JP2013022932A - Printing method, printing device, printing matter, and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a printing method, a printing device, a printing matter, and a molding excellent in processing when a first ink and a second ink are applied on a sheet-like print medium, for example, and machining is applied to the applied surface of the print medium.SOLUTION: The printing method applies a synthetic resin-made first ink 1 and a synthetic resin-made second ink 2 on the print medium as liquid droplets, then cures the liquid droplets, and carries out printing on the print medium. In the printing method, the first ink 1 is rich in extensibility and a glass transition point of the cured second ink 2 is higher than a glass transition point of the cured first ink 1. When the first ink 1 and second ink 2 are applied on the print medium, a first dot D1 formed by depositing the liquid droplet of the first ink 1 on the print medium and a plurality of second dots D2 formed by depositing a plurality of liquid droplets of the second ink 2 on the print medium are brought into contact with each other but adjacent second dots D2 are separated from each other.

Description

  The present invention relates to a printing method, a printing apparatus, a printed material, and a molded body.

For example, a display board that serves as a display unit of a speedometer as an interior part of an automobile has a substrate and a printed layer formed by printing with ink on the substrate (for example, Patent Document 1). reference). Ink used for automobile interior parts is generally ink having relatively high stretchability when cured. This is one of the reasons that the vehicle interior temperature in the hot summer is 50 ° C. or higher.
However, when the printing layer is formed using ink that has only high stretchability, if the display plate is subjected to mechanical processing such as drawing or punching, the printing layer is cracked or peeled off. However, there was a problem that it was unusable, that is, a defective product.

JP 2001-343260 A

  An object of the present invention is to provide a printing method and a printing apparatus that are excellent in workability when a first ink and a second ink are applied to a sheet-like print medium and the coated surface is processed. When a print layer formed of the first ink and the second ink is processed, a printed matter having excellent processability and a print layer formed of the first ink and the second ink Another object of the present invention is to provide a molded body that is favorably processed when it is machined.

Such an object is achieved by the present invention described below.
The printing method of the present invention includes a first ink containing a first polymerization initiator and a first polymerizable compound, and a second ink containing a second polymerization initiator and a second polymerizable compound; Is applied to the print medium as droplets, then cured and printed on the print medium,
When the first ink is cured to form a film having a thickness of 5 μm, the first ink is stretched by 70% or more when the film is stretched in an environment of 150 ° C.,
The glass transition point of the cured product obtained by curing the second ink is higher than the glass transition point of the cured product obtained by curing the first ink.
When applying the first ink and the second ink onto the print medium, the first dots formed by the droplets of the first ink landing on the print medium; and the second dots Applying each of the droplets such that a plurality of droplets of ink are in contact with a plurality of second dots formed on the print medium, but are adjacent to each other. It is characterized by.
Thereby, for example, the first ink and the second ink are applied on a print medium in the form of a sheet, and the processability when the applied surface is processed is excellent.

In the printing method of the present invention, it is preferable that the total amount of the first ink is larger than the total amount of the second ink on the print medium.
Thereby, it is possible to reliably prevent the stretchability of the cured first ink from being impaired by the cured second ink.
In the printing method of the present invention, the glass transition point of the cured product obtained by curing the first ink is less than 100 ° C., and the glass transition point of the cured product obtained by curing the second ink is 100 ° C. or more. It is preferable that
Thereby, for example, the first ink and the second ink are applied on a print medium in the form of a sheet, and the workability when processing the coated surface is extremely excellent.

In the printing method of the present invention, the difference between the glass transition point of the cured product obtained by curing the first ink and the glass transition point of the cured product obtained by curing the second ink is 300 ° C. or less. Is preferred.
Thereby, for example, the first ink and the second ink are applied on a print medium in the form of a sheet, and the workability when processing the coated surface is extremely excellent.

