer and printing on the foil.

  The present inventor has found that in an on-demand foil transfer printing apparatus, if an apparatus having an inkjet head arranged downstream of the foil transfer means is configured, multicolor foil transfer and printing on the foil can be performed. Thus, the present invention has been completed.

That is, the present invention provides the following (1) to (6).
(1) an on-demand type droplet delivery head for ejecting a liquid containing an active energy ray-polymerizable compound and a polymerization initiator in an image-like manner on either a recording medium or a foil;
Means (apparatus) for irradiating the liquid with active energy rays to form an image of a pressure-sensitive adhesive having adhesiveness on either the recording medium or the foil;
A foil image forming means (apparatus) for transferring one of the recording medium and the foil to the image of the formed adhesive to form an image of the foil on the recording medium;
An inkjet head disposed downstream of the foil image forming unit in the transport direction of the recording medium and forming an image on the recording medium on which the foil image is formed by ejecting ink containing at least a coloring material; An ink jet recording apparatus having image forming means (apparatus).
(2) The ink jet recording apparatus according to (1), wherein the on-demand type droplet discharge head performs droplet ejection by a single pass.
(3) The inkjet recording apparatus according to (1) or (2), wherein the inkjet head that ejects the ink including at least the color material performs droplet ejection in a single pass.
(4) The image forming unit includes at least an inkjet head that ejects ink onto a foil and an inkjet head that ejects ink onto a recording medium without a foil. Inkjet recording apparatus.
(5) The ink ejected from the inkjet head is an ink that is cured by irradiation with an active energy ray,
The image forming unit is further arranged on the downstream side of the ink jet head in the transport direction of the recording medium, and irradiates the image formed on the recording medium with active energy rays to form the image. The inkjet recording apparatus according to any one of (1) to (4), further comprising an image curing unit that cures the ink.
(6) The image forming unit includes at least two inkjet heads that eject different color inks;
Ink semi-curing means (apparatus) disposed between the ink-jet heads and semi-curing the ink constituting the image formed by the ink-jet head on the upstream side in the transport direction of the recording medium. The ink jet recording apparatus according to any one of (1) to (5).

By using the ink jet recording apparatus of the present invention, it is possible to perform high-quality foil transfer in which the foil and the recording medium are well bonded and the foil can be transferred easily and accurately. Also, multicolor foil transfer and printing on the foil are possible.
For example, if a silver foil is set, a gold color can be obtained by discharging yellow ink from the transferred foil. If cyan is ejected, it can be metallic blue. In addition, it is possible to change various metallic colors and colors on the same foil, to form images on the foil, and to print characters, depending on the process color, which greatly increases the degree of freedom of design. There are also advantages.

  Hereinafter, the present invention will be described in detail using preferred embodiments shown in the drawings, but the present invention is not limited to the embodiments shown in the drawings. In each of the following embodiments, actinic ray curing using an ultraviolet curable ink among actinic ray curable inks (also referred to as actinic energy ray curable inks) that are cured by irradiation with actinic rays (also referred to as actinic energy rays). The ink jet recording apparatus will be described as an example, but the present invention is not limited to this, and can be applied to an ink jet recording apparatus using various actinic ray curable inks.

As shown in FIG. 1, an inkjet recording apparatus 10 according to the present invention includes a transport unit 12 that transports a recording medium (base material) P, an on-demand droplet sending unit 13 that applies droplets to the recording medium P, and , A curing unit 14 that primarily cures the liquid delivered to the recording medium P, and a foil image forming unit (hereinafter referred to as a foil image forming unit) that forms a foil image by transferring the foil of the foil transfer sheet to the adhesive that has been primarily cured and becomes tacky. has a is) 15 that foil transfer unit, an image recording section 16 which records an image on the recording medium P, an image fixing section 18 that fixes the image recorded on the recording medium P. Furthermore, it has a control unit 20 for controlling the ejection of droplets from the on-demand droplet sending unit 13, the curing unit 14, the ejection of ink droplets from the image recording unit 16, and the image fixing unit 18, respectively. These control units may be provided separately, but may be provided in a lump or may be provided for each of a plurality of apparatuses.
An input / output device 22 is connected to the control unit 20 of the ink jet recording apparatus 10. As the input / output device 22, various devices that transmit and receive image data such as an image reading device such as a scanner and an image processing device such as a personal computer can be used. Various connection methods can be used as a connection method between the input / output device 22 and the control unit 20 regardless of wired or wireless.

The transport unit 12 includes a supply roll 30, a transport roll 32, a transport roll pair 34, and a collection roll 36. The transport unit 12 supplies, transports, and collects the recording medium P.
The supply roll 30 has a continuous paper-like recording medium P wound in a roll shape, and supplies the recording medium P.
The transport roll 32 is disposed on the downstream side of the supply roll 30 in the transport direction of the recording medium P, and transports the recording medium P sent out from the supply roll 30 to the downstream side in the transport direction.
The transport roll pair 34 is a pair of rolls, and sandwiches the recording medium P sent out from the supply roll 30 in the transport path of the recording medium P and transports the recording medium P downstream in the transport direction.
The collection roll 36 is disposed on the most downstream side of the conveyance path of the recording medium P. The collection roll 36 is supplied from the supply roll 30 and further conveyed by the conveyance roll pair 34 to the on-demand droplet sending unit 13, the curing unit 14, the foil transfer unit 15, the image recording unit 16, and the image fixing unit 18 described later. The recording medium P that has passed through the facing position is taken up.
Moreover, the conveyance roll 32, the conveyance roll pair 34, and the collection | recovery roll 36 are connected with the drive part which is not shown in figure, and are rotated by a drive part.

Next, the arrangement positional relationship of each part of the conveyance unit 12 will be described, and the conveyance path of the recording medium P will be described.
The supply roll 30, the transport roll 32, the transport roll pair 34, and the recovery roll 36 are arranged in a straight line in a direction parallel to the horizontal direction. Further, between the supply roll 30 and the transport roll pair 34, a foil transfer nip roller 42 that comes into contact with the recording medium P of the foil transfer unit 15 described later is arranged in a straight line in a direction parallel to the horizontal direction. In addition to the straight line shown in the figure, the transport unit can be arranged upside down by inverting the transport path of the recording medium P, or can be transported independently by interrupting the path.

  The transport unit 12 is configured as described above, and the recording medium P is pulled out of the supply roll 30 from the collection roll 36 and transported. Here, the recording medium P drawn from the supply roll 30 is conveyed toward the collection roll 36 in the horizontal direction with the image recording surface facing upward, and is taken up by the collection roll 36.

  As shown in FIG. 1, the on-demand droplet delivery unit 13 includes a droplet delivery head 24 and a liquid tank 26. Further, the droplet delivery head 24 has the tip of the droplet discharge portion facing the transport path of the recording medium P, that is, facing the recording medium P transported on the transport path by the transport section 12 ( Hereinafter, it is also simply referred to as “opposite to the recording medium P”. The droplet delivery head 24 preferably has a large number of ejection openings (nozzles, ink ejection sections) at regular intervals in a direction orthogonal to the conveyance direction of the recording medium P, that is, in the entire width direction of the recording medium P. This is a full-line and piezo-type droplet jet head arranged, and is connected to a control unit 20 and a liquid tank 26 described later. In the droplet delivery head 24, the ejection amount and ejection timing of the ink droplets are controlled by the control unit 20.

  During operation, the recording medium P is supplied from the supply roll 30 at an appropriate line speed, and moves substantially horizontally as shown in FIG. The droplet delivery head 24 is controlled by the control unit 20 to discontinuously drop the adhesive onto the upper surface of the recording medium P at intervals according to the line speed of the recording medium P. A pattern made of a discontinuous adhesive, that is, an adhesive pattern is formed at a desired interval. The droplet delivery head 24 is controlled by the control unit 20, and the control unit 20 is programmed. The computer can be controlled by appropriate computer software to form an image of the adhesive with various patterns of different complexity.

  The droplet delivery head 24 is preferably a full-line type head having nozzle rows that cover the entire width of the paper. The entire surface of the recording medium P can be obtained by performing the operation of moving the recording medium P relative to the droplet sending head 24 in the recording medium conveyance direction (sub-scanning direction) only once (that is, in one sub-scanning). In addition, the discharge liquid can be formed for an image. Such a single-pass droplet discharge head can discharge at a higher speed than the shuttle scan method in which liquid is discharged while reciprocating the head in the main scanning direction, and can improve productivity.

Next, the curing unit 14 will be described.
The curing unit 14 includes an ultraviolet light source 38 and an ultraviolet lamp 28, and is disposed to face the conveyance path of the recording medium P. Here, the ultraviolet lamp is a light source that emits ultraviolet light and irradiates the recording medium P side with ultraviolet light. As the ultraviolet lamp, various ultraviolet light sources such as a metal halide lamp and a high-pressure mercury lamp can be used.

  The ultraviolet lamp has a length corresponding to the maximum paper width of the recording medium P, and is fixed so as to extend in a direction substantially orthogonal to the conveyance direction of the recording medium P. For example, the ultraviolet lamp has a configuration in which ultraviolet LED elements or ultraviolet LD elements are arranged in a line. According to this configuration, light emission control can be selectively performed for each light emitting element, so that the light emitting element to be turned on and the amount of emitted light can be easily adjusted, and a desired irradiation range and light intensity (intensity) distribution can be realized for the ultraviolet irradiation area. it can.

  The curing unit 14 irradiates the entire area in the width direction of the recording medium P that has passed through the opposing position and has droplets discharged onto the surface thereof, and adheres the droplets applied to the surface of the recording medium P to an adhesive state. Adhesive. Here, it will be described later that the droplets are made into a sticky adhesive.

