JP2014008609A - Method of manufacturing recorded matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a recorded matter which can securely and efficiently manufacture a recorded matter having a printed part with excellent fixability and a desired shape.SOLUTION: A method of manufacturing a recorded matter includes: a process of providing a first ink containing a polymerizable compound polymerized by irradiation of an ultraviolet ray on an intermediate transfer medium; a process of polymerizing the polymerizable compound by irradiating the first ink with the ultraviolet ray; a process of providing a second ink containing colorant, thermoplastic resin, and volatile liquid on a part of the intermediate transfer medium with the first ink provided by an inkjet method; a first heating process of heating the intermediate transfer medium and volatilizing at least a part of the volatile liquid; a process of transferring the second ink and the first ink heated in the first heating process to a recording medium; and a process of heating the second ink transferred to the recording medium.

Description

  The present invention relates to a method for manufacturing a recorded matter.

As a method for producing a recorded matter, a method using an ink jet method is widely used. The ink jet method is excellent in that a fine pattern can be suitably formed, a plate is not required, and small lot production and multi-product production can be suitably handled.
However, when printing directly on a recording medium by the ink jet method, depending on the type of the recording medium (for example, a non-absorbing medium such as a plastic recording medium not provided with an ink receiving layer) Ink that does not dry (unsolidified) when ink flow or repelling occurs, or it takes time to dry (solidify) the ink applied to the recording medium, and when the recording medium to which the ink has been applied is discharged There has been a problem that the image is disturbed, and it has been difficult to reliably form a printing portion having a desired shape.
In order to solve such a problem, an intermediate transfer type recording method is used (for example, see Patent Document 1).

However, conventionally, it has been difficult to sufficiently prevent the above-described problems from occurring even if an intermediate transfer type recording method is used. In addition, the conventional intermediate transfer type recording method has a problem that it is difficult to sufficiently improve the fixing property of the printing portion on the recording medium.
In particular, the above-mentioned tendency has been remarkably generated when a plastic film material used for product packaging or the like is used as a recording medium.

Japanese Patent No. 3177985

  An object of the present invention is to provide a method for producing a recorded matter, which is capable of reliably and efficiently producing a recorded matter having a printing part having a desired shape and excellent fixability.

Such an object is achieved by the present invention described below.
The method for producing a recorded matter of the present invention includes a first ink application step of applying a first ink containing a polymerizable compound that is polymerized by irradiation of ultraviolet rays to an intermediate transfer medium;
A polymerization step of irradiating the first ink with ultraviolet rays to polymerize the polymerizable compound;
A second ink application step of applying a second ink containing a colorant, a thermoplastic resin, and a volatile liquid to a portion of the intermediate transfer medium to which the first ink has been applied by an inkjet method;
A first heating step of heating the intermediate transfer medium to volatilize at least a part of the volatile liquid;
A transfer step of transferring the second ink and the first ink heated in the first heating step to a recording medium;
And a second heating step of heating the second ink transferred to the recording medium.
As a result, it is possible to provide a method for producing a recorded matter that can reliably and efficiently produce a recorded matter that has excellent fixing properties and includes a printing unit having a desired shape. Further, in the obtained recorded matter, a three-dimensional hologram-like expression can be realized by the unevenness by the first ink and the coloring by the second ink.

In the method for producing a recorded matter of the present invention, in the first heating step, the intermediate transfer medium is heated from the side opposite to the side to which the second ink is applied, and at least a part of the volatile liquid is obtained. It is preferable to volatilize.
As a result, only the outer surface of the second ink applied on the intermediate transfer medium is dried, so that liquid (volatile liquid or the like) is more reliably trapped inside the film-like second ink. And the volatile liquid can be more efficiently removed from the entire second ink. As a result, the stability of the shape of the second ink is improved, and it is possible to more reliably prevent the pattern of the second ink from being disturbed during transfer or the like. Accordingly, it is possible to more reliably and more efficiently produce a recorded matter having a printing portion having a desired shape.

In the method for producing a recorded matter of the present invention, prior to the first ink application step, a surface treatment liquid application step of applying a surface treatment liquid to a portion of the intermediate transfer medium to which the first ink is to be applied. Furthermore, it is preferable to have.
As a result, the first ink and the second ink are particularly excellent in releasability from the intermediate transfer medium at the time of transfer while reliably preventing unintentional disturbances in the pattern of the second ink. The productivity and yield of the recorded matter can be made particularly excellent.

In the recorded matter manufacturing method of the present invention, the surface treatment liquid preferably contains a wax.
As a result, the first ink and the second ink can be more excellently released from the intermediate transfer medium during transfer while reliably preventing unintentional disturbances in the pattern of the second ink. The productivity and yield of recorded matter can be further improved. Further, in the transfer step, an appropriate amount of wax can be transferred to the recording medium together with the first ink and the second ink, and the finally obtained recorded matter has particularly excellent abrasion resistance. it can.

In the method for producing a recorded matter of the present invention, the surface treatment liquid preferably contains one or more selected from the group consisting of polyolefin wax, ethylene vinyl acetate wax and carnauba wax.
Thereby, the releasability of the first ink and the second ink from the intermediate transfer medium at the time of transfer can be made particularly excellent, and the productivity and yield of the recorded matter can be made particularly excellent. Can do. Further, in the transfer process, together with the first ink and the second ink, an appropriate amount of wax can be more reliably transferred to the recording medium, and the finally obtained recorded matter has particularly excellent abrasion resistance. can do.

In the method for producing a recorded matter according to the aspect of the invention, the first ink may include a liquid polymerizable compound that forms a liquid alone under the conditions of the first ink application step as the polymerizable compound. preferable.
As a result, it is not necessary to use a volatile solvent as a constituent component of the first ink, or the content of the volatile solvent can be made low. The process for volatilization can be omitted or simplified, and the productivity of recorded matter can be made particularly excellent. In addition, it is possible to more effectively prevent the occurrence of problems such as deterioration in the image quality of the printing unit due to the volatilization of the solvent during the manufacturing process of the recorded matter.

In the method for producing a recorded matter of the present invention, it is preferable that the first ink contains allyl glycol as the liquid polymerizable compound.
Thereby, the printing part which has a desired shape can be formed more reliably. Further, the productivity of recorded matter can be made particularly excellent. Further, the fixing strength of the printed part in the recorded matter can be made particularly excellent. Moreover, in the finally obtained recorded matter, the three-dimensional effect of the printing portion can be made more excellent.

In the recorded matter manufacturing method of the present invention, it is preferable that the second ink contains a liquid component having a boiling point of 110 ° C. or more and 250 ° C. or less as the volatile liquid.
Thereby, in a 1st heating process, a volatile liquid can be volatilized moderately and the stability of the shape of a 2nd ink can be improved more effectively. In the second heating step, the volatile liquid can be removed more reliably, and the occurrence of adverse effects due to the remaining volatile liquid in the finally obtained recorded matter can be more reliably prevented. .

In the recorded matter manufacturing method of the present invention, it is preferable that the second heating step is performed by heating from the surface of the recording medium opposite to the side on which the second ink is transferred. .
As a result, the portion of the second ink that comes into contact with the recording medium can be more reliably and efficiently softened, and the fixing strength of the printing unit with respect to the recording medium, the durability of the recorded matter, and the reliability can be particularly improved. It can be excellent.

It is a block diagram which shows typically suitable embodiment of the manufacturing apparatus of the recorded matter of this invention. It is a block diagram which shows typically other embodiment of the manufacturing apparatus of the recorded matter of this invention. It is a block diagram which shows typically other embodiment of the manufacturing apparatus of the recorded matter of this invention.

≪Recorded material manufacturing method, manufacturing equipment≫
First, the manufacturing method and manufacturing apparatus of the recorded matter of the present invention will be described.
The method for producing a recorded matter of the present invention includes a first ink application step of applying a first ink containing a polymerizable compound that is polymerized by irradiation of ultraviolet rays to an intermediate transfer medium, and irradiating the first ink with ultraviolet rays. And a second ink containing a colorant, a thermoplastic resin, and a volatile liquid at a portion of the intermediate transfer medium to which the first ink is applied, and a polymerization step of polymerizing the polymerizable compound. A second ink applying step applied by the first heating step, a first heating step of heating the intermediate transfer medium to volatilize at least a part of the volatile liquid, and the second heating heated in the first heating step. And a transfer step of transferring the first ink to a recording medium, and a second heating step of heating the second ink transferred to the recording medium.

  In this way, the first ink containing a polymerizable compound that is polymerized by irradiation with ultraviolet rays is applied in advance to the region to which the second ink containing the colorant, the thermoplastic resin, and the volatile liquid is to be applied. The first ink is irradiated with ultraviolet rays to polymerize the polymerizable compound, and before transferring to the recording medium, the intermediate transfer medium is heated to volatilize at least a part of the volatile liquid, whereby the second ink is obtained. It is possible to improve the efficiency of the transfer of the second ink from the intermediate transfer medium to the recording medium while reliably preventing the unintentional deformation of the ink pattern, and as a result A recorded matter having a printed portion having a shape can be produced reliably and efficiently.

  That is, by volatilizing at least a part of the volatile liquid by heating before transfer to the recording medium, the solid content increases, so that the stability of the shape of the second ink is improved, and at the time of transfer For example, it is possible to reliably prevent the pattern of the second ink from being disturbed. In particular, by heating the intermediate transfer medium, only the outer surface of the second ink is dried, and the liquid (volatile liquid) is reliably prevented from being trapped inside the film-like second ink. Therefore, the effect of stabilizing the shape of the second ink is reliably exhibited. In addition, the first ink is applied to the intermediate transfer medium in advance, and the polymerizable compound constituting the first ink is polymerized before the second ink is applied, so that the second ink is transferred from the intermediate transfer medium at the time of transfer. The releasability of is excellent. In other words, in the present invention, the above-described effects act synergistically, and a recorded matter including a printing unit having a desired shape can be reliably and efficiently manufactured.

  On the other hand, the present invention further includes a second heating step of heating the second ink after transfer to the recording medium. Therefore, the thermoplastic resin constituting the second ink can be softened after transfer to the recording medium, and in the finally obtained recorded matter, the fixing property of the printing part to the recording medium is sufficiently excellent. be able to. Further, in the obtained recorded matter, a three-dimensional hologram-like expression can be realized by the unevenness by the first ink and the coloring by the second ink.

DESCRIPTION OF EMBODIMENTS Hereinafter, preferred embodiments of a method and apparatus for manufacturing recorded matter according to the present invention will be described in more detail with reference to the accompanying drawings.
FIG. 1 is a configuration diagram schematically showing a preferred embodiment of the recorded product manufacturing apparatus of the present invention. Note that the drawings referred to in this specification show part of the configuration in an exaggerated manner, and do not accurately reflect actual dimensions and the like.