In the printing method of the present invention, the monofunctional polymerizable compound is 65% by mass or more of the total mass of the first polymerizable compound, and the polyfunctional polymerizable compound is included in the total mass of the second polymerizable compound. It is preferable that a compound is 50 mass% or more.
As a result, the portion composed of the ink after curing becomes rich in stretchability, and for example, it becomes excellent in impact resistance, abrasion resistance (abrasion resistance), scratch resistance, solvent resistance, Workability is further improved.

In the printing method of the present invention, it is preferable that the first ink and the second ink are each cured by being irradiated with ultraviolet rays having the same wavelength.
As a result, the first ink and the second ink can be cured together.
In the printing method of the present invention, each of the first ink and the second ink is cured by being irradiated with ultraviolet rays, and the wavelength of the ultraviolet rays is from 350 nm to 450 nm. preferable.
As a result, the first ink and the second ink can be easily and reliably cured together.
In the printing method of the present invention, it is preferable that the first ink and the second ink each have a viscosity at room temperature of 1 mPa · s to 1000 mPa · s.
Thereby, when each of the first ink and the second ink is ejected by the ink jet method, the ejection is stably performed.

In the printing method of the present invention, when the viscosity of the first ink in an environment of 40 ° C. is μ ₁ and the viscosity of the second ink in an environment of 40 ° C. is μ ₂ ((μ ₁ It is preferable to satisfy −μ ₂ ) / μ ₁ ) × 100 = ± 10 [%].
Thereby, when each of the first ink and the second ink is ejected by the ink jet method, the ejection is performed more stably.

In the printing method of the present invention, it is preferable that the first ink and the second ink each have a surface tension at room temperature of 5 mN / m or more and 200 mN / m or less.
As a result, when the first ink and the second ink are applied to the same region, the wetting and spreading in that region shows the same behavior, and each ink spreads uniformly and prevents uneven color. can do.

In the printing method of the present invention, when the surface tension of the first ink at 40 ° C. is f ₁ and the surface tension of the second ink at 40 ° C. is f ₂ , ((f ₁ −f ₂ ) / F ₁ ) × 100 = ± 10 [%] is preferably satisfied.
As a result, when the first ink and the second ink are applied to the same region, the wetting and spreading in the region exhibits the same behavior, and it is ensured that each ink spreads uniformly and color unevenness occurs. Can be prevented.

In the printing method of the present invention, it is preferable that the first ink or the second ink contains a pigment as a colorant.
Thereby, the part comprised with the ink after hardening is excellent in a weather resistance, and is rich in color reproducibility.
In the printing method of the present invention, it is preferable that the second ink is substantially colorless.
Thereby, even if the first ink and the second ink are mixed, it is possible to suppress or prevent the color change of the first ink from the original color.

In the printing method of the present invention, it is preferable that the ratio between the first ink and the second ink is constant at a plurality of different locations on the print medium.
Thereby, the influence of the 2nd ink with respect to a 1st ink can be made constant, and the extreme discoloration by the 2nd ink of a 1st ink can be prevented reliably.
In the printing method of the present invention, it is preferable that the amount of the second ink is constant and the amount of the first ink is changed at a plurality of different locations on the print medium.
Thereby, the part printed on the printing medium can have a desired stretchability.

The printing apparatus of the present invention includes a first ink containing a first polymerization initiator and a first polymerizable compound, and a second ink containing a second polymerization initiator and a second polymerizable compound. Is applied to the print medium as droplets, then cured to print on the print medium,
When the first ink is cured to form a film having a thickness of 5 μm, the first ink is stretched by 70% or more when the film is stretched in an environment of 150 ° C.,
The glass transition point of the cured product obtained by curing the second ink is higher than the glass transition point of the cured product obtained by curing the first ink.
When applying the first ink and the second ink onto the print medium, the first dots formed by the droplets of the first ink landing on the print medium; and the second dots Applying each of the droplets such that a plurality of droplets of ink are in contact with a plurality of second dots formed on the print medium, but are adjacent to each other. It is characterized by.
Thereby, for example, the first ink and the second ink are applied on a print medium in the form of a sheet, and the processability when the applied surface is processed is excellent.