  The foil image forming unit 15 includes a foil transfer nip roller 42 arranged as a pair of rollers with the recording medium sandwiched in the conveyance direction of the recording medium, and a foil feed spool that supplies the foil transfer sheet H to the foil transfer nip roller 42 40 and a take-up spool 44 for collecting unnecessary foil from the foil transfer nip roller 42. The foil transfer nip roller 42 presses and transfers the foil transfer sheet H supplied from the foil feed spool 40 to the adhesive image formed on the recording medium to form a foil image. The foil that is no longer necessary in the portion other than the foil image is taken up by the take-up spool 44 and removed from the recording medium.

  As another aspect, a liquid containing an active energy ray-polymerizable compound and a polymerization initiator may be ejected imagewise on a foil instead of a recording medium. The ink jet recording apparatus of the present invention shown in FIG. 2 includes the on-demand droplet sending unit 13 and the curing unit 14 at positions that oppose the foil transfer sheet H supplied from the foil sending spool 40. For this reason, the on-demand droplet sending unit 13 can eject droplets in an image-like manner on the foil transfer sheet H, and the curing unit 14 can cure the droplets on the foil to form an adhesive adhesive image. The foil transfer sheet H is reversed by the conveyance roller 32 and conveyed to the foil transfer nip roller 42. On the other hand, the recording medium P is supplied from the supply roller 30 to the foil transfer nip roller 42. The foil transfer sheet H, which is supplied from the foil delivery spool 40 by the foil transfer nip roller 42, is ejected by the on-demand droplet delivery unit 13, and the image of the adhesive is formed by the curing unit 14, is reversed to be a recording medium. Since the adhesive layer is pressed onto the recording medium, the foil is separated from the release layer and transferred to the recording medium to form a foil image. The foil that is no longer necessary in the portion other than the foil image is taken up by the take-up spool 44 and removed from the recording medium. The foil feed spool 40, the transport roller 32, the foil transfer nip roller 42, and the take-up spool 44 are the same as in the case of discharging a liquid that is cured on the recording medium P in FIG. The foil image forming unit 15 is configured.

  Next, the image recording unit 16 that discharges ink droplets onto the recording medium and records the image, and the image formed on the recording medium by the image recording unit 16 is cured and fixed on the recording medium. The unit 18 will be described.

As shown in FIG. 1, the image recording unit 16 includes a recording head unit 46 and an ink tank 50. The recording head unit 46 includes recording heads 48X, 48Y, 48C, 48M, and 48K (hereinafter also referred to as “each recording head 48” when five recording heads are shown at once). Here, 48X is not necessary, and is not shown in FIG. 1 but shown in FIG.
The recording heads 48 are arranged in the order of the recording head 48X, the recording head 48Y, the recording head 48C, the recording head 48M, and the recording head 48K from the upstream to the downstream in the conveyance direction of the recording medium P. In addition, each recording head 48 has the tip of each ink discharge portion facing the transport path of the recording medium P, that is, facing the recording medium P transported on the transport path by the transport section 12 ( Hereinafter, it is also simply referred to as “opposite to the recording medium P”.

Each recording head 48 preferably has a large number of ejection openings (nozzles, ink ejection portions) at regular intervals in a direction orthogonal to the conveyance direction of the recording medium P, that is, in the entire width direction of the recording medium P. It is a full line type and piezo type inkjet head arranged, and is connected to a control unit 20 and an ink tank 50 described later. In each recording head 48, the control unit 20 controls the ejection amount and ejection timing of the ink droplets. Further, the recording heads 48X, 48Y, 48C, 48M, and 48K eject special color (X), yellow (Y), cyan (C), magenta (M), and black (K) inks, respectively.
While the recording medium P is transported by the transporting section 12, each color ink of each of the special colors (X), yellow (Y), cyan (C), magenta (M), and black (K) is recorded from each recording head 48. By discharging toward the medium P, a color image can be formed on the recording medium P.

In the present embodiment, the droplet head and the recording head are of the piezo element (piezoelectric element) type, but the present invention is not limited to this. Instead of the piezo type, the ink is heated by a heating element such as a heater to generate bubbles. It is also possible to use various types of recording heads such as a thermal jet method that ejects ink droplets with the pressure.
Here, as the special color ink ejected from the recording head 48X, various inks such as white, orange, purple, and green can be used.
The ink ejected from the droplet head and the ink ejected from the recording head of this embodiment are ultraviolet curable inks.

  The ink tank 50 is provided corresponding to each recording head 48. Each ink tank 50 stores ink of each color corresponding to the recording head, and supplies the stored ink to each corresponding recording head 48.

  Each of the recording heads 48X, 48Y, 48C, 48M, and 48K preferably has a length corresponding to the maximum paper width of the recording medium P targeted by the inkjet recording apparatus 10, and the nozzle surface has a maximum size. This is a full-line head in which a plurality of nozzles for ink ejection are arranged over a length exceeding at least one side of the recording medium P (full width of the drawable range) (see FIG. 2).

  The recording heads 48X, 48Y, 48C, 48M, and 48K are fixedly installed so as to extend along a direction substantially orthogonal to the conveyance direction of the recording medium P.

  As described above, according to the configuration in which the full-line type recording heads 48X, 48Y, 48C, 48M, and 48K having nozzle rows covering the entire width of the paper are provided for each color, the recording medium is transported in the recording medium conveyance direction (sub-scanning direction). The recording heads 48X, 48Y, 48C, 48M, and 48K record the image on the entire surface of the recording medium P only once (ie, in one sub-scan). can do. Such a single-pass image forming apparatus can perform higher-speed printing than the shuttle scan method in which drawing is performed while reciprocating the recording head in the main scanning direction, and can improve print productivity.

In the apparatus of the present invention, since the foil image bonded to the adhesive is already formed on the recording medium P conveyed to the image recording unit 16, printing on the foil is possible, and multicolor printing of the foil is possible. You can also. Since the surface tension is different between the place with the foil image and the place without the foil image, the physical properties such as the viscosity of the ink discharged from the recording heads 48X, 48Y, 48C, 48M, and 48K and the discharge conditions are applied to the respective surfaces. It is preferable to control accordingly.
Such control can be performed by the control unit 20. The control condition may be performed by digital data such as an image or a document, but may be performed by providing a sensor or the like downstream of the foil image forming unit and inputting the detected condition to the input / output unit 22.
As another aspect, a dedicated recording head for discharging onto the foil may be provided separately from the recording head used in a place where there is no foil.

Further, a plate-like platen 56 is disposed at a position facing each recording head 48 on the side of the surface on which the image of the recording medium is not formed.
The platen 56 moves the recording medium P conveyed to a position facing each recording head to the surface side where no image is formed, that is, the side opposite to the surface where the recording head unit 46 of the recording medium P is disposed. Support from the surface. Thereby, the distance between the recording medium P and each recording head can be made constant, and a high-quality image can be formed on the recording medium P.
The shape of the platen 56 is not limited to a flat plate, and may be a curved surface convex toward the recording head. In this case, each recording head 48 is arranged such that the distance from the platen is constant.

  Next, the image fixing unit 18 includes a final curing ultraviolet irradiation unit 54 as shown in FIG. 1, and irradiates the image formed on the recording medium P by the image recording unit 16 with ultraviolet rays. That is, the adhesive or ink) is cured to fix the image. As will be described later, when a cationically polymerizable adhesive or ink is used, fixing can be further enhanced by warming the recording medium after irradiating ultraviolet rays through the foil. The heating temperature is 40 ° C to 60 ° C. The reason is to avoid deformation due to the temperature of the base material that is generally used.

  In another aspect, as shown in FIG. 2, the image fixing unit 18 includes a plurality of ultraviolet irradiation units 52 and a final curing ultraviolet irradiation unit 54, and the plurality of ultraviolet irradiation units 52 includes an image (ink). The final curing ultraviolet irradiation unit 54 may be configured to cure the image as described above.

  The plurality of ultraviolet irradiation units 52 are arranged on the downstream side of the recording heads 48X, 48Y, 48C, and 48M in the conveyance path of the recording medium P, respectively. Further, the final exposure ultraviolet irradiation unit 54 is arranged on the downstream side of the recording head 48K in the conveyance path of the recording medium P. That is, the final exposure ultraviolet irradiation unit 54 is arranged on the downstream side of the recording head arranged on the most downstream side in the conveyance path of the recording medium P.

  That is, each recording head, each ultraviolet irradiation unit 52, and the final exposure ultraviolet irradiation unit 54 are, as shown in FIG. 2, from the upstream side to the downstream side of the transport path, the recording head 48X, the ultraviolet irradiation unit 52, and the recording head. 48Y, ultraviolet irradiation unit 52, recording head 48C, ultraviolet irradiation unit 52, recording head 48M, ultraviolet irradiation unit 52, recording head 48K, and final curing ultraviolet irradiation unit 54 are arranged in this order.

Here, the ultraviolet irradiation unit 52 and the final curing ultraviolet irradiation unit 54 are different in the size of the apparatus and the target to be irradiated with ultraviolet rays. Specifically, the ultraviolet irradiation unit 52 is formed by each recording head. The image is cured, and the ultraviolet light unit 54 for final exposure irradiates light that is stronger than the other ultraviolet light irradiation units, thereby reliably curing the image of the adhesive and various inks applied on the recording medium P. However, since the apparatus configuration is basically the same as that of the ultraviolet irradiation unit 52, the ultraviolet irradiation unit 52 will be representatively described.
Moreover, since each ultraviolet irradiation unit 52 is the same structure, the one ultraviolet irradiation unit 52 is demonstrated.

The ultraviolet irradiation unit 52 includes an ultraviolet lamp, and is disposed so as to face the conveyance path of the recording medium P and extend in the width direction of the recording medium P.
The ultraviolet lamp is a light source that emits ultraviolet light, and irradiates the recording medium P side with ultraviolet light. As the ultraviolet lamp, various ultraviolet light sources such as a metal halide lamp and a high-pressure mercury lamp can be used.
The ultraviolet irradiation unit 52 irradiates the entire area in the width direction of the recording medium P passing through the opposing position, and semi-cures the ink landed on the recording medium P.
Further, the final curing ultraviolet irradiation unit 54 irradiates the entire area in the width direction of the recording medium P passing through the opposing position, and cures the adhesive, foil, and ink landed on the recording medium P. .