  In the method for producing a recorded matter of the present embodiment, the surface treatment liquid application step for applying the surface treatment liquid 50 to the intermediate transfer medium 11 and the portion of the intermediate transfer medium 11 to which the surface treatment liquid 50 is applied are irradiated with ultraviolet rays. A first ink applying step for applying the first ink 51 containing a polymerizable compound that is polymerized by the polymerization, a polymerization step for polymerizing the polymerizable compound constituting the first ink 51 by irradiating ultraviolet rays, and the intermediate transfer medium 11. A second ink application step in which a second ink 52 containing a colorant, a thermoplastic resin, and a volatile liquid is applied to the portion to which the first ink 51 is applied by an inkjet method; and the intermediate transfer medium 11 A first heating step of heating and volatilizing at least a part of the volatile liquid constituting the second ink 52, and the second ink 52 and the first ink 5 heated in the first heating step It has a transfer step of transferring to a recording medium 53, and a second heating step of heating the second ink 52 transferred to the recording medium 53 a. In the polymerization step, the polymerizable compound constituting the first ink 51 may be partially (partially) polymerized. In such a case, for example, after the transfer to the recording medium 53, the polymerization reaction of the polymerizable compound may be performed by further irradiating ultraviolet rays.

  As shown in FIG. 1, the manufacturing apparatus 100 includes an intermediate transfer medium 11, surface treatment liquid application means 12 for applying a surface treatment liquid 50 to the intermediate transfer medium 11, and surface treatment applied to the intermediate transfer medium 11. A drying unit 30 for drying the liquid 50; a first ink applying unit 13 for applying the first ink 51 to the intermediate transfer medium 11; a second ink applying unit 14 for applying the second ink 52; Ultraviolet irradiation means (first ultraviolet irradiation means) 15 for irradiating the first ink 51 on the transfer medium 11 with ultraviolet light, and first heating means 16 for heating the second ink 52 on the intermediate transfer medium 11 And a second heating means 17 for heating the second ink 52 transferred to the recording medium 53.

In the illustrated configuration, the intermediate transfer medium 11 has an endless belt shape. The intermediate transfer medium 11 is supported by the support rolls 18A and 18B and the pressure roll 19A so as to rotate while applying tension from the inner peripheral surface side. Further, the intermediate transfer medium 11 has a width equal to or greater than the width of the recording medium 53.
It is preferable that the intermediate transfer medium 11 has ultraviolet transparency. As a result, as will be described in detail later, the ultraviolet irradiation means 15 passes the intermediate transfer medium 11 (from the side opposite to the surface to which the first ink 51 of the intermediate transfer medium 11 is applied) to the first. The ink 51 can be irradiated with ultraviolet rays.

Examples of the constituent material of the intermediate transfer medium 11 include various resins (for example, polyimide, polyamideimide, polyester, polyurethane, polyamide, polyethersulfone, fluorine resin, etc.), various rubbers (for example, nitrile rubber, ethylene). Propylene rubber, chloroprene rubber, isoprene rubber, styrene rubber, butadiene rubber, butyl rubber, chlorosulfonated polyethylene, urethane rubber, epichlorohydrin rubber, acrylic rubber, silicone rubber, fluorine rubber, etc.), various metal materials, and the like. The intermediate transfer medium 11 may have a single layer configuration or a stacked configuration.
The ultraviolet transmittance of the intermediate transfer medium 11 is preferably 70% or more. Thereby, ultraviolet rays are efficiently supplied to the first ink 51, and the polymerization reaction of the polymerizable compound can be suitably advanced. In addition, heat generation due to the intermediate transfer medium 11 absorbing ultraviolet rays can be effectively prevented and suppressed.

  The surface treatment liquid application unit 12 applies the surface treatment liquid 50 to the intermediate transfer medium 11 in the surface treatment liquid application process. As described above, in this embodiment, prior to the first ink application step, the surface treatment liquid application step for applying the surface treatment liquid 50 to the portion of the intermediate transfer medium 11 to which the first ink 51 is to be applied is provided. doing. This ensures that the first ink 51 and the second ink 52 can be released from the intermediate transfer medium 11 during transfer while reliably preventing unintentional disturbance in the pattern of the second ink 52. It can be made particularly excellent, and the productivity and yield of the recorded matter can be made particularly excellent.

  The surface treatment liquid application unit 12 may be, for example, a bar coater, a coating roller, or a brush. In the illustrated configuration, the surface treatment liquid application unit 12 is a recording head (droplet discharge head) that performs droplet discharge by an inkjet method. Thereby, the surface treatment liquid 50 is efficiently and selectively applied to a predetermined area of the intermediate transfer medium 11 (for example, an area corresponding to an area to which the first ink 51 and the second ink 52 are applied). It is possible to suppress the amount of the surface treatment liquid 50 used while making the recorded product productivity particularly excellent, which is preferable from the viewpoint of resource saving.

As a droplet discharge method (inkjet method), a piezo method, a method in which ink is discharged by bubbles generated by heating ink, or the like can be used. From the viewpoints of difficulty, prevention of unintentional volatilization of volatile components constituting the surface treatment liquid 50, a piezo method is preferable.
The thickness of the surface treatment liquid 50 applied on the intermediate transfer medium 11 is preferably 0.1 μm or more and 5 μm or less.
The surface treatment liquid 50 will be described in detail later.

The drying unit 30 dries the surface treatment liquid 50 applied to the intermediate transfer medium 11.
As the drying means 30, for example, various heaters can be used.
Moreover, the heating temperature by the drying means 30 can be 60 degreeC or more and 90 degrees C or less, for example.

In the first ink application process, the first ink application unit 13 transfers the first ink 51 containing a polymerizable compound that is polymerized by irradiation of ultraviolet rays to the intermediate transfer medium 11 (particularly, in the present embodiment, the surface treatment liquid 50). To the area).
The first ink application unit 13 may be, for example, a bar coater, a coating roller, or a brush. In the illustrated configuration, the first ink application unit 13 is a recording head (droplet ejection head) that ejects droplets by an inkjet method. As a result, the first ink 51 can be efficiently and selectively applied to a predetermined area of the intermediate transfer medium 11 (an area corresponding to the area to which the second ink 52 is applied). While making the productivity particularly excellent, it is possible to reduce the amount of the first ink 51 used, which is preferable from the viewpoint of resource saving.

As a droplet discharge method (inkjet method), a piezo method, a method in which ink is discharged by bubbles generated by heating ink, or the like can be used. From the viewpoint of difficulty, etc., the piezo method is preferable.
The thickness of the first ink 51 applied on the intermediate transfer medium 11 is preferably 0.1 μm or more and 5 μm or less. The thickness of the first ink 51 may be different at each part. As a result, in the finally obtained recorded matter, a more three-dimensional expression is possible.
The first ink 51 will be described in detail later.

The second ink application unit 14 includes a second ink that includes a colorant, a thermoplastic resin, and a volatile liquid in a portion of the intermediate transfer medium 11 to which the first ink 51 is applied in the second ink application process. 52 is given.
The second ink applying unit 14 is a recording head (droplet discharge head) that discharges droplets by an inkjet method. Thereby, the 2nd ink 52 can be provided with a desired pattern, and the printed part of a fine pattern can be suitably formed in the recorded matter finally obtained, for example. In addition, since the ink jet method does not require a plate or the like and has excellent on-demand properties, it can be suitably adapted to small-lot production and multi-product production.

  In the illustrated configuration, the manufacturing apparatus 100 includes, as the second ink application unit 14, a second ink application unit 14 </ b> C that discharges the cyan second ink 52, and a magenta second ink application unit 14 </ b> C. The second ink applying unit 14M that discharges the ink 52, the second ink applying unit 14Y that discharges the yellow (yellow) second ink 52, and the second ink that discharges the white (white) second ink 52. The ink application unit 14 </ b> W and the second ink application unit 14 </ b> K that discharges the black second ink 52 are provided. As a result, the color gamut that can be expressed in the printed portion of the finally obtained recorded matter can be made wider.

As a droplet discharge method (inkjet method), a piezo method, a method of discharging ink by bubbles generated by heating ink, or the like can be used. From the viewpoints of difficulty and prevention of unintentional volatilization of the volatile components constituting the second ink 52, the piezo method is preferable.
The ultraviolet irradiation means (first ultraviolet irradiation means) 15 irradiates the first ink 51 on the intermediate transfer medium 11 with ultraviolet rays in the polymerization step. Thereby, the first ink 51 can be polymerized, and the second ink 52 applied later can be suitably transferred to the recording medium 53 in the transfer step.

  In particular, in the present embodiment, the ultraviolet irradiation unit 15 irradiates the first ink 51 via the intermediate transfer medium 11, that is, the surface opposite to the surface to which the first ink 51 of the intermediate transfer medium 11 is applied. Irradiation of ultraviolet rays from the surface side. Thereby, without completely polymerizing the polymerizable compound contained in the first ink 51, while maintaining only partial polymerization, among the polymerizable compounds contained in the first ink 51 having a predetermined thickness, What is included in the region on the side facing the intermediate transfer medium 11 can be preferentially polymerized. That is, the adhesiveness can be varied in the thickness direction of the first ink 51 on the intermediate transfer medium 11. As a result, the adhesion between the first ink 51 and the second ink 52 applied in a later step can be made particularly excellent. As a result, the second ink 52 from the intermediate transfer medium 11 can be obtained. The releasability (transferability to the recording medium 53) (which is a combination of the first ink 51 and the second ink 52) can be made particularly excellent, and the productivity and yield of recorded matter can be improved. It can be made particularly excellent.

Examples of the ultraviolet irradiation means 15 include a metal halide lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a deep ultraviolet lamp, a lamp that uses a microwave to excite a mercury lamp from the outside without an electrode, an ultraviolet laser, a xenon lamp, and a UV-LED Diode) or the like can be used, and among them, it is preferable to use a UV-LED.
The first heating unit 16 heats the second ink 52 on the intermediate transfer medium 11 in the first heating step. In particular, in the present embodiment, the first heating unit 16 heats the second ink 52 via the intermediate transfer medium 11, that is, the surface of the intermediate transfer medium 11 to which the second ink 52 is applied. Is heated from the opposite side. As a result, only the outer surface of the second ink 52 applied onto the intermediate transfer medium 11 is dried, and liquid (volatile liquid or the like) is trapped inside the film-like second ink 52. This can be prevented more reliably, and the volatile liquid can be more efficiently removed from the entire second ink 52. As a result, the stability of the shape of the second ink 52 is improved, and it is possible to more reliably prevent the pattern of the second ink from being disturbed during transfer. Accordingly, it is possible to more reliably and more efficiently produce a recorded matter having a printing portion having a desired shape.