In the printing apparatus of the present invention, a droplet having at least one first nozzle that ejects the first ink as a droplet and at least one second nozzle that ejects the second ink as a droplet. A discharge head;
A moving means for relatively reciprocating the droplet discharge head and the printing medium,
The droplet discharge head is configured such that the second nozzle is located behind the first nozzle in the direction of travel, and the first nozzle is disposed on the print medium from the first nozzle when it travels. It is preferable that ink is ejected, and further, the second ink is ejected from the second nozzle onto the first ink on the print medium.
As a result, in either case of the forward path or the return path, the first ink can be surely ejected prior to the second ink, and the second ink can be reliably stacked on the first ink.

In the printing apparatus of the present invention, the first ink contains a pigment as a colorant,
The droplet discharge head discharges the plurality of first inks having different colors of the pigment, respectively, and a plurality of the first nozzles arranged along the traveling direction of the droplet discharge head;
It is preferable that the second nozzles are disposed on the front side and the rear side in the traveling direction of the droplet discharge head with respect to the plurality of first nozzles.
As a result, in either case of the forward path or the return path, the first ink can be more reliably ejected prior to the second ink, and the second ink can be more reliably superimposed on the first ink. it can.

In the printing apparatus of the present invention, the input information having the color and material of the print medium, and the display color displayed by the first ink and the second ink mixed on the print medium, and the first A calibration curve indicating a relationship between output information having a mixing ratio of the first ink and the second ink, and configured to determine the output information from the input information based on the calibration curve. It is preferable.
Thereby, the reproducibility of the desired color in the part which printed on the printing medium is attained.

The printed matter of the present invention includes a print medium,
Drops of a first ink containing a first polymerization initiator and a first polymerizable compound and a second ink containing a second polymerization initiator and a second polymerizable compound onto a print medium And having a printed layer obtained by curing as
When the first ink is cured to form a film having a thickness of 5 μm, the first ink is stretched by 70% or more when the film is stretched in an environment of 150 ° C.,
The glass transition point of the cured product obtained by curing the second ink is higher than the glass transition point of the cured product obtained by curing the first ink.
When applying the first ink and the second ink onto the print medium, the first dots formed by the droplets of the first ink landing on the print medium; and the second dots Applying each of the droplets such that a plurality of droplets of ink are in contact with a plurality of second dots formed on the print medium, but are adjacent to each other. It is characterized by.
Thereby, when processing a printed layer formed of the first ink and the second ink, the processability is excellent.

The molded article of the present invention includes a printing medium, a first ink containing a first polymerization initiator and a first polymerizable compound, a second ink containing a second polymerization initiator and a second polymerizable compound. 2 is a molded body obtained by applying machining to a printed material having a printed layer formed by applying the ink of 2 as droplets on a printing medium and then curing the ink;
When the first ink is cured to form a film having a thickness of 5 μm, the first ink is stretched by 70% or more when the film is stretched in an environment of 150 ° C.,
The glass transition point of the cured product obtained by curing the second ink is higher than the glass transition point of the cured product obtained by curing the first ink.
When the first ink and the second ink are applied on the print medium, the first dots formed by the droplets of the first ink landing on the print medium, and the second Each droplet is applied so that a plurality of droplets of ink contact with a plurality of second dots formed on the print medium, but the adjacent second dots are separated from each other. It is characterized by that.
As a result, when machining is performed on the printing layer formed of the first ink and the second ink, the machining is performed satisfactorily.