Next, the control unit 20 is connected to each recording head 48, uses the image data sent from the input device 22 as a drawing signal, controls ink ejection / non-ejection of each recording head 48, and records the recording medium P. The top forms an image.
The ink jet recording apparatus 10 is basically configured as described above.

[Recording medium]
The recording medium to which the ink composition of the present invention can be applied is not particularly limited, and various kinds of non-absorbing resin materials used for ordinary non-coated paper, coated paper, so-called soft packaging, or the like. A resin film formed into a film can be used, and examples of the various plastic films include PET film, OPS film, OPP film, ONy film, PVC film, PE film, and TAC film. In addition, examples of the plastic that can be used as a recording medium material include polycarbonate, acrylic resin, ABS, polyacetal, PVA, and rubbers. Metals and glasses can also be used as the recording medium.

In the method of the present invention, the liquid ejected onto the recording medium using an on-demand liquid delivery head is not particularly limited, but is preferably a composition having the following characteristics.
(1) As a radiation polymerizable compound, a compound having at least a radical polymerizable group, and (2) a polymerization initiator having two absorption wavelength ranges in which the first and second wavelength ranges are different,
More preferably,
(1) A compound having at least a radical polymerizable group and a cationic polymerizable group, and (2) a photo radical generator and a photo acid generator having different absorption wavelength ranges as a polymerization initiator.
The composition may further contain an ultraviolet absorber, a sensitizer, an antioxidant, an anti-fading agent, a conductive salt, a solvent, a polymer compound, a surfactant and the like as desired.

<(1) Compound having at least a radical polymerizable group>
(A) [Radically polymerizable compound]
Examples of the radically polymerizable compound include compounds having an ethylenically unsaturated bond capable of addition polymerization as described below.

[Compound having an ethylenically unsaturated bond capable of addition polymerization]
Examples of the compound having an addition polymerizable ethylenically unsaturated bond that can be used in the composition of the present invention include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid). Etc.) and an aliphatic polyhydric alcohol compound, an amide of the unsaturated carboxylic acid and an aliphatic polyamine compound, and the like.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol di Acrylate, Tetraethylene glycol diacrylate, Pentaerythritol diacrylate, Pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (acryloxyethoxy) phenyl] dimethylmethane. Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.

  Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate. Furthermore, the mixture of the above-mentioned ester monomer can also be mention | raise | lifted. Specific examples of an amide monomer of an aliphatic polyvalent amine compound and an unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexa. Examples include methylene bis-methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.

Other examples include vinyls containing a hydroxyl group represented by the following general formula (A) in a polyisocyanate compound having two or more isocyanate groups per molecule described in JP-B-48-41708. Examples thereof include a vinylurethane compound containing two or more polymerizable vinyl groups in one molecule to which a monomer is added. CH ₂ = C (R) COOCH ₂ CH (R ') OH (A) (where R and R ′ represent H or CH ₃ )
Further, urethane acrylates as described in JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 are disclosed. Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid can be used. Furthermore, Journal of Japan Adhesion Association vol.20, No. 7, pages 300 to 308 (1984), those introduced as photocurable monomers and oligomers can also be used. In the present invention, these monomers can be used in a chemical form such as a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof.

<(1) Compound having at least radically polymerizable group and cationically polymerizable group>
It is a compound having both the above-mentioned radical polymerizable group and the cationic polymerizable group described below.

(B) Cationic polymerizable compound The (b) cationic polymerizable compound used in the present invention is a compound that undergoes a polymerization reaction with an acid generated from a compound that generates an acid upon irradiation with radiation, which will be described later, and cures. There is no restriction | limiting in particular, The various well-known cationically polymerizable monomer known as a photocationic polymerizable monomer can be used. Examples of the cationic polymerizable monomer include JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, JP-A-2001-310938, JP-A-2001-310937, and 2001-2001. Examples thereof include epoxy compounds, vinyl ether compounds, oxetane compounds and the like described in each publication such as No. 220526.

Examples of the epoxy compound include aromatic epoxides, alicyclic epoxides, and aliphatic epoxides.
Aromatic epoxides include di- or polyglycidyl ethers produced by the reaction of polyphenols having at least one aromatic nucleus or their alkylene oxide adducts and epichlorohydrin, such as bisphenol A or its alkylene oxides. Examples thereof include di- or polyglycidyl ethers of adducts, di- or polyglycidyl ethers of hydrogenated bisphenol A or its alkylene oxide adducts, and novolak-type epoxy resins. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

  As the alicyclic epoxide, cyclohexene oxide obtained by epoxidizing a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene ring with a suitable oxidizing agent such as hydrogen peroxide or peracid. Or a cyclopentene oxide containing compound is mentioned preferably.

  Examples of the aliphatic epoxide include dihydric polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. Typical examples include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol or diglycidyl ether of alkylene glycol such as diglycidyl ether of 1,6-hexanediol, di- or tri- or di- or tri-glycol or adducts thereof. Polyglycidyl ether of polyhydric alcohol such as glycidyl ether, diglycidyl ether of polyethylene glycol or alkylene oxide adduct thereof, diglycidyl ether of polyalkylene glycol represented by diglycidyl ether of polypropylene glycol or alkylene oxide adduct thereof, etc. Can be mentioned. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

The epoxy compound may be monofunctional or polyfunctional.
Examples of monofunctional epoxy compounds that can be used in the present invention include, for example, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3 -Vinylcyclohexene oxide etc. are mentioned.

  Examples of polyfunctional epoxy compounds include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol. S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxy 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclo) Xylmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6 '-Methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate) , Epoxyhexahydrophthalate dioctyl, epoxyhexahydrophthalate di-2-ethylhexyl, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether Glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradecadiene dioxide, limonene dioxide, 1,2,7,8- Examples include diepoxyoctane and 1,2,5,6-diepoxycyclooctane.

  Among these epoxy compounds, aromatic epoxides and alicyclic epoxides are preferable from the viewpoint of excellent curing speed, and alicyclic epoxides are particularly preferable.

  Examples of the vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, Di- or trivinyl ether compounds such as methylolpropane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexane dimethanol monovinyl ether, n-propyl Pills vinyl ether, isopropyl vinyl ether, isopropenyl ether -O- propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether.

The vinyl ether compound may be monofunctional or polyfunctional.
Specifically, examples of monofunctional vinyl ethers include, for example, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, Cyclohexylmethyl vinyl ether, 4-methylcyclohexyl methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether , Methoxypolyethyleneglycol Ruvinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, Examples include chloroethoxyethyl vinyl ether, phenylethyl vinyl ether, phenoxypolyethylene glycol vinyl ether, and the like.

  Examples of polyfunctional vinyl ethers include, for example, ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, and bisphenol F. Divinyl ethers such as alkylene oxide divinyl ether; trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol Hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide addition Examples thereof include polyfunctional vinyl ethers such as pentaerythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, and propylene oxide-added dipentaerythritol hexavinyl ether.

  As the vinyl ether compound, a di- or trivinyl ether compound is preferable from the viewpoints of curability, adhesion to a recording medium, surface hardness of the formed image, and the like, and a divinyl ether compound is particularly preferable.

The oxetane compound in the present invention refers to a compound having an oxetane ring, and a known oxetane compound is arbitrarily selected as described in JP-A Nos. 2001-220526, 2001-310937, and 2003-341217. Can be used.
The compound having an oxetane ring that can be used in the ink composition of the present invention is preferably a compound having 1 to 4 oxetane rings in the structure. By using such a compound, it becomes easy to maintain the viscosity of the ink composition within a good handling range, and obtain high adhesion between the cured ink composition and the recording medium. Can do.

The compound having such an oxetane ring is described in detail in JP-A-2003-341217, paragraph numbers [0021] to [0084], and the compounds described herein can be suitably used in the present invention. .
Among the oxetane compounds used in the present invention, it is preferable to use a compound having one oxetane ring from the viewpoint of the viscosity and tackiness of the ink composition.

  In the ink composition of the present invention, these cationic polymerizable compounds may be used alone or in combination of two or more, but from the viewpoint of effectively suppressing shrinkage during ink curing. Is preferably a combination of at least one compound selected from an oxetane compound and an epoxy compound and a vinyl ether compound.

In order to achieve foil transfer accuracy and adhesiveness to the recording medium with the same quality as the cold foil method that uses an offset printing press in the inkjet method, after being ejected from the inkjet onto the recording medium, it is adhered by ultraviolet irradiation. After securing the transferability of the foil as a property, it is desired to further cure and to obtain a composition that can secure the adhesive force between the foil and the recording medium. For this reason, it is preferable to set it as the curable liquid composition which contains the following compounds and can be hardened | cured in two steps.
<Compound having both (meth) acryloyl group and vinyl ether group>
The compound having both a radical polymerizable group and a cationic polymerizable group is more preferably a compound having both a (meth) acryloyl group and a vinyl ether group.
A compound having both a (meth) acryloyl group and a vinyl ether group may be used alone or in combination of two or more.
In addition, notations such as acrylate, acrylic acid, acryloyl group and methacrylate, methacrylic acid, and methacryloyl group are represented by (meth) acrylate and the like, and both compounds are shown. The compound having both the (meth) acryloyl group and the vinyl ether group may be a compound having at least one (meth) acryloyl group and a vinyl ether group in one molecule, but the following general formula (1) ;
_{^{CH 2 = CR 1 -COO-R}} 2 -O-CH = CH-R 3 (1)
(In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² represents an organic residue having 2 to 20 carbon atoms. R ³ represents a hydrogen atom or an organic residue having 1 to 11 carbon atoms. It is preferable that it is vinyl ether group containing (meth) acrylic acid ester represented by this.