  Examples of the first heating means 16 include a heat conduction type heating means (platen heater) provided on the platen, a warm air heater, and an infrared heater. As an example of the evaporation means in the case of using a platen heater, heating with a platen heater from the back surface of the substrate, and warm air is brought into contact with the ink adhered to the substrate. By taking such an evaporation means, heat is transmitted almost evenly to the ink on the substrate, so that the evaporation amount can be easily adjusted, and curling can be prevented when the substrate is paper or the like. it can. Specifically, the evaporation amount of the component excluding the solid content in the ink attached to the base material is adjusted by controlling the heating temperature, heating time, hot air temperature, air volume, etc. of the platen part by the heater. Is possible. It is preferable to set conditions for the heater by measuring the evaporation amount in advance before the experiment.

  The heating of the second ink 52 by the first heating means 16 (heating in the first heating step) may volatilize all of the volatile liquid constituting the second ink 52, You may volatilize only a part. Even when only a part of the volatile liquid constituting the second ink 52 is volatilized by the heating by the first heating unit 16 (heating in the first heating step), the second heating unit 17 is used. Residual volatile liquid can be removed by heating (heating in the second heating step).

The heating temperature of the second ink 52 by the first heating unit 16 (heating temperature in the first heating step) is the heating temperature of the second ink 52 by the second heating unit 17 (in the second heating step). The heating temperature is preferably lower than the heating temperature. Thereby, it is possible to surely prevent the thermoplastic resin constituting the second ink 52 from being softened on the intermediate transfer medium 11 and the pattern of the second ink 52 from being disturbed.
The heating temperature of the second ink 52 by the first heating means 16 varies depending on the composition of the second ink 52, etc., but is preferably 40 ° C. or higher and 200 ° C. or lower, and is 50 ° C. or higher and 150 ° C. or lower. Is more preferable.

  The second ink 52 is intermediated by a pressure roll 19A provided on the inner peripheral surface side of the intermediate transfer medium 11 and a pressure roll 19B that also functions as a conveyance means (recording medium conveyance means) for the recording medium 53. A transfer portion that is transferred from the transfer medium 11 to the recording medium 53 is configured. In the transfer portion, the recording medium 53 is deformed so as to follow the surface shape of the pressure roll (recording medium conveying means) 19B.

  The shape of the intermediate transfer medium and the shape of the recording medium (the shape of the recording medium conveying means) in the transfer unit may be any, for example, at least one of these may be planar. In the illustrated configuration, the intermediate transfer medium 11 and the recording medium 53 are curved in a convex shape toward each other. Thereby, the transfer (transfer process) of the second ink 52 can be performed more efficiently, and the productivity and yield of the recorded matter can be made particularly excellent. Further, the fixing strength of the printed part in the recorded matter can be made particularly excellent. Further, it is advantageous from the viewpoint of downsizing the manufacturing apparatus 100.

  Further, it is preferable that the curvature of the intermediate transfer medium 11 is larger than the curvature of the recording medium 53 at a portion of the transfer portion where the second ink 52 is transferred in the transfer process. Thereby, the transfer (transfer process) of the second ink 52 can be performed more efficiently, and the productivity and yield of the recorded matter can be made particularly excellent. Further, the fixing strength of the printed part in the recorded matter can be made particularly excellent.

  The second heating unit 17 heats the second ink 52 transferred to the recording medium 53 in the second heating step. Thereby, the thermoplastic resin constituting the second ink 52 transferred to the recording medium 53 can be softened, and the fixing strength of the formed printing portion with respect to the recording medium 53 can be made sufficiently excellent. it can. Further, it is possible to reliably prevent the volatile liquid from remaining in the finally obtained recorded matter.

The heating temperature of the second ink 52 by the first heating means 16 (heating temperature in the first heating step) is T ₁ [° C.], and the heating temperature of the second ink 52 by the second heating means 17 (first temperature). when the heating temperature) in two heating step was _{T 2} [° C.], it is preferable to satisfy the relation of _{0 ≦ T 2 -T 1 ≦ 50} , satisfies 10 ≦ _T 2 -T ₁ ≦ 30 relationship More preferably. Thereby, on the intermediate transfer medium 11, the thermoplastic resin constituting the second ink 52 is softened, and the pattern by the second ink 52 is reliably prevented from being disturbed, and the printing portion to the recording medium 53 is prevented. The fixing strength can be made particularly excellent.
The heating temperature of the second ink 52 by the second heating means 17 varies depending on the composition of the second ink 52, etc., but is preferably 40 ° C. or higher and 250 ° C. or lower, and is 60 ° C. or higher and 180 ° C. or lower. Is more preferable.

  In the configuration shown in the figure, the second heating means 17 heats the second ink 52 from the surface opposite to the surface (printing surface) of the recording medium 53 on which the second ink 52 is transferred. It is. As a result, the portion of the second ink 52 that contacts the recording medium 53 can be more reliably and efficiently softened, and the fixing strength of the printing unit with respect to the recording medium 53, the durability of the recorded matter, and the reliability The property can be made particularly excellent.

As the second heating means 17, for example, an infrared heater (IR heater), a warm air heater, a halogen lamp, a ceramic heater, a heat roller, or the like can be used. Among them, an infrared heater and / or a heat roller is used. Is preferred.
When a heat roller is used as the second heating unit 17, the recording medium 53 to which the second ink 52 is transferred is pressed (without a heat source) on the side opposite to the side where the heat roller is provided. It is preferable that the rollers are arranged opposite to each other. Thereby, the recording medium 53 to which the second ink 52 is transferred can be transported more smoothly.

  Further, the manufacturing apparatus 100 includes a cleaning unit 20 that cleans the intermediate transfer medium 11 on the downstream side of the transfer unit. As a result, the first ink 51 and the second ink 52 are applied again in a state in which foreign matter (for example, a constituent component of the second ink 52 or a residue such as a modified product thereof) is attached on the recording medium 53. It is possible to prevent such occurrence, and it is possible to produce a highly reliable recorded matter repeatedly over a long period of time.

Next, the surface treatment liquid, the first ink, the second ink, and the recording medium will be described in detail.
[Surface treatment solution]
The surface treatment liquid 50 is applied to a portion of the intermediate transfer medium 11 where the first ink 51 is to be applied prior to the first ink application step.
By applying the surface treatment liquid 50 prior to the first ink 51, the transfer properties of the first ink 51 and the second ink 52 can be made particularly excellent, and the productivity and yield of recorded matter. Can be made particularly excellent.

The surface treatment liquid 50 may be any liquid as long as it has the functions described above. For example, a volatile liquid, a liquid containing wax, or the like can be preferably used.
When a volatile liquid is used as the surface treatment liquid 50, it is preferable to reduce the surface free energy of the intermediate transfer medium 11. Thereby, the transferability of the first ink 51 and the second ink 52 from the intermediate transfer medium 11 to the recording medium 53 can be made particularly excellent, and a printing portion having a desired shape can be more reliably formed. In addition, the productivity of recorded matter can be made particularly excellent.

  Note that the surface free energy value is determined by measuring the contact angle using three types of liquids whose surface free energy and each component value are known, and using these values as the Young-Dupre equation and the extended Fowkes equation. It is obtained from the formula. As an apparatus, measurement and calculation of surface free energy can be performed using solid surface energy analyzer CA-XE (manufactured by Kyowa Interface Chemical Co., Ltd.).

  Among these, the surface treatment liquid 50 is preferably a liquid containing wax. Accordingly, the first ink 51 and the second ink 52 can be released from the intermediate transfer medium 11 at the time of transfer while reliably preventing unintentional disturbance in the pattern of the second ink 52. The transferability to the recording medium 53 can be further improved, and the productivity and yield of the recorded matter can be further improved. Further, in the transfer step, an appropriate amount of wax can be transferred to the recording medium 53 together with the first ink 51 and the second ink 52, and the finally obtained recorded matter has particularly excellent abrasion resistance. can do.

Hereinafter, the surface treatment liquid 50 containing wax will be mainly described.
Various known waxes can be used as the wax. Examples of the wax constituting the surface treatment liquid 50 include polyolefin wax (polyethylene wax, polypropylene wax, etc.); ethylene vinyl acetate (EVA) wax; long chain hydrocarbon (paraffin wax, sasol wax, etc.); Examples thereof include carbonyl group-containing waxes.

  Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecandiol-bis-stearate, etc.); polyalkanol esters (trimellitic acid tristearyl, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearylamide) Etc.); dialkyl ketone (distearyl ketone) and the like.

  Especially, it is preferable that the surface treatment liquid 50 contains 1 type (s) or 2 or more types selected from the group which consists of polyolefin wax, ethylene vinyl acetate wax, and carnauba wax. Thereby, the releasability (transferability to the recording medium 53) of the surface treatment liquid 50 from the intermediate transfer medium 11 at the time of transfer can be made particularly excellent, and the productivity and yield of the recorded matter are particularly excellent. Can be. In addition, since the surface treatment liquid 50 contains the wax as described above, an appropriate amount of wax can be more reliably transferred to the recording medium 53 together with the first ink 51 and the second ink 52 in the transfer step. The rub resistance of the finally obtained recorded matter can be made particularly excellent. In particular, when polyethylene wax is used among polyolefin waxes, the above-described effects can be exhibited more remarkably.

The surface treatment liquid 50 preferably constitutes a water-based wax emulsion. Thereby, the releasability (transferability to the recording medium 53) of the first ink 51 and the second ink 52 from the intermediate transfer medium 11 at the time of transfer can be made sufficiently excellent, and the recorded matter can be obtained. Productivity and yield can be sufficiently improved, and in the transfer process, it is possible to more effectively prevent the wax from being transferred to the recording medium 53. Make the final recorded material particularly excellent in abrasion resistance while preventing the harmful effects of wax (for example, shifting to other recorded materials, dirt on the user's hands, etc.) Can do. In addition, the content of the organic solvent in the surface treatment liquid 50 can be lowered, and adverse effects on the environment due to volatilization of the organic solvent during the production of recorded matter can be effectively prevented.
In this specification, an aqueous wax emulsion refers to a dispersion in which a dispersoid composed of a material containing wax is dispersed in a dispersion medium composed of a material containing water.

Further, the surface treatment liquid 50 may include a curable wax (curable wax) as a wax. As a result, adverse effects caused by the presence of liquid wax (particularly an excessive amount of liquid wax) in the finally obtained recorded matter (for example, shifting to another recorded matter, the user of the recorded matter, etc.) In addition, it is possible to make the finally obtained recorded matter particularly excellent in abrasion resistance (particularly, abrasion resistance over a long period of time). In particular, when the curable wax (curable wax) has ultraviolet curable properties, in the polymerization step, the polymerization reaction of the curable wax is allowed to proceed together with the polymerization of the polymerizable compound constituting the first ink 51. It is possible to further improve the releasability (transferability to the recording medium 53) of the first ink 51 and the second ink 52 from the intermediate transfer medium 11 at the time of transfer. The productivity and yield can be further improved.
In the present invention, the curable wax refers to a wax that is composed of a compound having a polymerizable group and has a property of being cured by polymerization.