1 is a perspective view showing a first embodiment of a printing apparatus of the present invention. FIG. 2 is a side view illustrating a schematic configuration of a carriage of the printing apparatus illustrated in FIG. 1. FIG. 2 is a bottom view illustrating a schematic configuration of a carriage of the printing apparatus illustrated in FIG. 1. It is a figure which shows schematic structure of the droplet discharge head of the printing apparatus shown in FIG. It is a perspective view for demonstrating the characteristic of the 1st ink. It is a graph which shows the recovery rate (displacement recovery amount / maximum displacement amount) of the film | membrane consisting of 1st ink, the film | membrane consisting of 2nd ink, and the film | membrane consisting of mixed ink of 1st ink and 2nd ink. It is a fragmentary sectional view which shows in order the process which manufactures the printed matter of this invention, and also manufactures a molded object therefrom. It is a fragmentary sectional view which shows in order the process which manufactures the printed matter of this invention, and also manufactures a molded object therefrom. It is a fragmentary sectional view which shows in order the process which manufactures the printed matter of this invention, and also manufactures a molded object therefrom. It is a fragmentary sectional view which shows in order the process which manufactures the printed matter of this invention, and also manufactures a molded object therefrom. It is a fragmentary sectional view which shows in order the process which manufactures the printed matter of this invention, and also manufactures a molded object therefrom. It is a fragmentary sectional view which shows in order the process which manufactures the printed matter of this invention, and also manufactures a molded object therefrom. It is a fragmentary sectional view which shows in order the process which manufactures the printed matter of this invention, and also manufactures a molded object therefrom. It is a fragmentary sectional view which shows in order the process which manufactures the printed matter of this invention, and also manufactures a molded object therefrom. It is a top view which shows the state which each provided the 1st ink and the 2nd ink on the printing medium using the printing apparatus shown in FIG. It is a top view which shows the state (2nd Embodiment) which respectively provided the 1st ink and the 2nd ink on the printing medium using the printing apparatus of this invention. It is a top view which shows the state (3rd Embodiment) which each provided the 1st ink and the 2nd ink on the printing medium using the printing apparatus of this invention. It is a top view which shows the state (4th Embodiment) which each provided the 1st ink and the 2nd ink on the printing medium using the printing apparatus of this invention. It is a top view which shows the state (5th Embodiment) which each provided the 1st ink and the 2nd ink on the printing medium using the printing apparatus of this invention. It is a top view which shows the state (6th Embodiment) which each provided the 1st ink and the 2nd ink on the printing medium using the printing apparatus of this invention. It is a top view which shows the state (7th Embodiment) which each provided the 1st ink and the 2nd ink on the printing medium using the printing apparatus of this invention. It is a table as a calibration curve which the printing apparatus (8th Embodiment) of this invention memorize | stores.

Hereinafter, a printing method, a printing apparatus, a printed material, and a molded body of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.
<First Embodiment>
1 is a perspective view showing a first embodiment of a printing apparatus according to the present invention, FIG. 2 is a side view showing a schematic configuration of a carriage of the printing apparatus shown in FIG. 1, and FIG. 3 is a drawing of the printing apparatus shown in FIG. 4 is a bottom view showing a schematic configuration of the carriage, FIG. 4 is a diagram showing a schematic configuration of a droplet discharge head of the printing apparatus shown in FIG. 1, and FIG. 5 is a perspective view for explaining the characteristics of the first ink. 6 is a graph showing the recovery rate (displacement recovery amount / maximum displacement amount) of the film made of the first ink, the film made of the second ink, and the film made of the mixed ink of the first ink and the second ink. 7 to 14 are partial cross-sectional views sequentially showing the steps for producing the printed matter of the present invention and further producing the molded body therefrom, and FIG. 15 is a diagram showing the printing apparatus shown in FIG. It is a top view which shows the state which each provided the 1st ink and the 2nd ink. Hereinafter, for convenience of explanation, the upper side in FIGS. 1, 2, 4 (b), (c), 5, and 7 to 14 is referred to as “upper”, and the lower side is referred to as “lower”. . Further, the left side in FIGS. 7 to 14 is referred to as “left”, and the right side is referred to as “right”.