In the general formula (1), the organic residue represented by R ² is a linear, branched or cyclic alkylene group having 2 to 20 carbon atoms, and an ether bond and / or an ester bond in the structure. An alkylene group having 2 to 20 carbon atoms having an oxygen atom and an optionally substituted aromatic group having 6 to 11 carbon atoms are preferred. Among these, a C2-C6 alkylene group and a C2-C9 alkylene group which has an oxygen atom by an ether bond in a structure are used suitably.

In the general formula (1), the organic residue having 1 to 11 carbon atoms represented by R ³ is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or 6 to 11 carbon atoms. Aromatic groups which may be substituted are preferred. Among these, an alkyl group having 1 to 2 carbon atoms and an aromatic group having 6 to 8 carbon atoms are preferably used.

As the vinyl ether group-containing (meth) acrylic acid esters represented by the general formula (1), the following compounds are suitable.
(Meth) acrylic acid 2-vinyloxyethyl, (meth) acrylic acid 3-vinyloxypropyl, (meth) acrylic acid 1-methyl-2-vinyloxyethyl, (meth) acrylic acid 2-vinyloxypropyl, (meth) acrylic acid 4 -Vinyloxybutyl, 1-methyl-3-vinyloxypropyl (meth) acrylate, 1-vinyloxymethylpropyl (meth) acrylate, 2-methyl-3-vinyloxypropyl (meth) acrylate, (meth) acrylic acid 1,1-dimethyl-2-vinyloxyethyl, 3-vinyloxybutyl (meth) acrylate, 1-methyl-2-vinyloxypropyl (meth) acrylate, 2-vinyloxybutyl (meth) acrylate, 4- (meth) acrylic acid 4- Vinyloxycyclohexyl, 6-vinyloxyhexyl (meth) acrylate, (meth) acrylic 4-vinyloxymethylcyclohexylmethyl oxalate, 3-vinyloxymethylcyclohexylmethyl (meth) acrylate, 2-vinyloxymethylcyclohexylmethyl (meth) acrylate, p-vinyloxymethylphenylmethyl (meth) acrylate, ( (Meth) acrylic acid m-vinyloxymethylphenylmethyl, (meth) acrylic acid o-vinyloxymethylphenylmethyl.

2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxy) propyl (meth) acrylate, 2- (meth) acrylic acid 2- (Vinyloxyethoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyisopropoxy) propyl, (meth) acrylic acid 2- (vinyloxyisopropoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyethoxyethoxy) Ethyl, 2- (vinyloxyethoxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) ethyl (meth) acrylate , (Meth) acrylic acid 2- (vinyloxyethoxyethoxy) pro 2- (vinyloxyethoxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) propyl (meth) acrylate 2- (vinyloxyethoxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) isopropyl (meth) acrylate, (meta ) 2- (vinyloxyisopropoxyisopropoxy) isopropyl acrylate, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, (meth) Acrylic acid -(Isopropenoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropenoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- (isopropenoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid 2- ( Isopropenoxyethoxyethoxyethoxyethoxy) ethyl, (meth) acrylic acid polyethylene glycol monovinyl ether, (meth) acrylic acid polypropylene glycol monovinyl ether.
Among these, 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, (meth ) 4-vinyloxybutyl acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 5-vinyloxypentyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4-vinyloxymethyl (meth) acrylate Cyclohexylmethyl, p-vinyloxymethyl phenylmethyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) ethyl (meth) acrylate, (meth) acrylic acid 2- (vinyloxyethoxyethoxyethoxy) ethyl is preferred .

  As a manufacturing method of the vinyl ether group containing (meth) acrylic acid ester represented by the said General formula (1), the method of esterifying (meth) acrylic acid and hydroxyl group containing vinyl ether (manufacturing method A), (meth) Method of esterifying acrylic acid halide and hydroxyl group-containing vinyl ether (Production method B), Method of esterifying (meth) acrylic anhydride and hydroxyl group-containing vinyl ethers (Production method C), (meth) acrylic acid esters And esterification of hydroxyl-containing vinyl ethers (Production Method D), method of esterifying (meth) acrylic acid and halogen-containing vinyl ethers (Production Method E), (meth) acrylic acid alkali (earth) metal salt and Method of esterifying halogen-containing vinyl ethers (Production Method F), hydroxyl group-containing (meth) acrylic acid ester How to vinyl exchanging the carboxylic acid vinyl and (Process G), hydroxyl group-containing (meth) How to ether exchange and acrylic acid esters and alkyl vinyl ethers (method H) is preferred. Among these, the method (production method D) of transesterifying (meth) acrylic acid esters and hydroxyl group-containing vinyl ethers is suitable, and the effects of the present invention can be more fully exhibited.

  The amount of the compound having at least a radical polymerizable group, preferably a compound having both a radical polymerizable group and a cationic polymerizable group, is suitably 10 to 95% by mass, preferably 30%, based on the total solid content of the composition. It is -90 mass%, More preferably, it is the range of 50-85 mass%.

  An example of a compound VEEA having both a radical polymerizable group and a cationic polymerizable group and the polymerization state thereof will be described with reference to FIG.

<Polymerization initiator contained in the composition of the present invention>
Any kind of two polymerization initiators having different absorption wavelength ranges may be used. Preferably, two kinds of photo radical generators and photo acid generators are used. Preferably, the first and second absorption wavelength regions are two kinds of polymerization initiators different from each other by 50 nm or more.

  The photoradical polymerization initiator generates a polymerization initiating radical by irradiation with light, and the photocationic polymerization initiator generates a polymerization initiating cation by irradiation with light. Preferred radical photopolymerization initiators include (a) aromatic ketones, (b) aromatic onium salt compounds, (c) organic peroxides, (d) hexaarylbiimidazole compounds, (e) ketoxime ester compounds, (F) borate compounds, (to) azinium compounds, (thi) metallocene compounds, (li) active ester compounds, (nu) compounds having a carbon halogen bond, and the like.

Examples of the radical photopolymerization initiator include the following compounds.
Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl Phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1 Acetophenones such as [4- (1-methylvinyl) phenyl] propanone oligomer; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, o-benzoyl Methyl perfume, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxylcarbonyl) benzophenone, 2,4,6-trimethylbenzophenone Benzophenones such as 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride; Isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl- 9H-thioxanthone-9 Thioxanthones such as Onmesokurorido. Among these, acetophenones, benzophenones, and acyl phosphine oxides are preferable. In particular, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one are preferable.

[(B) Photoacid generator]
Photoacid generator that generates acid upon irradiation with active energy as a cationic polymerization initiator, for example, onium salts such as diazonium salt, ammonium salt, phosphonium salt, iodonium salt, sulfonium salt, selenonium salt, arsonium salt, organic Halogen compounds, organometallic / organic halides, photoacid generators having o-nitrobenzyl type protecting groups, compounds that generate sulfonic acids upon photolysis, such as iminosulfonates, disulfone compounds, diazoketosulfones And diazodisulfone compounds.

  As the photoacid generator, oxazole derivatives and s-triazine derivatives described in JP-A No. 2002-122994, paragraphs [0029] to [0030] are also preferably used. Furthermore, onium salt compounds and sulfonate compounds exemplified in JP-A No. 2002-122994, paragraph numbers [0037] to [0063] can also be suitably used as the photoacid generator in the present invention.

(B) Two types of polymerization initiators having different absorption wavelength ranges are used. Each kind can be used individually by 1 type or in combination of 2 or more types, as needed. (B) Content of a polymerization initiator is 0.1-20 mass% in conversion of the total solid of a composition, More preferably, it is 0.5-10 mass%, More preferably, it is 1-7 mass%. It is.

  As the photocationic polymerization initiator, the following compounds are suitable. Arylsulfonium salts such as triphenylsulfonium hexafluorophosphate and triphenylsulfonium hexafluoroantimonate; aryliodines such as diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, (tolylcumyl) iodonium tetrakis (pentafluorophenyl) borate Nium salts; aryldiazonium salts such as phenyldiazonium tetrafluoroborate.

  The amount of the photopolymerization initiator used is preferably 0.1% by mass or more, and more preferably 20% by mass or less with respect to 100% by mass of the ink jet discharge liquid. More preferably, it is 0.5% by mass or more and 15% by mass or less.

  As an example of a set of polymerization initiators having different absorption wavelengths, phenyl-bis (2,4,6-trimethyl) having absorption peak wavelengths at 295 and 370 nm as a photopolymerization initiator (photo radical generator) for the first curing Benzoyl) phosphine oxide (product name: Ciba Specialty Chemicals IRGACURE819), UV LED having a peak emission wavelength of 365 nm (NSHA 550B manufactured by Nichia Corporation) as a light source for curing, a polymerization initiator for second curing ( As a photoacid generator, (4-methylphenyl) [4- (2-methylpropyl) phenyl], which has an absorption peak wavelength at 240 nm and hardly absorbs at 340 nm or more, hexafluorophosphate iodonium (Ciba Specialty) High pressure mercury lamp (for example, bovine) using IRGACURE250 made by Tea Chemicals as the second curing light source A combination of UM-4525 manufactured by O Denki.

  The liquid for active energy ray-curable on-demand type droplet delivery head of the present invention may be used in combination with the essential components (1) and (2) above and other polymerizable monomers and curable resins. Various additives can be used in combination depending on the purpose. These optional components will be described.