Hereinafter, the curable wax will be described in detail.
The curable wax (wax molecule) is not particularly limited as long as it has a polymerizable functional group in its molecular structure, but preferably has a radical polymerizable functional group. Examples of the radical polymerizable functional group include acryloyl group, methacryloyl group, acrylamide group, vinyl group, vinylamino group, vinyl ether group, vinyl thioether group, propenyl group, and vinylidene group. Among these, an acryloyl group and a methacryloyl group are preferable, and an acryloyl group is more preferable.

The above curable wax can be easily synthesized by introducing the above radical polymerizable group as long as it has a functional group such as a carboxyl group, a hydroxyl group, a glycidyl group in the structure of a general wax. .
Although it does not specifically limit as a wax which has a hydroxyl group among the said functional groups, For example, a hydroxyl terminal polyethylene wax is mentioned preferably. Examples of the wax include a compound having a chain length n represented by the chemical formula CH ₃ — (CH ₂ ) _n —CH ₂ OH, or a mixture of compounds having different chain lengths n, and the chain length n (mixture). In this case, a mixture of a polymer having an average chain length) of 16 or more and 50 or less and a linear low molecular weight polyethylene having the same chain length can be mentioned. Commercially available products of this wax include, but are not limited to, UNILIN® series materials, such as UNILIN® 350, whose Mn (number average molecular weight) is approximately equal to 375, 460, 550 and 700 g / mol, respectively. UNILIN (registered trademark) 425, UNILIN (registered trademark) 550, UNILIN (registered trademark) 700, and the like. These waxes are available from Baker-Petrolite Corpotion.

Hereinafter, an example of the synthesis of a curable wax using a wax having a hydroxyl group as a raw material will be described.
First, to a mixture of the above-mentioned terminal hydroxyl group polyethylene wax and acrylic acid slightly larger than the equimolar amount of the hydroxyl group of the polyethylene wax (about 1.1 to 1.2 times amount), p- Toluenesulfonic acid (about 1,000 to several thousand ppm) and hydroquinone monomethyl ether (about 1,000 to several thousand ppm) as a polymerization inhibitor are added, and the mixture is refluxed in dehydrated toluene at 80 ° C. in an air stream. The produced water is removed while the esterification reaction proceeds.

  Then, the reaction is terminated when the amount of produced water reaches the theoretical amount, and analysis is performed by gas chromatography, FT-IR, NMR or the like. Thereafter, it is washed with water to remove unreacted acrylic acid and p-toluenesulfonic acid. In some cases, it is further washed with an aqueous sodium hydroxide solution to remove unreacted acrylic acid, and again washed with water to evaporator. Etc. to remove toluene. Thereafter, water remaining in a trace amount is removed with a dehydrating agent, and about 500 ppm of hydroquinone monomethyl ether as a polymerization inhibitor is added to obtain a desired curable wax.

  Preferred examples of the compound having a hydroxyl group among the functional groups include Guerbet alcohol (2,2-dialkyl-1-ethanol). Typical Gerve alcohols include those having 16 to 36 carbon atoms in the molecule. A commercial product of Gerve Alcohol is available from Jarchem Industries Inc., Newark, NJ. Also, PRIPOL® 2033, a dimer diol available from Uniqema Chemicals Ltd. of Newcastle, Delaware, can be used as a mixture having the above hydroxyl group.

As the wax having a carboxyl group among the above functional groups, for example, a carboxylic acid-terminated polyethylene wax is preferably exemplified. Examples of the wax include a compound having a chain length n represented by the chemical formula CH ₃ — (CH ₂ ) _n —COOH or a mixture of compounds having different chain lengths n, and the chain length n (average in the case of a mixture). And a mixture of a linear low molecular weight polyethylene having a similar chain length. Commercially available products of this wax include, but are not limited to, UNICID® 350, UNICID® 425, UNICID® 550 and UNICID (Mn equal to about 390, 475, 565 and 720 g / mol, respectively). Registered trademark) 700 and the like. Examples of the wax include, for example, n = 14 hexadecanoic acid (palmitic acid), n = 15 heptadecanoic acid (margaric acid, daturic acid), n represented by the chemical formula CH ₃ — (CH ₂ ) _n —COOH, = 16 octadecanoic acid (stearic acid), n = 18 eicosanoic acid (arachidic acid), n = 20 docosanoic acid (behenic acid), n = 22 tetracosanoic acid (lignoceric acid), n = 24 hexacosanoic acid ( Serotic acid), n = 25 heptacosanoic acid (carboceric acid), n = 26 octacosanoic acid (montanic acid), n = 28 triacontanoic acid (melicinic acid), n = 30 dotriacontanoic acid (Russell) Acid), n = 31 tritriacontanoic acid (cellomericinic acid, psylic acid), n = 32 tetratriacontanoic acid (geda acid) n = 33 pentatriacontanone acid (Seropurasuchin acid).

Hereinafter, an example of synthesis of a curable wax using a wax having a carboxyl group as a raw material will be described.
First, as a catalyst, a mixture of the above carboxylic acid-terminated polyethylene wax, a carboxylic acid group of the polyethylene wax and 2-hydroxyethyl acrylate, which is slightly larger than the equimolar amount (about 1.1 to 1.2 times the amount), is used. P-toluenesulfonic acid (about 1,000 to several thousand ppm) and hydroquinone monomethyl ether (about one thousand to several thousand ppm) as a polymerization inhibitor are added, and the mixture is heated to 80 ° C. in dehydrated toluene under an air stream. The produced water is removed while refluxing to advance the esterification reaction.

  Then, the reaction is terminated when the amount of produced water reaches the theoretical amount, and analysis is performed by gas chromatography, FT-IR, NMR or the like. Thereafter, it is washed with water to remove unreacted 2-hydroxyethyl acrylate and p-toluenesulfonic acid, and toluene is removed with an evaporator or the like. Thereafter, water remaining in a trace amount is removed with a dehydrating agent, and about 500 ppm of hydroquinone monomethyl ether as a polymerization inhibitor is added to obtain a desired curable wax.

  Of the functional groups, a compound having a carboxyl group is also preferably exemplified by gerbeic acid (2,2-dialkylethanol acid). Typical examples of gerbeic acid include those having 16 to 36 carbon atoms in the molecule. A commercial product of gerbeic acid is available from Jalchem Industries. Further, PRIPOL (registered trademark) 1009 available from Unikema can also be used as the mixture having the carboxyl group.

The surface treatment liquid 50 may include other components in addition to the wax described above. Examples of such components include volatile liquid components, photopolymerization initiators, humectants, ultraviolet absorbers, dispersants, dispersion aids, surfactants, thermal polymerization inhibitors, antioxidants, preservatives, Examples include fungicides, pH adjusters, metal trapping agents, fillers, adhesion promoters, and the like.
By including a volatile liquid component, the ejection stability and coating property of the surface treatment liquid 50 by the ink jet method can be made particularly excellent.

  Examples of such volatile liquid components include pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, 2-pyrrolidone, dimethyl sulfoxide, ε-caprolactam, methyl lactate, ethyl lactate, isopropyl lactate, butyl lactate, and ethylene glycol. Monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol isopropyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene Recall dimethyl ether, 1,4-dioxane, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, hexylene glycol, 2,3-butanediol, ethanol, n-propanol, iso -Propanol, n-butanol, 1,2-hexanediol, 1,3-hexanediol, 1,2-heptanediol, 1,3-heptanediol, 1,2-octanediol, 1,3-octanediol, 1 , 2-pentanediol, triethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monopropyl ether, diethylene glycol monopentyl ether, propylene glycol monobutyl ether, Water etc. are mentioned, The 1 type (s) or 2 or more types selected from these can be used.

Among these, the surface treatment liquid 50 preferably includes a liquid component having a boiling point of 110 ° C. or higher and 250 ° C. or lower as a volatile liquid component, and more preferably includes 1,2-hexanediol and / or propylene glycol. More preferably, it contains 1,2-hexanediol and propylene glycol. Thereby, the discharge stability and coating property by the inkjet method of the surface treatment liquid 50 can be further improved. In addition, it is possible to prevent the inkjet head from drying and to enable stable droplet ejection over a longer period of time.
In addition, when the surface treatment liquid 50 contains water, an aqueous wax emulsion as described above can be suitably formed.

The content of the liquid component having a boiling point of 110 ° C. or more and 250 ° C. or less in the surface treatment liquid 50 is preferably 10% by mass or more and 40% by mass or less. Thereby, the effects as described above can be exhibited more significantly while the effects of including the wax are sufficiently exhibited. In addition, when the surface treatment liquid 50 includes a plurality of types of components as liquid components having a boiling point of 110 ° C. or higher and 250 ° C. or lower, it is preferable that the sum of these content ratios satisfies the above conditions.
The water content in the surface treatment liquid 50 is preferably 45% by mass or more and 87.5% by mass or less.

  The content of the wax in the surface treatment liquid 50 is preferably 2.0% by mass or more and 25% by mass or less, and more preferably 3.0% by mass or more and 15% by mass or less. Thereby, the effect by using the surface treatment liquid 50 containing the wax as described above can be exhibited more remarkably while making the discharge stability of the surface treatment liquid 50 by the inkjet method particularly excellent. In addition, when the surface treatment liquid 50 contains several types of components as a wax, it is preferable that the sum of these content rates satisfies the above conditions. Further, when the surface treatment liquid 50 constitutes an aqueous wax emulsion, the content of the wax content is the content of a component that actually functions as a wax (for example, a dispersoid excluding water). It is preferable that the rate satisfies the above conditions.

[First ink]
The first ink 51 contains a polymerizable compound that is polymerized by irradiation with ultraviolet rays. The first ink 51 is used for forming a printed portion of a recorded matter.
(Polymerizable compound)
The polymerizable compound is a component that is polymerized by irradiation with ultraviolet rays.
As the polymerizable compound, a monomer, oligomer, polymer (prepolymer) having a polymerizable functional group can be used.

  Examples of the monomer as the polymerizable compound include allyl glycol, N-vinylformamide, (2-methyl-2-ethyl-1,3-dioxolan-4-yl-) methyl acrylate, phenoxyethyl acrylate, and isobornyl acrylate. , Methoxydiethylene glycol monoacrylate, acryloylmorpholine, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tripropylene glycol diacrylate, 1,9-nonanediol diacrylate, polyethylene glycol # 400 diacrylate, tetraethylene glycol dimethacrylate, 1,6- Hexanediol dimethacrylate, neopentyl glycol dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane, Trimethylolpropane trimethacrylate, trimethylolpropane modified triacrylate trimethylolpropane PO-modified triacrylate, glycerin PO-modified triacrylate.

  Preferable specific examples of the oligomer as the polymerizable compound include urethane oligomers such as polyester urethane acrylate, polyether urethane acrylate, polybutadiene urethane acrylate and polyol urethane acrylate having a molecular weight in the range of 500 to 20,000. It is done. More specifically, U-4HA and U-15HA (both manufactured by Shin-Nakamura Chemical Co., Ltd.) are preferable.