A printing apparatus 700 shown in FIG. 1 is an apparatus that manufactures the printed matter 100 shown in FIG. 13 with the ink set 10 loaded therein. And this printed matter 100 becomes a base material of the molded object 200 shown in FIG. The molded body 200 is used as, for example, an automobile interior part such as a speedometer, an exterior part of an electric product, a mask, a signboard, and the like.
The ink set 10 includes a first ink 1Y of Y (yellow), a first ink 1C of C (cyan), a first ink 1M of M (magenta), and a first ink of K (black). 1K and W (colorless and transparent) second inks 2a and 2b. In the present embodiment, the first ink 1Y is stored in the tank 11Y, the first ink 1C is stored in the tank 11C, and the first ink 1M is stored in the tank 11M. 1K is stored in the tank 11K, the second ink 2a is stored in the tank 11Wa, and the second ink 2b is stored in the tank 11Wb, and is ejected as droplets L by an ink jet method. Hereinafter, when the first inks 1Y, 1C, 1M, and 1K are not distinguished, they may be simply referred to as “first ink 1”. Similarly, when the second inks 2a and 2b are not distinguished from each other, they may be simply referred to as “second ink 2”. Further, when the first ink 1 and the second ink 2 are not distinguished from each other, they may be simply referred to as “ink”.

First, the printed material 100 will be described.
[Printed matter]
As shown in FIG. 13, the printed material 100 includes a base material (substrate) 101 as a print medium and a print layer 102 formed on the base material 101.
The constituent material of the substrate 101 is not particularly limited. For example, various resins, various glasses, various metals, and the like can be used, but a resin material is preferable from the viewpoint that it can be deformed by machining. .

  The resin material is not particularly limited. For example, polyolefin such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (EVA), cyclic polyolefin, modified polyolefin, polyvinyl chloride, poly Vinylidene chloride, polystyrene, polyamide, polyimide, polyamideimide, polycarbonate, poly- (4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile Styrene copolymer (AS resin), butadiene-styrene copolymer, polyoxymethylene, polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate Polyester (PET), polybutylene terephthalate (PBT), polycyclohexane terephthalate (PCT) and other polyesters, polyether, polyether ketone (PEK), polyether ether ketone (PEEK), polyether imide, polyacetal (POM), Examples include polyphenylene oxide, modified polyphenylene oxide, polysulfone, polyethersulfone, polyphenylene sulfide, polyarylate, aromatic polyester (liquid crystal polymer), and copolymers, blends, and polymer alloys mainly composed of these. 1 type or 2 types or more can be used in combination (for example, as a laminate of two or more layers).

  The print layer 102 is printed using the first ink 1, that is, the ink of at least one of the first inks 1 Y, 1 C, 1 M, and 1 K and the second ink 2. . The first ink 1 and the second ink 2 are supplied onto the base material 101 by ejecting (applying) each ink as droplets L on the ink jet printing apparatus 700. Done. Then, the ink on the substrate 101 is cured by irradiating with ultraviolet rays to form the printing layer 102.

Further, the thickness of the base material 101 and the thickness of the printing layer 102 depend on what the molded body 200 is, that is, what the molded body 200 is used for. In the case of an automobile speedometer panel, the thickness of the substrate 101 is preferably 0.1 mm to 2 mm, and more preferably 0.3 to 0.8 mm. The thickness of the printing layer 102 is preferably 5 to 200 μm, and more preferably 5 to 100 μm.
By performing machining on the printed matter 100 as described above, a molded body 200 is obtained.

Next, the molded body 200 will be described.
[Molded body]
As shown in FIG. 14, the molded body 200 includes a bottomed cylindrical portion 103 and an opening 104 at a position different from the bottomed cylindrical portion 103 in a portion where the printed layer 102 of the printed material 100 is formed. Have. The bottomed cylindrical portion 103 is formed by drawing. The opening 104 is formed by punching. A machine tool such as an NC machine can be used as an apparatus used for such processing.

Next, the ink set 10 will be described.
[Ink set]
The ink set 10 includes a first ink 1 that is a radiation curable (ultraviolet curable) ink containing a pigment as a colorant, and a second ink that is a radiation curable (ultraviolet curable) ink that does not contain a pigment. 2 is provided.