[Ultraviolet absorber]
In the present invention, an ultraviolet absorber can be used from the viewpoint of improving the weather resistance of the obtained image and preventing discoloration.
Examples of the ultraviolet absorber are described in JP-A-58-185679, JP-A-61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Benzotriazole compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194433, US Pat. No. 3,214,463, etc. Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP The triazine compounds described in JP-A-8-501291, Research Disclosure No. Examples thereof include compounds described in No. 24239, compounds that emit ultraviolet light by absorbing ultraviolet rays typified by stilbene and benzoxazole compounds, so-called fluorescent brighteners, and the like.
The addition amount is appropriately selected according to the purpose, but is generally about 0.5 to 15% by mass in terms of solid content.

[Sensitizer]
A sensitizer may be added to the ink composition of the present invention as necessary for the purpose of improving the acid generation efficiency of the photoacid generator and increasing the photosensitive wavelength. Any sensitizer may be used as long as the photoacid generator is sensitized by an electron transfer mechanism or an energy transfer mechanism. Preferably, aromatic polycondensed compounds such as anthracene, 9,10-dialkoxyanthracene, pyrene and perylene, aromatic ketone compounds such as acetophenone, benzophenone, thioxanthone and Michlerketone, heterocyclic compounds such as phenothiazine and N-aryloxazolidinone Is mentioned. The addition amount is appropriately selected according to the purpose, but is generally 0.01 to 1 mol%, preferably 0.1 to 0.5 mol%, based on the photoacid generator.

〔Antioxidant〕
An antioxidant can be added to improve the stability of the ink composition. Examples of the antioxidant include European Patent Nos. 223739, 309401, 309402, 310551, 310552, 455416, and German Patent No. 3435443. JP, 47-54535, 62-262447, 63-113536, 63-163351, JP-A-2-262654, JP-A-2-71262, JP-A. Examples thereof include those described in JP-A-3-121449, JP-A-5-61166, JP-A-5-119449, US Pat. No. 4,814,262, US Pat. No. 4,980,275, and the like.
The addition amount is appropriately selected according to the purpose, but is generally about 0.1 to 8% by mass in terms of solid content.

[Anti-fading agent]
In the ink composition of the present invention, various organic and metal complex anti-fading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. Examples of the metal complex anti-fading agent include nickel complexes and zinc complexes. No. 17643, VII, I to J, No. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of representative compounds described in JP-A-62-215272, pages 127 to 137 can be used. .
The addition amount is appropriately selected according to the purpose, but is generally about 0.1 to 8% by mass in terms of solid content.

[Conductive salts]
Conductive salts such as potassium thiocyanate, lithium nitrate, ammonium thiocyanate, and dimethylamine hydrochloride can be added to the ink composition of the present invention for the purpose of controlling ejection properties.

〔solvent〕
In order to improve the adhesion to the recording medium, it is also effective to add a very small amount of an organic solvent to the ink composition of the present invention.
Examples of the solvent include ketone solvents such as acetone, methyl ethyl ketone, and diethyl ketone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, and tert-butanol, and chlorine such as chloroform and methylene chloride. Solvents, aromatic solvents such as benzene and toluene, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, glycols such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether And ether solvents.
In this case, it is effective to add the solvent within a range that does not cause the problem of solvent resistance and VOC. % Range.

[Polymer compound]
Various polymer compounds can be added to the ink composition of the present invention in order to adjust film physical properties. High molecular compounds include acrylic polymer, polyvinyl butyral resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, vinyl resin, acrylic resin. Rubber resins, waxes and other natural resins can be used. Two or more of these may be used in combination. Of these, vinyl copolymer obtained by copolymerization of acrylic monomers is preferred. Furthermore, a copolymer containing “carboxyl group-containing monomer”, “methacrylic acid alkyl ester”, or “acrylic acid alkyl ester” as a structural unit is also preferably used as the copolymer composition of the polymer binder.

[Surfactant]
A surfactant may be added to the ink composition of the present invention.
Examples of the surfactant include those described in JP-A Nos. 62-173463 and 62-183457. For example, anionic surfactants such as dialkylsulfosuccinates, alkylnaphthalenesulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene blocks Nonionic surfactants such as copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts. An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compounds include fluorine surfactants, oily fluorine compounds (eg, fluorine oil) and solid fluorine compound resins (eg, tetrafluoroethylene resin). No. (columns 8 to 17) and those described in JP-A Nos. 62-135826.

In addition to this, for example, leveling additives, matting agents, waxes for adjusting film physical properties, polymerization to improve adhesion to a recording medium such as polyolefin or PET, and the like. It can contain a tackifier that does not obstruct.
As the tackifier, specifically, a high molecular weight adhesive polymer described in JP-A-2001-49200, 5-6p (for example, (meth) acrylic acid and an alkyl group having 1 to 20 carbon atoms). An ester with an alcohol having, an ester of (meth) acrylic acid with an alicyclic alcohol having 3 to 14 carbon atoms, a copolymer comprising an ester of (meth) acrylic acid with an aromatic alcohol having 6 to 14 carbon atoms) And a low molecular weight tackifying resin having a polymerizable unsaturated bond.

(Coloring agent)
At least the ink or the liquid for the ink and on-demand droplet delivery head contains at least one colorant. The colorant may be contained in other liquids besides ink. This is because the ultraviolet curability may be changed or colored for identification.

  The colorant is not particularly limited, and can be appropriately selected from known water-soluble dyes, oil-soluble dyes, pigments, and the like. In particular, when the ink and the undercoat liquid are composed of a water-insoluble organic solvent system that can suitably obtain the effects of the present invention, the colorant is an oil-soluble material that is easily dispersed and dissolved in a water-insoluble medium. It is preferable to use dyes and pigments.

  The content of the colorant in the ink is preferably 1 to 30% by mass, more preferably 1.5 to 25% by mass, and particularly preferably 2 to 15% by mass. When the undercoat liquid contains a white pigment as the colorant, the content of the colorant in the undercoat liquid is preferably 2 to 45% by mass, and more preferably 4 to 35% by mass.

Hereinafter, the pigment suitable for the present invention will be mainly described.
<Pigment>
An embodiment using a pigment as the colorant is preferred.
As the pigment, either an organic pigment or an inorganic pigment can be used, and as the black pigment, a carbon black pigment or the like is preferable. In general, pigments of three primary colors of black and cyan, magenta, and yellow are used, but other hues such as pigments having hues such as red, green, blue, brown, white, gold, silver, etc. Metal luster pigments, colorless or light extender pigments, and the like can also be used depending on the purpose.

  The organic pigment is not limited in hue, for example, perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, triaryl carbo Examples thereof include nium, dioxazine, aminoanthraquinone, diketopyrrolopyrrole, thioindigo, isoindoline, isoindolinone, pyranthrone, isoviolanthrone pigment, and mixtures thereof.

  More specifically, for example, C.I. I. Pigment red 190 (C.I. No. 71140), C.I. I. Pigment red 224 (C.I. No. 71127), C.I. I. Perylene pigments such as CI Pigment Violet 29 (C.I. No. 71129); I. Pigment orange 43 (C.I. No. 71105) or C.I. I. Perinone pigments such as CI Pigment Red 194 (C.I. No. 71100); I. Pigment violet 19 (C.I. No. 73900), C.I. I. Pigment violet 42, C.I. I. Pigment red 122 (C.I. No. 73915), C.I. I. Pigment red 192, C.I. I. Pigment red 202 (C.I. No. 73907), C.I. I. Pigment red 207 (C.I. No. 73900, 73906), or C.I. I. Pigment Red 209 (C.I. No. 73905), a quinacridone pigment, C.I. I. Pigment red 206 (C.I. No. 73900/73920), C.I. I. Pigment orange 48 (C.I. No. 73900/73920), or C.I. I. Quinacridone quinone pigments such as CI Pigment Orange 49 (C.I. No. 73900/73920); I. Anthraquinone pigments such as C.I. Pigment Yellow 147 (C.I. No. 60645); I. Anthanthrone pigments such as CI Pigment Red 168 (C.I. No. 59300); I. Pigment brown 25 (C.I. No. 12510), C.I. I. Pigment violet 32 (C.I. No. 12517), C.I. I. Pigment yellow 180 (C.I. No. 21290), C.I. I. Pigment yellow 181 (C.I. No. 11777), C.I. I. Pigment orange 62 (C.I. No. 11775), or C.I. I. Benzimidazolone pigments such as CI Pigment Red 185 (C.I. No. 12516); I. Pigment yellow 93 (C.I. No. 20710), C.I. I. Pigment yellow 94 (C.I. No. 20038), C.I. I. Pigment yellow 95 (C.I. No. 20034), C.I. I. Pigment yellow 128 (C.I. No. 20037), C.I. I. Pigment yellow 166 (C.I. No. 20003), C.I. I. Pigment orange 34 (C.I. No. 21115), C.I. I. Pigment orange 13 (C.I. No. 21110), C.I. I. Pigment orange 31 (C.I. No. 20050), C.I. I. Pigment red 144 (C.I. No. 20735), C.I. I. Pigment red 166 (C.I. No. 20730), C.I. I. Pigment red 220 (C.I. No. 20055), C.I. I. Pigment red 221 (C.I. No. 20065), C.I. I. Pigment red 242 (C.I. No. 20067), C.I. I. Pigment red 248, C.I. I. Pigment red 262, or C.I. I. Disazo condensation pigments such as CI Pigment Brown 23 (C.I. No. 20060),