  Examples of the polymer (prepolymer) as the polymerizable compound include dendrimers, hyperbranched polymers, dendrigraft polymers, and hypergraft polymers that are solid at room temperature and have a molecular weight in the range of 2,000 to 50,000. (See “Dendritic Polymers—The World of Higher Functionality Expanded by Multi-Branched Structures”) Keigo Aoi / Masaaki Anemoto, see NTS Corporation).

  In particular, the first ink 51 includes a liquid polymerizable compound that forms a liquid alone under the conditions of the first ink application step (for example, at 25 ° C. and 1 atm) as the polymerizable compound. Is preferred. As a result, it is not necessary to use a volatile solvent as a constituent component of the first ink 51, or the content of the volatile solvent can be reduced. The process for volatilizing can be omitted or simplified, and the productivity of recorded matter can be made particularly excellent. In addition, it is possible to more effectively prevent the occurrence of problems such as deterioration in the image quality of the printing unit due to the volatilization of the solvent during the manufacturing process of the recorded matter.

In particular, the liquid polymerizable compound is preferably the main component (main solvent) of the liquid components constituting the first ink 51. Thereby, the above effects can be obtained more remarkably.
It is preferable that the liquid polymerizable compound is contained in a proportion of 50 parts by weight or more with respect to 100 parts by weight of all liquid components constituting the first ink 51. Thereby, the above effects can be obtained more remarkably.

The first ink 51 preferably contains allyl glycol as a liquid polymerizable compound. Thereby, the printing part which has a desired shape can be formed more reliably. Further, the productivity of recorded matter can be made particularly excellent. These effects are more prominent when the first ink 51 contains allyl glycol as the liquid polymerizable compound and the surface treatment liquid 50 constitutes an aqueous wax emulsion. . In addition, when the first ink 51 contains allyl glycol as the liquid polymerizable compound, the fixing strength of the printed part in the recorded matter can be made particularly excellent. In addition, when the first ink 51 contains allyl glycol as the liquid polymerizable compound, the three-dimensional effect of the printed portion can be further improved in the finally obtained recorded matter.
The content of the polymerizable compound in the first ink 51 is not particularly limited, but is preferably 30% by mass or more and 80% by mass or less.

(Other ingredients)
The first ink 51 may include components other than the polymerizable compound (other components). Examples of such components include a photopolymerization initiator, a humectant, a dispersant, a dispersion aid, a surfactant, a thermal polymerization inhibitor, an antioxidant, a filler, an adhesion promoter, an ultraviolet absorber, and an aggregation inhibitor. Agent, volatile liquid component, curable component that is polymerized / cured by methods other than ultraviolet irradiation, resin component that does not have polymerization reactivity / curability, preservative / fungicide, pH adjuster, metal trapping agent , Fillers, adhesion promoters and the like.

Specific examples of the photopolymerization initiator include benzyldimethyl ketal, α-hydroxyalkylphenone, α-aminoalkylphenone, acylphosphine oxide, oxime ester, thioxanthone, α-dicarbonyl, anthraquinone and the like.
Also, Vice 10, 30 (above, manufactured by Stauffer Chemical), Irgacure 127, 184, 500, 651, 2959, 907, 369, 379, 754, 1700, 1800, 1850, 819, OXE01, Darocur 1173, TPO, ITX Photopolymerization available under the trade names of Ciba Specialty Chemicals, Quantacure CTX (Aceto Chemical), Kayacure DETX-S (Nippon Kayaku) and ESCURE KIP150 (Lamberti) Agents can also be used.

The content of the photopolymerization initiator in the first ink 51 is preferably 3% by mass or more and 10% by mass or less.
By including the surfactant in the first ink 51, it is possible to improve the droplet discharge stability by the ink jet method.
As the surfactant, for example, a silicone-based surfactant such as polyester-modified silicone or polyether-modified silicone is preferably used, and polyether-modified polydimethylsiloxane or polyester-modified polydimethylsiloxane is more preferably used. Specific examples include BYK-347, 348, BYK-UV3500, 3510, 3530, 3570 (manufactured by Big Chemie Japan, Inc.), but are not limited thereto.

When the first ink 51 contains a thermal polymerization inhibitor, the storage stability of the first ink 51 can be made particularly excellent.
Examples of the thermal polymerization inhibitor include Irgastab UV-10 (manufactured by Ciba Specialty Chemicals), but are not limited thereto.
The first ink 51 may contain a colorant, but usually has a lower colorant content than the second ink 52, and in particular does not contain a colorant. Is preferred. Thereby, the effects as described above can be exhibited more remarkably.

[Second ink]
The second ink 52 includes a colorant, a thermoplastic resin, and a volatile liquid. The second ink 52 is used for forming a printed portion of a recorded matter.
(Coloring agent)
As the colorant, various pigments and various dyes can be used, and it is particularly preferable to use a pigment. Thereby, the light resistance, heat resistance, etc. of the printed part are particularly excellent, and a stable appearance can be maintained over a long period of time.

In the manufacturing apparatus 100 having the configuration shown in the figure, as the second ink 52, the second ink 52 of cyan purple, the second ink 52 of reddish purple (magenta), and the second ink 52 of yellow (yellow). White (white) second ink 52 and black (black) second ink 52 are used.
The second ink 52 of each color usually contains a colorant of a color corresponding to each ink.

  As pigments constituting the chromatic color second ink 52 (cyan second ink 52, magenta second ink 52, yellow second ink 52) For example, quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, ansanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments Examples thereof include pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, isoindolinone pigments, azomethine pigments and azo pigments.

In particular, as a pigment constituting the second ink 52 of cyan purple (cyan purple pigment), for example, C.I. I. Pigment Blue 1, 2, 3, 15: 3, 15: 4, 15:34, 16, 22, 60; I. Bat blue 4, 60 and the like, preferably C.I. I. Pigment blue 15: 3, 15: 4, 60.
Further, examples of the pigment constituting the red-purple (magenta) second ink 52 include C.I. I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 112, 122, 123, 168, 184, 202; I. Pigment violet 19 and the like, preferably C.I. I. Pigment red 122, 202, 209; I. And CI pigment violet 19.

  Examples of the pigment constituting the yellow (yellow) second ink 52 include C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14C, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 119, 110, 114, 128, 129, 138, 150, 151 154, 155, 180, 185, 14, 34, 35, 35: 1, 37, 37: 1, 42, 43, 53, 55, 81, 94, 108, 109, 110, 139, 153, 157, 168, 184, etc., preferably C.I. I. Pigment yellow 74, 109, 110, 128, 138.

  Further, chromatic pigments other than those described above may be used. Examples of such pigments include C.I. I. Pigment Red 2,3, 17, 22, 23, 38, 81, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 52: 1, 53: 1, 63: 1, 144 146, 149, 166, 170, 176, 177, 178, 179, 185, 207, 209, 254, 101, 102, 105, 106, 108, 108: 1; I. Pigment Green 7, 15, 17, 18, 19, 26, 36, 50; C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 6, 17: 1, 18, 27, 28, 29, 35, 36, 80; I. Pigment violet 1, 3, 23, 50, 14, 16; I. Pigment Orange 5, 13, 16, 36, 43, 20, 20: 1, 104; I. Pigment brown 25, 7, 11, 33, and the like.

The pigment constituting the white second ink 52 is, for example, titanium oxide (for example, chlorine-based titanium oxide (rutile type) CR-50 (ISHIHARA SANGYO KAISHA, LTD.). Trade name)), barium sulfate, hollow white resin emulsion and the like.
Moreover, as a pigment which comprises the black (black) 2nd ink 52, carbon black is mentioned, for example. Specifically, no. 2300, 900, MCF88, no. 20B, no. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, No2200B, etc. (all trade names, manufactured by Mitsubishi Chemical Corporation), color black FW1, FW2, FW2V, FW18, FW200, S150, S160, S170, Pretex 35, U, V, 140U , Special Black 6, 5, 4A, 4, 250, etc. (all trade names, manufactured by Degussa), Conductex SC, Raven 1255, 5750, 5250, 5000, 3500, 1255, 700, etc. (all trade names, Colombia) (Manufactured by Carbon Co., Ltd.), Regar 400R, 330R, 660R, Mogul L, Monarch 700, 800, 880, 900, 1000, 1100, 1300, 1400, Elftex 12, etc. (all trade names, manufactured by Cabot Corporation).

Note that toning may be performed by using a combination of a plurality of colorant components in one type of ink. More specifically, for example, the black (black) second ink 52 may be a combination of two or more colorant components other than black and exhibit a black color as a whole.
Moreover, as a coloring agent, you may use the pigment etc. which have glossiness like a metal powder etc., for example.

The pigment may be subjected to a surface treatment. Thereby, it is possible to improve the tint, the dispersion stability of the pigment particles in the second ink 52, the ejection stability of the second ink 52, the storage stability, and the like.
The content of the colorant in the second ink 52 is not particularly limited, but is preferably 0.5% by mass or more and 10% by mass or less.

(Thermoplastic resin)
The thermoplastic resin is a component that contributes to the fixing of the printing unit to the recording medium 53 by the second ink 52.
The thermoplastic resin may be soluble in volatile liquids, or may be insoluble (insoluble).

As the thermoplastic resin, a so-called resin emulsion may be used.
When a resin emulsion is used as the thermoplastic resin, the particle diameter is not particularly limited, but is preferably 150 nm or less, more preferably 5 nm or more and 100 nm or less.
Specific examples of the thermoplastic resin include acrylic polymers such as polyacrylic acid esters or copolymers thereof, polymethacrylic acid esters or copolymers thereof, polyacrylonitrile or copolymers thereof, polycyanoacrylates, poly Acrylamide, polyacrylic acid, or polymethacrylic acid; polyolefin polymers such as polyethylene, polypropylene, polybutene, polyisobutylene, polystyrene, or copolymers thereof, petroleum resins, coumarone-indene resins, or terpene resins; vinyl acetate, Vinyl alcohol polymers such as polyvinyl acetate or copolymers thereof, polyvinyl alcohol, polyvinyl acetals, or polyvinyl ethers; halogen-containing polymers such as polyvinyl chloride or copolymers thereof. Polymer, polyvinylidene chloride, fluororesin, or fluororubber; nitrogen-containing vinyl polymer, such as polyvinyl carbazole, polyvinyl pyrrolidone or copolymer thereof, polyvinyl pyridine, or polyvinyl imidazole; diene polymer, such as polybutadiene or its A copolymer, polychloroprene, or polyisoprene (butyl rubber); or other ring-opening polymerization resin, condensation polymerization resin, natural polymer resin, or the like can be used.

  Further, for example, Hitech E-7525P, Hitech E-2213, Hitech E-9460, Hitech E-9015, Hitech E-4A, Hitech E-5403P, Hitech E-8237 (all trade names, manufactured by Toho Chemical Co., Ltd.) , AQUACER 507, AQUACER 515, AQUACER 840 (all are trade names, manufactured by Big Chemie Japan Co., Ltd.) and the like.