  The radiation curable ink is required to be cured with high sensitivity in order to form a high-quality image. By achieving high sensitivity of the ink, high curability is imparted by irradiation with actinic radiation, so in addition to reducing power consumption and extending life by reducing the load on the radiation generator, uncured low molecular weight It has various advantages such as the ability to suppress the volatilization of the substance and the decrease in the intensity of the formed image.

The first ink 1 contains (a-1) a polymerization initiator (first polymerization initiator) and (b-1) a polymerizable compound (first polymerizable compound). ) Of the total mass of the polymerizable compound, the monofunctional polymerizable compound (hereinafter also referred to as “monofunctional monomer”) is preferably 65% by mass or more.
The second ink 2 contains (a-2) a polymerization initiator (second polymerization initiator) and (b-2) a polymerizable compound (second polymerizable compound). ) Of the total mass of the polymerizable compound, the polyfunctional polymerizable compound (hereinafter also referred to as “polyfunctional monomer”) is preferably 50% by mass or more.

  In the ink, the mass ratio of the monofunctional polymerizable compound to the total mass of the polymerizable compound in the ink is also referred to as “monofunctional monomer ratio”, and the mass of the polyfunctional polymerizable compound relative to the total mass of the polymerizable compound in the ink. The ratio is also referred to as “polyfunctional monomer ratio”. The monofunctional monomer ratio (%) and polyfunctional monomer ratio (%) shall be rounded off to the nearest whole number.

  The ink is a radiation curable ink that can be cured by irradiation with actinic radiation. The “actinic radiation” is not particularly limited as long as it is an actinic radiation capable of imparting energy capable of generating a starting species in the ink by the irradiation, and widely includes α rays, γ rays, X rays, ultraviolet rays. (UV), visible light, electron beam and the like are included, and among them, ultraviolet light and electron beam are preferable from the viewpoint of curing sensitivity and availability of the apparatus, and ultraviolet light is particularly preferable. Therefore, the ink is preferably an ink that can be cured by irradiating ultraviolet rays as radiation.

Hereinafter, each component of the ink will be described.
(A) Polymerization initiator As the polymerization initiator in both the first ink 1 and the second ink 2, a known radical polymerization initiator or a known cationic polymerization initiator can be used. A polymerization initiator may be used individually by 1 type, and may use 2 or more types together. Moreover, you may use together a radical polymerization initiator and a cationic polymerization initiator.

The polymerization initiator is a compound that absorbs external energy to generate a polymerization initiating species. External energy used for initiating polymerization is roughly divided into heat and actinic radiation, and a thermal polymerization initiator and a photopolymerization initiator are used, respectively. Examples of the active radiation include γ rays, β rays, electron beams, ultraviolet rays, visible rays, and infrared rays.
In addition, the ink preferably contains a radical polymerization initiator when a radical polymerizable compound is used as the polymerizable compound, and the cationic polymerization initiator is used when a cationic polymerizable compound is used as the polymerizable compound. It is preferable to contain.

<Radical polymerization initiator>
As radical polymerization initiators, aromatic ketones, acylphosphine compounds, aromatic onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, Examples thereof include active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds. These radical polymerization initiators may be used alone or in combination. The radical polymerization initiator is suitably used alone or in combination of two or more.

<Cationic polymerization initiator>
As the cationic polymerization initiator (photoacid generator), for example, chemically amplified photoresists and compounds used for photocationic polymerization are used (Organic Materials Research Group, “Organic Materials for Imaging”, Bunshin Publishing) (1993), pages 187-192).

First, diazonium, ammonium, iodonium, sulfonium, _B aromatic onium compounds such as phosphonium ^{_{(C 6 F 5) 4 -}} , PF6 -, AsF 6 -, SbF 6 -, CF 3 SO 3 - and the like salts Can do. Secondly, sulfonated products that generate sulfonic acid can be mentioned. Thirdly, a halide that generates hydrogen halide can also be used. Fourthly, iron arene complexes can be mentioned.