C. I. Pigment yellow 13 (C.I. No. 21100), C.I. I. Pigment yellow 83 (C.I. No. 21108), or C.I. I. Disazo pigments such as CI Pigment Yellow 188 (C.I. No. 21094); I. Pigment red 187 (C.I. No. 12486), C.I. I. Pigment red 170 (C.I. No. 12475), C.I. I. Pigment yellow 74 (C.I. No. 11714), C.I. I. Pigment yellow 150 (C.I. No. 48545), C.I. I. Pigment red 48 (C.I. No. 15865), C.I. I. Pigment red 53 (C.I. No. 15585), C.I. I. Pigment orange 64 (C.I. No. 12760), or C.I. I. Azo pigments such as C.I. Pigment Red 247 (C.I. No. 15915), C.I. I. Indanthrone pigments such as CI Pigment Blue 60 (C.I. No. 69800); I. Pigment green 7 (C.I. No. 74260), C.I. I. Pigment green 36 (C.I. No. 74265), C.I. I. Pigment green 37 (C.I. No. 74255), C.I. I. Pigment blue 16 (C.I. No. 74100), C.I. I. Phthalocyanine pigments such as CI Pigment Blue 75 (C.I. No. 74160: 2) or 15 (C.I. No. 74160); I. Pigment blue 56 (C.I. No. 42800) or C.I. I. Triarylcarbonium pigments such as C.I. Pigment Blue 61 (C.I. No. 42765: 1); I. Pigment violet 23 (C.I. No. 51319) or C.I. I. Dioxazine pigments such as CI Pigment Violet 37 (C.I. No. 51345); I. Aminoanthraquinone pigments such as C.I. Pigment Red 177 (C.I. No. 65300); I. Pigment red 254 (C.I. No. 56110), C.I. I. Pigment Red 255 (C.I. No. 561050), C.I. I. Pigment red 264, C.I. I. Pigment red 272 (C.I. No. 561150), C.I. I. Pigment orange 71, or C.I. I. Diketopyrrolopyrrole pigments such as C.I. Pigment Orange 73; I. Thioindigo pigments such as CI Pigment Red 88 (C.I. No. 7313), CI Pigment Yellow 139 (C.I. No. 56298), C.I. I. Pigment Orange 66 (C.I. No. 48210) and the like, isoindoline pigments such as C.I. I. Pigment yellow 109 (C.I. No. 56284), or C.I. Pigment Orange 61 (C.I. No. 11295) and the like, isoindolinone pigments such as C.I. I. Pigment Orange 40 (C.I. No. 59700), or C.I. I. Pyranthrone pigments such as CI Pigment Red 216 (C.I. No. 59710), or C.I. I. And isoviolanthrone pigments such as CI Pigment Violet 31 (60010).
As the colorant, two or more kinds of organic pigments or solid solutions of organic pigments can be used in combination.

  In addition, particles having silica, alumina, resin, or the like as a core material and having a dye or pigment fixed on the surface, an insoluble raked product of a dye, a colored emulsion, a colored latex, or the like can also be used as a pigment. Furthermore, resin-coated pigments can also be used. This is called a microcapsule pigment, and commercially available products such as those manufactured by Dainippon Ink and Chemicals and Toyo Ink are available.

  The volume average particle diameter of the pigment particles contained in the liquid is preferably in the range of 10 to 250 nm, more preferably 50 to 200 nm, from the viewpoint of balance between optical density and storage stability. Here, the volume average particle diameter of the pigment particles can be measured by a particle size distribution measuring device such as LB-500 (manufactured by HORIBA).

  The colorant may be used alone or in combination of two or more. Different colorants may be used for each droplet and liquid to be ejected, or the same colorant may be used.

[Preferred physical properties of composition or ink]
The composition of the present invention preferably has a viscosity of 20 mPa · s or less, more preferably 10 mPa · s or less at the temperature at the time of injection in consideration of injection properties, and the composition ratio is appropriately adjusted to be in the above range. It is preferable to adjust and determine the value.

  The common surface tension of the composition of the present invention is preferably 20 to 40 mN / m, more preferably 25 to 35 mN / m. When recording on various recording media such as polyolefin, PET, coated paper, and uncoated paper, 20 mN / m or more is preferable from the viewpoint of bleeding and penetration, and 40 mN / m or less is preferable in terms of wettability.

  The composition prepared in this manner is ejected by ink jet, irradiated with an active energy ray in the first wavelength region, polymerized, and suitably used as an adhesive for foil transfer.

The foil transfer method using the inkjet recording apparatus of the present invention includes the following steps a) to f).
a) Recording medium comprising a liquid having at least an active energy ray polymerizable group as an active energy ray polymerizable compound and a polymerization initiator having two absorption wavelength ranges in which the first and second wavelength ranges are different To discharge,
b) irradiating the discharged liquid with an active energy ray in the first wavelength region and polymerizing the liquid to form an adhesive image on the recording medium;
c) transfer the foil to the image of the formed adhesive;
d) An image is formed by ejecting ultraviolet ink containing a color material from the recording medium to which the foil has been transferred. When yellow is solidly dropped on a silver foil, it can be gold. Moreover, various metallic colors can be expressed by ejecting various process colors on the foil. Further, by forming a process color gradation image on the foil, a metallic color gradation can also be expressed. Examples of usable ultraviolet ink include: Uvijet EG ink (Y, M, C, K) manufactured by FUJIFILM Sericol.
A place where there is no foil can reproduce an arbitrary printed image in the same manner as a normal ultraviolet inkjet.
e) irradiating the image again with ultraviolet light to cure and fix the formed image f) winding the recording medium on a take-up roll.

  FIG. 3 shows a typical foil 11 structure suitable for use in the present invention. The foil 11 includes, for example, a polyester holding layer 1 having a release layer 2 mainly composed of wax. Below the release layer 2, a lacquer layer 3 and a metal layer 4 are provided in this order, and finally an auxiliary adhesive layer 5 is provided. A person skilled in the art can understand that the structure of the foil can be changed, for example, by providing a colored layer. A lacquer layer may not be required and a holographic layer may be provided as an additional layer. The auxiliary adhesive layer 5 is not provided on all the foils. However, in order to assist the adhesion of the foils, for example, when attaching the foils to a recording medium in a large area, before transferring the foils, such as an IC tag. This is useful in certain applications, such as when other necessary components are embedded in the adhesive.

The lacquer layer 3 can also be embossed to include a holographic pattern. This layer can then be covered with a metal layer 4 or if it is desired to make the underlying information visible, the metal layer 4 has a higher refractive index than the lacquer layer embossed to be holographic. It can be replaced with a different transparent material. Examples of refractive materials that can be used for this purpose include zinc sulfide (ZnS), zirconium dioxide (ZrO ₂ ), and titanium dioxide (TiO ₂ ). These materials have a high refractive index and are sufficiently transparent. Other materials with higher refractive index and other materials with lower refractive index are known and can also be used.

  Examples of highly reflective metals suitable for the metal layer 4 include aluminum (Al) silver (Ag) and copper (Cu). Aluminum is preferred. However, other effects such as an improvement in durability, a reduction in cost, and an improvement in conductivity can be obtained by a layer made of another metal.

  In the following, the adhesive layer and the transfer of the metal layer from the foil to the recording medium by this layer will be described. This technique is equally applicable to the transfer of other transferable layers such as colored layers or holographic layers, or two or more of these transfers. This technique can also be used to transfer other types of transfer layers. The transfer layer can be a composite layer composed of two or more sublayers of the same or different materials.

The steps a) to d) shown in FIG. 4 will be described below.
a) Step of discharging liquid onto a recording medium (discharge step)
As shown in FIG. 4A, the compound having at least a radical polymerizable group and the first and second wavelength ranges are different from the droplet sending head 24 disposed on the recording medium P above the recording medium. A liquid 25 containing a polymerization initiator in two types of absorption wavelength ranges is ejected to form an image-like liquid layer on the recording medium.

b) A step of forming a sticky adhesive image on a recording medium by irradiating the discharged liquid with radiation in the first wavelength region and polymerizing the first liquid (first curing step).
As shown in FIG. 1, a first ultraviolet lamp 28 is disposed on the downstream side of the droplet delivery head 24 and is controlled by the control unit 20. As shown in FIG. 4B, the discharged liquid 25 is irradiated with ultraviolet light in the first wavelength region to form an image of the adhesive 6.
In the polymerization initiator, preferably a radical generator (radical polymerization initiator) and an acid generator (cationic polymerization initiator), it is possible to selectively polymerize a part of the discharged liquid polymerizable group. This is possible by selecting a polymerization initiator having a different absorption wavelength range. In order to effectively polymerize only one polymerizable group, polymerization is performed with different absorption wavelength ranges between a radical generator (radical polymerization initiator) and an acid generator (cation polymerization initiator). Select an initiator. As the light source for the first curing (hereinafter referred to as “first curing”), a light source having a narrow half-value width of the emission wavelength, a light emitting diode (LED) or a laser diode (LD) is suitable. As a specific combination, an LED is used as a light source for the first curing, and a compound having an absorption peak near the absorption wavelength of the LED is selected as the first curing initiator.
The first curing is preferably radical curing and the second curing is cation curing. In the first curing, the curing needs to be completed early, but in general, the radical polymerization reaction is faster than the cationic polymerization reaction, and is suitable as the first curing.

  The molar ratio of the group cured by the first curing and the group cured by the second curing is preferably a high ratio of the group cured by the first curing, more preferably 80% or more of the group cured by the first curing. 98% or less. The light source of the first curing may be set to a predetermined energy range, and the group that is cured by the first curing may be 80% or more and 98% or less. Of course, if all are cured by the first curing, the effect of the present invention cannot be obtained.