  When the thermoplastic resin is obtained in the form of an emulsion, it can be prepared by mixing the resin particles in water together with a surfactant. For example, an emulsion of an acrylic resin or a styrene-acrylic acid copolymer resin is composed of a (meth) acrylic ester resin or a styrene- (meth) acrylic ester resin, and optionally a (meth) acrylic resin, It can be obtained by mixing the active agent with water. The mixing ratio of the resin component and the surfactant is usually preferably 50: 1 to 5: 1. When the amount of the surfactant used is less than the lower limit, it is difficult to form an emulsion, and when the amount exceeds the upper limit, the water resistance of the second ink 52 is reduced or the printing portion is closely attached to the recording medium 53. There is a tendency for the sex to decline.

The surfactant used here is not particularly limited. For example, an anionic surfactant (for example, sodium dodecyl benzan sulfonate, sodium lauryl sulfate, ammonium salt of polyoxyethylene alkyl ether sulfate, etc.), nonionic interface Activators (for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl amines, polyoxyethylene alkyl amides, etc.) can be mentioned. .
An emulsion of a thermoplastic resin can also be obtained by emulsion polymerization of the above resin component monomer in water in the presence of a polymerization catalyst and an emulsifier.

  As the polymerization initiator, those used for normal radical polymerization are used, for example, potassium persulfate, ammonium persulfate, hydrogen peroxide, azobisisobutyronitrile, benzoyl peroxide, dibutyl peroxide, Examples include peracetic acid, cumene hydroperoxide, t-butyl hydroxy peroxide, paramentane hydroxy peroxide, and the like. When the polymerization reaction is performed in water, a water-soluble polymerization initiator is preferable. Examples of the emulsifier include sodium lauryl sulfate, those generally used as an anionic surfactant, nonionic surfactant or amphoteric surfactant, and mixtures thereof.

When a resin emulsion is used as the thermoplastic resin, a known resin emulsion can also be used. For example, the resin emulsions described in JP-B-62-1426, JP-A-3-56573, JP-A-3-79678, JP-A-3-160068, or JP-A-4-18462 are used. It can be used as it is. Commercially available resin emulsions can also be used. For example, Microgel E-1002, E-5002 (styrene-acrylic resin emulsion; manufactured by Nippon Paint Co., Ltd.), Boncoat 4001 (acrylic resin emulsion; large Nippon Ink Chemical Co., Ltd.), Boncoat 5454 (styrene-acrylic resin emulsion; Dainippon Ink and Chemicals Co., Ltd.), SAE1014 (styrene-acrylic resin emulsion; manufactured by Nippon Zeon Co., Ltd.), Cybinol SK-200 ( Acrylic resin emulsion; manufactured by Seiden Chemical Co., Ltd.).
Examples of the water-soluble resin include water-insoluble polymers such as polyethylene glycol, polyvinyl pyrrolidone, polyvinyl alcohol, and polyvinyl acetal.

  The content of the thermoplastic resin in the second ink 52 is preferably 0.5% by mass or more and 15% by mass or less, and more preferably 1.5% by mass or more and 15% by mass or less. When the content is less than the lower limit value, the adhesion of the formed printing section to the recording medium 53 tends to be lowered. If the content rate exceeds the upper limit, the storage stability of the second ink 52 may be reduced.

(Volatile liquid)
The volatile liquid constituting the second ink 52 is a volatile liquid component. As a result, the volatile liquid is removed in the manufacturing process of the recorded matter (for example, the first heating step and the second heating step), and the durability and reliability of the finally obtained recorded matter are improved. It can be made particularly excellent.

  Examples of the volatile liquid constituting the second ink 52 include pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, 2-pyrrolidone, N-methylpyrrolidone, dimethylsulfoxide, ε-caprolactam, methyl lactate, ethyl lactate, Isopropyl lactate, butyl lactate, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol isopropyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, Dipropylene glycol Nomethyl ether, dipropylene glycol dimethyl ether, 1,4-dioxane, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, hexylene glycol, 2,3-butanediol, ethanol N-propanol, iso-propanol, n-butanol, 1,2-hexanediol, 1,3-hexanediol, 1,2-heptanediol, 1,3-heptanediol, 1,2-octanediol, 1, 3-octanediol, 1,2-pentanediol, triethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monopropyl ether, diethylene glycol monopentyl ether, propylene Glycol glycol monobutyl ether and the like, and one or more selected from these can be used.

  Among them, the second ink 52 preferably contains a liquid component having a boiling point of 110 ° C. or higher and 250 ° C. or lower as a volatile liquid, and is more preferable than 1,2-hexanediol, 2-pyrrolidone, N-methylpyrrolidone and propylene glycol. More preferably, it includes one or more selected from the group consisting of: Thereby, in a 1st heating process, a volatile liquid can be volatilized moderately and the stability of the shape of the 2nd ink 52 can be improved more effectively. In the second heating step, the volatile liquid can be removed more reliably, and the occurrence of adverse effects due to the remaining volatile liquid in the finally obtained recorded matter can be more reliably prevented. . Further, the ejection stability and coating property of the second ink 52 by the ink jet method can be further improved. In addition, it is possible to prevent the inkjet head from drying and to enable stable droplet ejection over a longer period of time.

  The second ink preferably contains water as a volatile liquid. Thereby, in a 1st heating process, a volatile liquid can be volatilized moderately and the stability of the shape of the 2nd ink 52 can be improved more effectively. In the second heating step, the volatile liquid can be removed more reliably, and the occurrence of adverse effects due to the remaining volatile liquid in the finally obtained recorded matter can be more reliably prevented. . Further, the ejection stability and coating property of the second ink 52 by the ink jet method can be further improved. In addition, it is possible to prevent the inkjet head from drying and to enable stable droplet ejection over a longer period of time. Water is a material that has a particularly low load on the human body and the environment. Therefore, it is preferable also from the viewpoint of worker safety and environmental protection.

  The content of the volatile liquid in the second ink 52 is preferably 50% by mass or more and 90% by mass or less, and more preferably 60% by mass or more and 85% by mass or less. Thereby, the discharge stability of the second ink 52 can be made particularly excellent, and the volatile liquid can be appropriately volatilized in the first heating step, and the shape of the second ink 52 Can be more effectively improved. In the second heating step, the volatile liquid can be removed more reliably, and the occurrence of adverse effects due to the remaining volatile liquid in the finally obtained recorded matter can be more reliably prevented. .

(Other ingredients)
The second ink 52 may include components other than those described above (other components). Examples of such components include preservatives and fungicides, pH adjusters, antioxidants, metal trapping agents, moisturizers, dispersants, dispersion aids, surfactants, fillers, adhesion promoters, and agglomerates. Examples include an inhibitor photocurable resin, a thermosetting resin, a polymerization initiator, and a polymerization inhibitor.

  Examples of antiseptics and fungicides include sodium benzoate, sodium pentachlorophenol, 2-pyridinethiol-1-oxide sodium, sodium sorbate, sodium dehydroacetate, 1,2-dibenzisothiazoline-3-one (Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL-2, Proxel TN from ICI) and the like.

Examples of the pH adjuster include inorganic alkalis such as sodium hydroxide and potassium hydroxide, ammonia, diethanolamine, triethanolamine, triisopropanolamine, morpholine, potassium dihydrogen phosphate, and disodium hydrogen phosphate.
Examples of the metal trapping agent include ethylenediaminetetraacetic acid disodium.

By including the surfactant in the second ink 52, it is possible to improve the droplet discharge stability by the ink jet method.
As the surfactant, for example, a silicone-based surfactant such as polyester-modified silicone or polyether-modified silicone is preferably used, and polyether-modified polydimethylsiloxane or polyester-modified polydimethylsiloxane is more preferably used. Specific examples include BYK-347, 348, BYK-UV3500, 3510, 3530, 3570 (manufactured by Big Chemie Japan, Inc.), but are not limited thereto.

[recoding media]
The recording medium 53 is composed of, for example, plain paper, art paper, coated paper, matte paper, paper for exclusive use for inkjet, plastic materials such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, polystyrene, polyurethane, polyethylene, and polypropylene. Molded products (films, etc.) made of metal, molded products (films, etc.) made of metal, molded products (films, etc.) made of ceramics, natural fibers / synthetic fibers such as cotton, polyester, wool, etc., non-woven fabrics, etc. Can do.

  As the recording medium 53, a non-ink-absorbing or low-absorbing material can be suitably used. In the conventional intermediate transfer recording method, when a non-ink-absorbing or low-absorbing recording medium is used, problems such as the inability to reliably form a printing portion of a desired shape occur. However, in the present invention, even if the recording medium is non-ink-absorbing or low-absorbing, it is possible to reliably prevent the above problems from occurring. That is, when the recording medium is a non-ink-absorbing or low-absorbing material, the effect of the present invention is more remarkably exhibited.

Here, the “ink non-absorptive or low absorptive” recording medium refers to a recording medium whose printing surface has a water absorption of 10 mL / m ² or less from the start of contact to 30 msec in the Bristow method. . This Bristow method is the most popular method for measuring the amount of liquid absorbed in a short time, and is also adopted by the Japan Paper Pulp Technology Association (JAPAN TAPPI). For details of the test method, refer to Standard No. of “JAPAN TAPPI Paper Pulp Test Method 2000”. 51 "Paper and paperboard-Liquid absorbency test method-Bristow method".

The recording medium 53 is preferably a film made of a plastic material (including those formed into a cylindrical shape, a bag shape, or the like). Conventionally, when the recording medium is a film made of a plastic material, it is difficult to reliably form a printing portion having a desired shape, and the fixing property of the printing portion to the recording medium is sufficient. The problem that it was difficult to make excellent was particularly noticeable. On the other hand, according to the present invention, even when the recording medium is a film made of a plastic material, it is possible to reliably prevent the occurrence of the above problems. That is, when the recording medium is a film made of a plastic material, the effect of the present invention is more remarkably exhibited. In addition, when the recording medium 53 is a film made of a plastic material, it is possible to more suitably form a three-dimensional printing portion.
As described above, according to the manufacturing method and the manufacturing apparatus of the present invention described above, it is possible to reliably and efficiently manufacture a recorded matter including a printing unit having excellent fixability and a desired shape.

≪Recordings≫
Next, the recorded matter of the present invention will be described.
The recorded matter of the present invention is manufactured using the above-described manufacturing method of the present invention. As a result, it is possible to provide a recorded matter that is excellent in fixability and includes a printing unit having a desired shape.

The recorded matter of the present invention may be used for any purpose, and examples thereof include packaging materials for various products such as foods and daily necessities, various decorative items, and the like.
As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to these.
For example, in the above-described embodiment, the case where the intermediate transfer medium has an endless belt shape has been representatively described. However, in the present invention, the intermediate transfer medium may have any shape, for example, a drum. The shape (roll shape) may be made.