The hardened | cured material of 1st hardening needs to have adhesiveness. The glass transition temperature (Tg) of the cured product polymerized by the first curing needs to be room temperature or lower (specifically, 25 ° C. or lower).
Tg is measured by applying a polymerizable compound to a thickness of 0.1 mm with a bar coater and irradiating it with ultraviolet light to form a polymer film. What sampled 5 mg from this film | membrane can be measured as a measurement temperature range from -100 degreeC to 150 degreeC using a differential scanning calorimetry DSC (Differential Scanning Calorimetry DSC).

c) Step of transferring the foil onto the image of the formed adhesive (foil transfer step)
Since the liquid 25 ejected onto the recording medium P forms an image of the adhesive 6 that is cured in the step of FIG. 4B and has adhesiveness, as shown in FIG. 1 and FIG. Then, the foil transfer sheet H is supplied onto the adhesive 6 from the foil feed spool 40, pressed and adhered by the nip roller 42 (upper roller 42a and lower roller 42b), and pulled by the take-up spool 44, as shown in FIG. As shown in 2), the metal layer 4 of the foil is transferred only on the adhesive 6 and the unnecessary foil transfer sheet H is collected by the take-up spool 44.

d) Step (second curing)
The foil-recorded recording medium is further irradiated with ultraviolet rays by a second ultraviolet irradiation unit 54 provided on the downstream side, the adhesive is further cross-linked, and the recording medium with foil after transfer is collected on a collection roll 36. .
The second curing by irradiation with the second ultraviolet lamp does not require the use of a light source having a narrow emission wavelength, and has a wide emission wavelength so as to include the absorption wavelength of the second polymerization initiator for the second curing. A light source can be used. For example, a low-pressure mercury lamp or a high-pressure mercury lamp can be used.
Possible by selecting a compound that has an absorption peak at a shorter wavelength than the absorption peak wavelength of the polymerization initiator for the first curing as the polymerization initiator for the second curing and has almost no absorption at the LED emission peak wavelength. It is. As described above, the emission spectrum of the second curing light source may be broad as long as it includes the absorption wavelength of the second curing polymerization initiator.

  In the present invention, after the foil is first transferred to the substrate, the ink containing the colorant is discharged onto the substrate or the transferred foil. Usually, since there is a difference in surface energy between the base material and the foil, a difference occurs in the spread diameter of the landed ink, which is not preferable in terms of image quality. As described above, in addition to optimally adjusting the image data on the base material and the foil, after the foil transfer, the entire surface including the transferred foil is primed to form a uniform surface and ink is formed. It is also possible to do. In this case, it is preferable to drop the ink of the next color onto the ink obtained by semi-curing the ink containing the undercoat liquid because a higher quality image can be obtained.

Here, the semi-curing of the ink will be described.
In the present invention, “semi-curing of ink” means partially cured (partially cured) and refers to a state where the ink is partially cured but not completely cured. In addition, when the ink liquid applied on the recording medium (base material) P is semi-cured, the degree of curing may be non-uniform, and the liquid is cured in the depth direction. preferable.
For example, when a radical polymerizable liquid is cured in air or air partially substituted with an inert gas, radical polymerization tends to be inhibited on the surface of the liquid because of the action of suppressing radical polymerization of oxygen. is there. As a result, the semi-curing becomes non-uniform, the curing progresses more inside the liquid, and the surface curing tends to be delayed.

  In the present invention, a radical photopolymerizable liquid is used in the presence of radical polymerization-inhibiting oxygen and partially photocured, so that the degree of cure of the liquid is higher in the interior than in the exterior. Can do.

In addition, when curing a cationically polymerizable undercoat liquid in humid air, there is a tendency for moisture to be inhibited in the undercoat liquid due to the action of inhibiting the cationic polymerization of the water, leading to a delay in surface hardening. It becomes.
Even if the liquid is partially photocured using humidity under a cationic polymerization inhibitory action, the degree of cure of the liquid can be higher in the interior than in the exterior.

  When the ink liquid is semi-cured and an ink liquid having a different hue is ejected onto the semi-cured ink liquid, a technical effect favorable to the quality of the obtained printed matter can be obtained. Moreover, the action mechanism can be confirmed by observing the cross section of the printed matter. For example, when the apparatus of FIG. 2 is used, if transparent ink is ejected by the recording head 48X and semi-cured by the ultraviolet irradiation unit 52, and then yellow ink is ejected by the recording head 48Y, it is ejected into the semi-cured transparent ink. Thus, a clear yellow color can be obtained, which can be fixed on the recording medium by the ultraviolet exposure unit 54 for final exposure.

FIG. 6 is a schematic cross-sectional view showing a recording medium in which the ink liquid db is ejected onto the semi-cured ink liquid da, and FIGS. 7A and 7B show the uncured ink liquid, respectively. FIG. 7C is a schematic cross-sectional view showing an example of a recording medium on which ink liquid db is deposited on da, and FIG. 7C is a recording target on which ink liquid is deposited on the completely cured ink liquid. It is a typical sectional view showing an example of a medium.
When a secondary color is formed by depositing the ink liquid db on the ink liquid da after the ink liquid da has been deposited, it is preferable to apply the ink liquid db onto the semi-cured ink liquid da. .
Here, the semi-cured state of the ink liquid da means that, as shown in FIG. 6, when the ink liquid db is deposited on the ink liquid da, (1) a part of the ink liquid db is the surface of the ink liquid da. (2) a part of the ink liquid db is submerged in the ink liquid da, and (3) the ink liquid da is present in the lower layer of the ink liquid db.
By semi-curing the ink liquid in this manner, the cured film of the ink liquid da (colored film A) and the cured film of the ink liquid db (colored film B) can be suitably stacked, and good color reproduction is possible. It becomes.

On the other hand, when the ink liquid db is ejected onto the uncured ink liquid da, as shown in FIG. 7 (A), all of the ink liquid db sinks into the ink liquid da and / or As shown in FIG. 7B, the ink liquid da does not exist below the ink liquid db. In this case, even if the ink liquid db droplet is applied at a high density, the droplets are independent from each other, which causes a decrease in the saturation of the secondary color.

  Further, when the ink liquid db is ejected onto the completely cured ink liquid da, the ink liquid db does not enter the ink liquid da as shown in FIG. In this case, droplet ejection interference occurs, a uniform ink liquid film layer cannot be formed, and color reproducibility is reduced.

Here, when droplets of the ink liquid db are applied at a high density, the droplets are not independent of each other, and a uniform ink liquid db film layer is formed, and the occurrence of droplet ejection interference is suppressed. Therefore, the amount of the uncured portion of the ink liquid da per unit area is preferably smaller than the maximum droplet amount of the ink liquid db applied per unit area, and more preferably sufficiently small. That is, the weight Mda (also referred to as M (ink liquid A)) per unit area of the uncured portion of the ink liquid da layer and the maximum weight mdb (m (ink liquid B) of the ink liquid ejected per unit area. )) Preferably satisfies (mdb / 30) <Mda <mdb, more preferably satisfies (m (db / 20) <Mda <(mdb / 3), and (mdb / 10) < It is particularly preferable to satisfy Mda <(mdb / 5).
By setting (mdb / 30) <Mda, the occurrence of droplet ejection interference can be prevented, and the dot size reproducibility can be increased. In addition, by setting Mda <mdb, the film layer of the ink liquid da can be formed uniformly, and the decrease in density can be prevented.

Here, the weight of the uncured portion of the ink liquid da per unit area is obtained by a transfer test. Specifically, after the end of the semi-curing process (for example, after irradiation with active energy rays) and before the droplets of the ink liquid db are ejected, the penetrating medium such as plain paper is removed from the semi-cured ink liquid. The amount of the ink liquid da pressed against the da layer and transferred to the permeation medium is measured by weight measurement, and the measured value is defined as the weight of the uncured portion of the ink liquid.
For example, if the maximum discharge amount of the ink liquid db is 12 picoliters per pixel at a droplet ejection density of 600 × 600 dpi, the maximum weight mdb of the ink liquid db discharged per unit area is 0.04 g / cm ^2. (The density of the ink liquid db is about 1.1 g / cm ³ ). Therefore, in this case, the weight Mda uncured portions per unit area of the ink da layer is preferably to increase 0.04 g / cm less than ² than ^{0.0013g / cm 2, 0.002g / cm} 2 more preferably to greater 0.013 g / cm less than ^2, and particularly preferably larger 0.008 g / cm less than ² than 0.004 g / cm ^2.

  When the semi-cured state of the ink liquid is realized by a polymerization reaction of a polymerizable compound initiated by irradiation with active energy rays or heating, a non-polymerization rate (that is, A (after polymerization) from the viewpoint of improving the scratching property of the printed matter. / A (before polymerization)) is preferably 0.2 or more and 0.9 or less, more preferably 0.3 or more and 0.9 or less, and 0.5 or more and 0.9 or less. Particularly preferred.

Here, A (before polymerization) is the absorbance of the infrared absorption peak due to the polymerizable group before the polymerization reaction, and A (after polymerization) is the absorbance of the infrared absorption peak due to the polymerizable group after the polymerization reaction. .
For example, when the polymerizable compound contained in the undercoat liquid and / or the ink liquid is an acrylate monomer or a methacrylate monomer, an absorption peak based on a polymerizable group (acrylate group, methacrylate group) can be observed in the vicinity of 810 cm ^−1. The non-polymerization rate is preferably defined by the peak absorbance. When the polymerizable compound is an oxetane compound, an absorption peak based on a polymerizable group (oxetane ring) can be observed in the vicinity of 986 cm ⁻¹ , and it is preferable to define the non-polymerization rate based on the absorption light intensity of the peak. . When the polymerizable compound is an epoxy compound, an absorption peak based on a polymerizable group (epoxy group) can be observed in the vicinity of 750 cm ⁻¹ , and the non-polymerization rate is preferably defined by the absorption luminous intensity of the peak.

  In addition, as a means for measuring the infrared absorption spectrum, a commercially available infrared spectrophotometer can be used, which may be either a transmission type or a reflection type, and is preferably selected as appropriate in the form of a sample. For example, it can be measured using an infrared spectrophotometer FTS-6000 manufactured by BIO-RAD.

  In the case of a curing reaction based on an ethylenically unsaturated compound or cyclic ether, the non-polymerization rate can be quantitatively measured by the reaction rate of the ethylenically unsaturated group or cyclic ether group.

  In addition, as a method of semi-curing the ink liquid, (1) a so-called agglomeration phenomenon such as imparting a basic compound to an acidic polymer, or imparting an acidic compound or a metal compound to a basic polymer. (2) A method in which an ink liquid is prepared to have a high viscosity in advance, and a low-boiling point organic solvent is added thereto to reduce the viscosity, and the low-boiling point organic solvent is evaporated to return to the original high viscosity. 3) A method of heating an ink liquid prepared to a high viscosity and returning it to the original high viscosity by cooling, (4) a method of causing an active energy ray or heat to the ink liquid and causing a curing reaction, etc. Can be mentioned. Among these, (4) a method in which an active energy ray or heat is applied to the ink liquid to cause a curing reaction is preferable.

  Note that the method of causing a semi-curing reaction by applying an active energy ray or heat is a method in which the polymerization reaction of the polymerizable compound on the surface of the lower ink liquid applied to the recording medium is insufficiently performed. On the surface of the ink liquid, the polymerization reaction tends to be hindered by the influence of oxygen in the air, compared to the inside. Therefore, the semi-curing reaction of the ink liquid can be caused by controlling the application conditions of the active energy ray or heat.

The amount of energy required for semi-curing the lower ink liquid varies depending on the type and content of the polymerization initiator, but when energy is applied by active energy rays, it is generally preferably about 1 to 500 mJ / cm ² . Further, when energy is applied by heating, it is preferable to heat for 0.1 to 1 second under the condition that the surface temperature of the recording medium is in a temperature range of 40 to 80 ° C.

Generation of active species due to decomposition of the polymerization initiator is promoted by application of active energy rays such as actinic light and heating, or heat, and polymerizability or cross-linkability caused by the active species is increased by increasing the active species or increasing the temperature. The curing reaction by polymerization or crosslinking of the material is accelerated.
Moreover, thickening (viscosity increase) can also be suitably performed by irradiation of actinic light or heating.

  The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these.

Example 1
Liquid 2 having the following composition was stirred with a high-speed water-cooled stirrer to obtain an ultraviolet ink jet adhesive precursor liquid.
[Liquid 2]
・ N-vinylcaprolactam 4.1 parts ・ 2-ethylhexyl acrylate 39.5 parts ・ Light acrylate IO-A 22.8 parts ・ First cure ST-1 0.05 parts ・ Lucirin TPO 8.5 parts ・ Irgacure 819 (bis AcylPhosphine)
5.0 parts · 2- (2 vinyloxyethoxy) ethyl acrylate 10.0 parts · Irgacure 250 (iodonium salt polymerization initiator)
5.0 parts BYK 307 0.05 parts Acrylic resin a (2-ethylhexyl methacrylate / n-butyl methacrylate / butyl acrylate / 2-hydroxyl methacrylate methacrylate, glass transition temperature-20 ° C., 5 parts by weight average molecular weight)

Note Light acrylate IO-A: Isooctyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd.
First cure ST-1: (Polymerization inhibitor, manufactured by Chem First)
Lucirin TPO: (photopolymerization initiator (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide), manufactured by BASF)
Irgacure 819: Radical polymerization initiator (bisacylphosphine): Photopolymerization initiator, 2- (2-vinyloxyethoxy) ethyl acrylate manufactured by Ciba Specialty Chemicals: Nippon Shokubai Co., Ltd.

Using the apparatus shown in FIG. 1, the liquid 2 is ejected from an on-demand liquid delivery head, and an ultraviolet LED having a peak emission wavelength of 365 nm (NSHA 550B manufactured by Nichia Corporation) is used as a light source for curing at the curing unit 14. Used to irradiate ultraviolet light, phenyl-bis (2,4,6-trimethylbenzoyl) phosphine oxide (product name: Ciba Specialty Chemicals IRGACURE819) radical photopolymerization initiator with absorption peak wavelength at 295 and 370 nm Irgcure819 Was activated and polymerized to obtain an image of a sticky adhesive layer. In the foil image forming unit, a silver foil image was formed using the silver foil transfer sheet H. Yellow ink was partially ejected from the ink head from above the silver foil image. Characters were ejected in color on portions other than the foil image. Then, as a light source for the second curing, the image fixing unit 18 equipped with a high-pressure mercury lamp (UMIOH UM-452) is irradiated with ultraviolet light, and as a cationic photopolymerization initiator, it has an absorption peak wavelength at 240 nm, Activating and cationically polymerizing (4-methylphenyl) [4- (2-methylpropyl) phenyl], hexafluorophosphate iodonium (IRGACURE250 manufactured by Ciba Specialty Chemicals), which has almost no absorption above 340 nm, and adhesive The layer and the ink layer were sufficiently cured to obtain a clear printed matter having a golden or silver foil image and color letter printing.
As described in this example, by using a compound having both a radical polymerizable group and a cationic polymerizable group as a liquid of an adhesive precursor for transferring a foil, a two-stage curing is performed. Since transferability and adhesion between the recording medium and the foil can be compatible, it is preferable. In particular, since the apparatus of the present invention has an ultraviolet light source for curing an adhesive and a light source for ink curing, the above-described aspect can be obtained without adding an expensive ultraviolet light source. .

(Example 2)
The following liquid 1 was stirred with a high-speed water-cooled stirrer in the same manner as in Example to obtain liquid 1 as an ultraviolet inkjet liquid.
[Liquid 1]
・ N-vinylcaprolactam 5.0 parts ・ 2-ethylhexyl acrylate 48.4 parts ・ Light acrylate IO-A 28.0 parts ・ First cure ST-1 0.05 part ・ Lucirin TPO 8.5 parts ・ Irgacure 819 (bisacyl Phosphine) 5.0 parts BYK 307 0.05 parts Acrylic resin (2-ethylhexyl methacrylate / n-butyl methacrylate / butyl acrylate / 2-hydroxyl methacrylate methacrylate, glass transition temperature-20 ℃, weight average molecular weight 50,000) 5 parts

The first curing was performed with an LED-type ultraviolet light irradiation device (ultraviolet LED having an emission peak wavelength of 365 nm (NSHA 550B array manufactured by Nichia Corporation)) mounted on a carriage. The integrated light quantity was set to 3000 mJ / cm ^2. Using the apparatus shown in Fig. 1, foil transfer and ink jet printing were performed in the same manner as in Example 1.
In the second curing, an ultraviolet lamp and a HAN250NL high-cure mercury lamp (manufactured by GS Yuasa Corporation) were irradiated so that the integrated light amount was 6000 mJ / cm ² .
By reducing the integrated light quantity of the first curing, a sticky adhesive layer was obtained, and the second curing thereafter could be sufficiently cured.

(Example 3)
Using the apparatus shown in FIG. 2, foil transfer similar to that in Example 1 is performed using the liquid 2 used in Example 1, and then ultraviolet rays are discharged after ink is ejected by the recording heads 48X, 48Y, 48C, 48M, and 48K. Each of the inks was semi-cured by the irradiation unit 52, and finally the ink was sufficiently cured by the final curing ultraviolet irradiation unit 54 for printing. A particularly clear printed matter having golden and silver foil images and color letter printing was obtained. The adhesion between the recording medium and the foil was good.

1 is a front view showing a schematic configuration of an example of an ink jet recording apparatus of the present invention. It is a front view which shows schematic structure of the other example of the inkjet recording device of this invention. It is sectional drawing which shows one example of foil structure. It is a schematic diagram which shows the process using the apparatus of this invention. (A) is a discharge process, (b) is a first curing process, (c-1) and (c-2) are foil transfer processes, and (d) is a second curing process. It is a schematic diagram explaining the example of the compound which has both the radically polymerizable group and cation polymerizable group used for this invention method, and its polymerization state. FIG. 5 is a schematic cross-sectional view illustrating an example of a recording medium in which an ink liquid is ejected onto a semi-cured ink liquid. (A) and (B) are schematic cross-sectional views showing an example of a recording medium in which an ink liquid is ejected onto an uncured ink liquid, respectively, and (C) is a completely cured state. FIG. 3 is a schematic cross-sectional view illustrating an example of a recording medium on which ink liquid is ejected onto the ink liquid.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Protective layer 2 Peeling layer 3 Lacquer layer 4 Metal layer 5 Auxiliary adhesive 6 Adhesive 8 Adhesive layer 10 Inkjet recording apparatus 11 Foil 12 Transport part 13 On-demand type droplet sending part 14 Curing part 15 Foil image forming part 16 Image Recording unit 18 Image fixing unit 20 Control unit 22 Input / output device 24 Droplet delivery head 25 Liquid (adhesion liquid)
26 Composition tank 28 UV lamp 30 Supply roll 32 Transport roll 34 Transport roll pair 36 Collection roll 38 UV light source 40 Foil feed spool 42 Foil transfer nip roller 44 Take-up spool 46 Recording head units 48, 48X, 48Y, 48C, 48M, 48K Recording head 50, 50X, 50Y, 50C, 50M, 50K Ink tank 52, 54 Ultraviolet irradiation unit 56 Platen P Recording medium H Foil transfer sheet

Claims (2)

An on-demand droplet delivery head for ejecting a liquid containing an active energy ray-polymerizable compound and a polymerization initiator imagewise on either a recording medium or a foil;
Means for irradiating the liquid with active energy rays to form an image of a pressure-sensitive adhesive having adhesiveness on either the recording medium or the foil;
Foil image forming means for transferring either one of the recording medium and the foil to the image of the formed adhesive and forming an image of the foil on the recording medium;
An inkjet head disposed downstream of the foil image forming unit in the transport direction of the recording medium and forming an image on the recording medium on which the foil image is formed by ejecting ink containing at least a coloring material; Inkjet recording, comprising: an image forming unit, wherein after transferring the foil, the entire surface including the transferred foil is undercoated, and the next color can be ejected onto the ink obtained by semi-curing the ink including the undercoat liquid. apparatus. The ink jet recording apparatus according to claim 1, wherein the on-demand type droplet discharge head performs droplet ejection by a single pass.

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