  Moreover, each part which comprises the manufacturing apparatus of this invention can be substituted with the thing of the arbitrary structures which can exhibit the same function. Moreover, arbitrary components may be added. For example, the manufacturing apparatus of the present invention may include a recovery mechanism that recovers a volatile liquid. The manufacturing apparatus of the present invention also applies to the first ink transferred to the recording medium, in addition to the ultraviolet irradiation means (first ultraviolet irradiation means) for irradiating the first ink on the intermediate transfer medium with ultraviolet rays. Further, it may be provided with ultraviolet irradiation means (second ultraviolet irradiation means) for irradiating ultraviolet rays.

In the above-described embodiment, the first heating unit and the second heating unit are provided on the inner surface side, that is, the first heating unit is a surface to which the second ink of the intermediate transfer medium is applied. The case where the first heating means heats from the surface opposite to the side where the second ink of the recording medium is transferred will be mainly described. However, at least one of the first heating means and the second heating means may be provided on the outer surface side (see FIGS. 2 and 3). Further, at least one of the first heating unit and the second heating unit may be provided on both the inner surface side and the outer surface side.
Moreover, in the manufacturing method of this invention, in addition to the process as mentioned above, you may have another process (a pre-processing process, an intermediate processing process, a post-processing process).

[1] Manufacture of recorded matter A recorded matter was produced as follows.
Example 1
First, a manufacturing apparatus as shown in FIG. 2 was prepared.
The intermediate transfer medium constituting the manufacturing apparatus is composed of a transparent PET film Teijin Tetron film G2 and a thickness of 100 μm (manufactured by Teijin DuPont Films, Inc., UV transmittance: 70% or more). I had it. Further, in the transfer portion, the curvature of the intermediate transfer medium is larger than the curvature of the pressure roll as the recording medium conveying means.

<Surface treatment liquid application step>
First, the surface treatment liquid was ejected in a predetermined pattern from the surface treatment liquid application unit toward the intermediate transfer medium by an inkjet method. In this step, the layer thickness of the surface treatment liquid was set to 1 μm. Thereafter, high-speed drying was performed with warm air at 80 ° C. as a surface treatment liquid drying means.

The composition of the surface treatment liquid is as shown below.
(Surface treatment liquid)
As a wax emulsion, AQUACER 515 (trade name, polyethylene wax emulsion manufactured by Big Chemie Japan Co., Ltd., nonvolatile content: 35% by mass)
15% by mass
1,2-hexanediol as a volatile liquid component (boiling point: 223-224 ° C.)
5% by mass
5% by mass of propylene glycol (boiling point: 188.2 ° C.) as a volatile liquid component
BYK-348 0.5% by mass as a surfactant
Pure water 74.5% by mass

<First ink application step>
Next, the first ink was selectively applied from the first ink applying means toward the portion to which the surface treatment liquid of the intermediate transfer medium was applied by an inkjet method. In this step, the thickness of the first ink layer was set to 1 μm.
The composition of the first ink is as shown below.

(First ink)
Allyl glycol as monomer (polymerizable compound) 84.8% by mass
10% by mass of U-15HA as an oligomer (polymerizable compound)
Irgacure 127 3% by weight as a photopolymerization initiator
Irgacure 819 2% by weight as a photopolymerization initiator
BYK-UV3500 0.2% by mass as a silicone-based surfactant

<Polymerization process>
Next, ultraviolet rays are irradiated from the surface opposite to the surface to which the first ink of the intermediate transfer medium is applied using an ultraviolet irradiation means (D lamp, manufactured by Fusion System). The polymerizable compound contained was polymerized. In this step, ultraviolet rays were irradiated in a 20 cm wide region, and the ultraviolet irradiation intensity was 100 mW / cm ² .

<Second ink application step>
Next, the second ink was selectively applied from the second ink applying means toward the portion of the intermediate transfer medium to which the first ink was applied by an inkjet method. The second ink includes indigo violet (cyan) ink (cyan ink), crimson violet (magenta) ink (magenta ink), yellow (yellow) ink (yellow ink), and black (black) ink (black). Ink) and white ink (white ink) were used. At this time, the white ink was deposited so as to overlap the second ink of each color. Further, a thermoplastic resin emulsion having an effect of improving the adhesion performance to the recording medium at the time of transfer was added to the white ink.

The composition of each ink is as shown below.
[Preparation of second ink]
[Black ink 1]
4 parts by mass of diethylene glycol monobutyl ether (hereinafter also referred to as “DEGmBE”), 1 part by mass of BYK-348 (silicone surfactant, trade name manufactured by Big Chemie Japan Co., Ltd.), and 30 parts by mass of ion-exchanged water Were mixed and stirred at room temperature for 20 minutes to obtain a premixed solution. Next, 5 parts by mass of JONCRYL 678 (acrylic water-soluble resin, trade name of BASF, molecular weight 8,500, oxidation 215) as a water-soluble resin, and 0.1 parts by mass of potassium hydroxide (as a pH adjuster) KOH) was added to the premix and stirred at 40 ° C. for 1 hour.

  To this liquid after stirring, 10 parts by mass of carbon black MA100 (trade name, manufactured by Mitsubishi Chemical Corporation) was added to obtain a mixed liquid, and 1 of the mixed liquid was obtained in a desktop sand mill (manufactured by Hayashi Shoten). Along with zirconia glass beads (diameter: 1.5 mm) having a mass of 5 times, the mixture was stirred and dispersed at 2,160 rpm for 2 hours. After dispersion, the mixture was filtered through a 0.1 mm SUS mesh filter to prepare a dispersion.

  In the dispersion, 2-pyrrolidone (hereinafter also referred to as “2-Py”), propylene glycol (hereinafter also referred to as “PG”), and Polysol AM-710 (acrylic resin emulsion, manufactured by Showa Denko KK) as a resin emulsion. Name, average particle diameter 150 nm, active ingredient 50.5 mass%), Proxel-XL2 (preservative, trade name manufactured by Arch Chemicals), and ion-exchanged water are added in the amounts (parts by mass) shown in Table 1, Stir at 40 ° C. for 20 minutes. After stirring, the mixture was filtered through a membrane filter having a diameter of 5 μm to prepare a black ink having the composition shown in Table 1.

[Cyan ink 2]
3 parts by mass of DEGmBE, 0.7 parts by mass of BYK-348, and 30 parts by mass of ion-exchanged water were mixed and stirred at room temperature for 20 minutes to obtain a premixed solution. Next, 2 parts by weight of JONCRYL680 (acrylic water-soluble resin, trade name of BASF, molecular weight 4,900, oxidation 215) and 0.1 part by weight of KOH are added to this premixed solution as a water-soluble resin. And stirred at 40 ° C. for 1 hour.
To this liquid after stirring, 5 parts by mass of cyan pigment (CI Pigment Blue 15: 3, manufactured by DIC) was added to obtain a mixed liquid, and then dispersed under the same conditions as in the case of Black Ink 1. A dispersion was prepared by filtration.

  In the dispersion, 1,2-hexanediol (hereinafter also referred to as “1,2-HD”), 2-Py, PG, and Polysol AM-2300 (styrene / acrylic resin emulsion, manufactured by Showa Denko KK) as a resin emulsion Name, minimum film-forming temperature (MFT) 70 ° C., average particle diameter 90 nm, active ingredient 40% by mass), Proxel-XL2, and ion-exchanged water are added in the amounts (parts by mass) shown in Table 1, and then black The mixture was stirred and filtered under the same conditions as in the case of Ink 1 to prepare a cyan ink having the composition shown in Table 1.

[Magenta ink 3]
3 parts by mass of DEGmBE, 0.2 parts by mass of BYK-348 and 30 parts by mass of ion-exchanged water were mixed and stirred at room temperature for 20 minutes to obtain a premixed solution. Next, 1 part by mass of JONCRYL680 and 0.1 part by mass of KOH were added to this premixed solution and stirred at 40 ° C. for 1 hour.
4 parts by mass of a magenta pigment (CI Pigment Red 122, manufactured by BASF) is added to the liquid after stirring to obtain a mixed liquid, and then dispersed and filtered under the same conditions as in the case of Black Ink 1. A dispersion was prepared.

  In the dispersion, 1,2-HD, AE373D (carboxy-modified styrene / acrylic resin emulsion, trade name, average particle size 150 nm, active ingredient 50% by mass), Proxel-XL2, and ion-exchanged water as a resin emulsion Were added in the amounts (parts by mass) shown in Table 1, and then stirred and filtered under the same conditions as in Black Ink 1 to prepare magenta inks having compositions shown in Table 1.

[Yellow ink 4]
3 parts by mass of DEGmBE, 0.8 parts by mass of BYK-348, and 30 parts by mass of ion-exchanged water were mixed and stirred at room temperature for 20 minutes to obtain a premixed solution. Next, 2 parts by mass of JONCRYL 680 and 0.1 parts by mass of KOH were added to the premixed solution and stirred at 40 ° C. for 1 hour.
To this liquid after stirring, 4 parts by mass of yellow pigment (CI Pigment Yellow 180, manufactured by Dainichi Seika Kogyo Co., Ltd.) was added to obtain a mixed liquid, and then dispersed under the same conditions as in Black Ink 1. And filtered to prepare a dispersion.

  In the dispersion, 1,2-HD, 2-Py, PG, Polysol AT860 (acrylic resin emulsion, trade name, Showa Denko, trade name, average particle size 120 nm, Tg 60 ° C., active ingredient 50% by mass) as a resin emulsion, Surfynol 465 (acetylene glycol surfactant, product name manufactured by Air Products and Chemicals Inc.), Proxel-XL2, and ion-exchanged water are added in the amounts (parts by mass) shown in Table 1, and then black ink A-1 The yellow ink having the composition shown in Table 1 was prepared by stirring and filtering under the same conditions as in.

[White ink 5]
1 part by weight of BYK-348, 4.7 parts by weight of Denkapoval H-12 (polyvinyl alcohol, trade name, manufactured by Denki Kagaku Kogyo Co., Ltd., pure content: 94% by weight) as water-soluble resin, and 30 parts by weight of ion-exchanged water Were mixed and stirred at 40 ° C. for 1 hour.
To the liquid after stirring, 9.5 parts by mass of CR-50 (rutile-type titanium oxide, trade name, manufactured by Ishihara Sangyo Co., Ltd., 95% by mass of TiO ₂ active ingredient, average particle diameter of 0.25 μm) as a pigment was added and mixed. A liquid was obtained, and then dispersed and filtered under the same conditions as in the case of Black Ink 1 to prepare a dispersion.

Polysol AP-4735 (acrylic resin emulsion, trade name, manufactured by Showa Denko KK, Tg 21 ° C., active ingredient 50%), 1,2-HD, PG, Proxel-XL2, and ion-exchanged water as a resin emulsion in the dispersion, It added by the quantity (mass part) shown in Table 1, and stirred for 20 minutes at 40 degreeC. After stirring, the mixture was filtered through a 10 μm diameter SUS mesh filter to prepare a white ink having the composition shown in Table 1.
The compositions of the black ink 1 to the white ink 5 are summarized in Table 1. In Table 1, “resin EM” means a resin emulsion, and the numerical value represents the converted amount (parts by mass) of the resin component. A blank part means no addition. The amount of ion-exchanged water is the amount of ion-exchanged water contained in the obtained ink.

<First heating step>
Next, using an infrared heater (IR heater) as a first heating means, infrared light is irradiated from the side of the intermediate transfer medium to which the second ink is applied, and the second ink is heated to 100 ° C. The volatile liquid was removed.
<Transfer process>
Next, in the transfer unit, the second ink heated in the first heating step, the first ink, and the surface treatment liquid are used as a PVC film as a recording medium: ViewCAL (manufactured by Sakurai Co., Ltd., model number VC9700). Transcribed. The transfer pressure in this step was 30 kg / cm ² .
In the transfer portion, the curvature of the intermediate transfer medium was larger than the curvature of the recording medium. That is, the radius of curvature of the intermediate transfer medium at the transfer portion was 30 mm, and the radius of curvature of the recording medium at the transfer portion was 50 mm.

<Second heating step>
Thereafter, using an infrared heater (IR heater) as a second heating means, infrared light is irradiated from the surface of the recording medium opposite to the side on which the second ink is transferred, and the second ink is irradiated at 100 ° C. And the remaining liquid component was removed, and the thermoplastic resin was softened to fix the printing portion on the recording medium. As a result, a recorded matter was obtained.

(Example 2)
A recorded matter was produced in the same manner as in Example 1 except that the production apparatus as shown in FIG. 1 was used.
In FIG. 1, the polymerization process is the same as in FIG. 1, and an infrared heater (IR heater) is used as the first heating means and is opposite to the surface to which the second ink of the intermediate transfer medium is applied. Infrared rays were irradiated from the surface side, and the second ink was heated to 100 ° C. to remove the volatile liquid.

  Further, the manufacturing apparatus used in this example includes a heat roller as the second heating unit, and the recording medium on which the second ink is transferred is on the side opposite to the side on which the heat roller is provided. The pressure roller without a heat source was disposed oppositely. Heat is applied by contacting a heat roller (40 ° C.) as a second heating means from the side opposite to the side on which the second ink is transferred to remove the remaining liquid component and thermoplasticity. The resin was softened and the printing part was fixed on the recording medium. As a result, a recorded matter was obtained.

(Example 3)
A recorded matter was produced in the same manner as in Example 1 except that the production apparatus as shown in FIG. 3 was used.
In FIG. 3, the polymerization process is the same as in FIG. 1, and a second air is applied from the surface of the intermediate transfer medium to which the second ink is applied using a warm air heater as the first heating means. Heat to 80 ° C. to remove volatile liquid.
Further, as a second heating means, heating is performed from the surface on which the second ink is transferred with hot air of 80 ° C. to remove the remaining liquid component, and the thermoplastic resin is softened so that the printing portion is recorded on the recording medium. Fixed to. As a result, a recorded matter was obtained.

(Comparative Example 1)
Using a manufacturing apparatus that does not have the first ink application means (a structure in which the first ink application means is omitted from the manufacturing apparatus as shown in FIG. 2), the first ink application process and the polymerization process are performed. A recorded matter was produced in the same manner as in Example 2 except that the description was omitted.
(Comparative Example 2)
Except for using a manufacturing apparatus that does not have the first heating means (a structure in which the first heating means is omitted from the manufacturing apparatus as shown in FIG. 2), and that the first heating step is omitted. A recorded matter was produced in the same manner as in Example 2.
(Comparative Example 3)
Except for using a manufacturing apparatus that does not have the second heating means (a structure in which the second heating means is omitted from the manufacturing apparatus as shown in FIG. 2) and omitting the second heating step. A recorded matter was produced in the same manner as in Example 2.

Table 2 summarizes the configuration of the manufacturing apparatus and the manufacturing conditions for each of the examples and comparative examples.
In the table, the wax component (non-volatile content) of AQUACER 515 (trade name, polyethylene wax emulsion manufactured by Big Chemie Japan Co., Ltd., non-volatile content: 35% by mass) is “W1”, and 1,2-hexanediol is “HD”. ”,“ PG ”for propylene glycol, and“ BYK ”for BYK-348 as a surfactant. In the column of “Position of ultraviolet irradiation means” in the table, “inner surface side” means that the surface of the intermediate transfer medium placed on the side opposite to the surface to which the second ink is applied, and the intermediate transfer medium. The second ink is provided on the surface side to which the second ink is applied, and is indicated by “outer surface side”. In the “position of the first heating means” column, the second ink of the intermediate transfer medium is applied. The surface disposed on the side opposite to the surface is indicated as “inside surface”, and the surface disposed on the surface to which the second ink of the intermediate transfer medium is applied is indicated as “outside surface”. In the “position of means” column, the “inner surface side” is the surface of the recording medium opposite to the surface to which the second ink is applied, and the surface of the recording medium to which the second ink is applied. The one installed on the side is indicated by “outside side”. In the table, the heating temperature of the second ink by the first heating means (heating temperature in the first heating step) is T ₁ [° C.], and the heating temperature of the second ink by the second heating means ( The heating temperature in the second heating step) was indicated by T ₂ [° C.]. Moreover, in the Example using what contains a wax and water as a structural component of a surface treatment liquid, the said surface treatment liquid made | formed water-based wax emulsion. Further, the recording media used in the examples and comparative examples were all non-absorbing.

[2] Evaluation Regarding the recorded matter obtained as described above, the following evaluation was performed.
[2.1] Appearance evaluation (existence of appearance defects)
Each recorded matter produced in each of the examples and comparative examples was visually observed and evaluated according to the following criteria.

A: A printing part having a desired shape is formed reliably, and printing defects due to flow, repellency, etc. are not recognized.
B: Slight disturbance was observed only in the thin line portion of the printed portion.
C: Obvious disturbance was observed in the thin line portion of the printed portion, but no disturbance was observed in other portions.
D: In addition to the disturbance in the thin line portion, slight disturbance was also observed in other parts.
E: In addition to the disturbance in the thin line portion, clear disturbance was also observed in other parts.

[2.2] Evaluation of stereoscopic effect In each of the above examples and comparative examples, a kamaboko pattern having a width of 1 mm and a height of 10 μm with a lenticular effect was printed by an inkjet method during the first ink application step. Each obtained recorded matter was visually observed and evaluated according to the following criteria.
A: The printing part is full of stereoscopic effect.
B: The printed part has an excellent stereoscopic effect.
C: The printing part has a three-dimensional effect.
D: The printed part is inferior in stereoscopic effect.

[2.3] Evaluation of Fixing Strength For each recorded matter produced in each of the above Examples and Comparative Examples, the II type was applied to the 100% duty solid color printing portion of each ink in accordance with the method described in Japanese Industrial Standard JISL0849. Using a Gakushin friction fastness tester AB-301S (manufactured by Tester Sangyo Co., Ltd.), a dry white cotton cloth is attached to the tip of the friction element, and the reciprocating speed is 30 times per minute at a load of about 2 N / 100 mm ^2. The fastness test was conducted 100 times. The density of the printed part before and after the test was measured with X-Rite model 404 (manufactured by X-Rite Inc.), the average density residual ratio at 10 locations was calculated, and judged according to the following criteria. It can be said that the larger the residual density ratio, the better the fixing strength of the printing part with respect to the recording medium.

AA: The average concentration residual ratio is 90% or more.
A: The average concentration residual ratio is 80% or more and less than 90%.
B: The average concentration residual ratio is 60% or more and less than 80%.
C: The average concentration residual ratio is 40% or more and less than 60%.
D: The average concentration remaining rate is 20% or more and less than 40%.
E: Average density residual ratio is less than 20%, or fixing is impossible.
These results are shown in Table 3.

  As is apparent from Table 3, in the recorded matter of the present invention, a printing part having a desired shape was surely formed, and the fixing strength of the printing part to the recording medium was excellent. In the recorded matter of the present invention, the three-dimensional effect of the printed part was excellent, and a hologram-like expression was possible. Further, according to the present invention, recorded matter can be produced with excellent productivity and yield. Further, in the present invention, a recorded matter can be produced with low energy. On the other hand, in the comparative example, a satisfactory result was not obtained.

  DESCRIPTION OF SYMBOLS 100 ... Manufacturing apparatus 11 ... Intermediate transfer medium 12 ... Surface treatment liquid provision means 13 ... First ink provision means 14, 14C, 14M, 14Y, 14W, 14K ... Second ink provision means 15 ... Ultraviolet irradiation means 16 ... First 1 heating means 17 ... second heating means 18A, 18B ... support roll 19A ... pressure roll 19B ... pressure roll (recording medium conveying means) 20 ... cleaning means 30 ... drying means 50 ... surface treatment liquid 51 ... first Ink 52 ... Second ink 53 ... Recording medium

Claims (9)

A first ink application step of applying to the intermediate transfer medium a first ink containing a polymerizable compound that is polymerized by irradiation with ultraviolet rays;
A polymerization step of irradiating the first ink with ultraviolet rays to polymerize the polymerizable compound;
A second ink application step of applying a second ink containing a colorant, a thermoplastic resin, and a volatile liquid to a portion of the intermediate transfer medium to which the first ink has been applied by an inkjet method;
A first heating step of heating the intermediate transfer medium to volatilize at least a part of the volatile liquid;
A transfer step of transferring the second ink and the first ink heated in the first heating step to a recording medium;
And a second heating step of heating the second ink transferred to the recording medium.   2. The recorded matter according to claim 1, wherein in the first heating step, at least a part of the volatile liquid is volatilized by heating from the surface of the intermediate transfer medium opposite to the surface to which the second ink is applied. Manufacturing method.   3. The surface treatment liquid application step of applying a surface treatment liquid to a portion of the intermediate transfer medium to which the first ink is to be applied prior to the first ink application step. Manufacturing method of recorded matter.   The method for manufacturing a recorded matter according to claim 3, wherein the surface treatment liquid contains a wax.   5. The method for producing a recorded matter according to claim 4, wherein the surface treatment liquid contains one or more selected from the group consisting of polyolefin wax, ethylene vinyl acetate wax, and carnauba wax.   6. The first ink according to claim 1, wherein the first ink includes a liquid polymerizable compound that forms a liquid alone under the conditions of the first ink application step as the polymerizable compound. Manufacturing method of recorded matter.   The method for producing a recorded matter according to claim 6, wherein the first ink contains allyl glycol as the liquid polymerizable compound.   The method for producing a recorded matter according to claim 1, wherein the second ink includes a liquid component having a boiling point of 110 ° C. or more and 250 ° C. or less as the volatile liquid.   9. The method according to claim 1, wherein the second heating step is performed by heating from the surface of the recording medium opposite to the side on which the second ink is transferred. Manufacturing method of recorded matter.

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