In the ink, the total amount of the polymerization initiator used is preferably 0.01 to 35% by mass, and preferably 0.5 to 20% by mass, based on the total amount of the polymerizable compound used. Is more preferable, and it is still more preferable that it is 1.0-20 mass%. If it is 0.01% by mass or more, the ink can be sufficiently cured, and if it is 35% by mass or less, a cured film having a uniform degree of curing can be obtained.
Moreover, when using the sensitizer mentioned later for an ink, the total usage-amount of a polymerization initiator is mass ratio of a polymerization initiator: sensitizer, and polymerization initiator: sensitizer = 200: 1-1: 200. Preferably, it is 50: 1 to 1:50, more preferably 20: 1 to 1: 5.

(B) Polymerizable compound Both the first ink 1 and the second ink 2 contain a polymerizable compound.
The polymerizable compound preferably has a molecular weight of 1,000 or less, more preferably 50 to 800, and still more preferably 60 to 500.
The polymerizable compound is not particularly limited as long as it is a compound that undergoes a polymerization reaction such as a radical polymerization reaction, a cationic polymerization reaction, or an anion polymerization reaction by applying some energy, and is a curing compound. Although it can be used regardless, various known polymerizable compounds known as photopolymerizable compounds that cause a polymerization reaction by an initiating species generated from the polymerization initiator can be used.
Moreover, as a polymeric compound, a radically polymerizable compound and a cationically polymerizable compound can be illustrated preferably.

<Radically polymerizable compound>
The radical polymerizable compound is not particularly limited, and a known radical polymerizable compound can be used, but an ethylenically unsaturated compound is preferable, and a (meth) acrylate compound, a (meth) acrylamide compound, N-vinyl is preferable. More preferably, it is a compound and / or a vinyl ether compound, and more preferably a (meth) acrylate compound and / or an N-vinyl compound. “(Meth) acryl” means both acrylic and methacrylic.

  When the radically polymerizable compound is used for the first ink 1, the first ink 1 has 67 to 100% by mass of the monofunctional radically polymerizable compound in the total mass of the (b-1) polymerizable compound. It is preferable that it is 70-100 mass%, It is more preferable that it is 85-95 mass%. Within the above range, the printed layer 102 is rich in stretchability.

  When using a radically polymerizable compound for the 2nd ink 2, the 2nd ink 2 is 55-100 mass% of polyfunctional radically polymerizable compounds among the total mass of (b-2) polymeric compound. It is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and 100% by mass, that is, (b-2) all polymerizable compounds are polyfunctional radical polymerizable compounds. It is particularly preferred that Within the above range, the printed layer 102 is excellent in, for example, impact resistance, abrasion resistance (abrasion resistance), scratch resistance, and solvent resistance. In the present specification, impact resistance, abrasion resistance (abrasion resistance), scratch resistance, and solvent resistance may be collectively referred to as “durability”.

Moreover, the radically polymerizable compound may be monofunctional or polyfunctional.
The monofunctional radically polymerizable compound is preferably an N-vinyl compound described later, and more preferably an N-vinyl lactam.
Moreover, when using a radically polymerizable compound as (b-1) polymeric compound in the 1st ink 1, it is more preferable that the 1st ink 1 contains the N-vinyl compound mentioned later, and N-vinyl lactam. It is particularly preferred that

The polyfunctional radical polymerizable compound is preferably a polyfunctional (meth) acrylate compound described later. “(Meth) acrylate” means both acrylate and methacrylate.
The polyfunctional radical polymerizable compound is preferably a combination of a bifunctional radical polymerizable compound and a trifunctional or higher functional radical polymerizable compound, and is preferably a bifunctional radical polymerizable compound and a trifunctional radical polymerizable compound. More preferably, it is used in combination with a compound.

  When a radical polymerizable compound is used as the (b-2) polymerizable compound in the second ink 2, the second ink 2 is bifunctional radical polymerizable among the total mass of the (b-2) polymerizable compound. It is preferable that a compound is 30-100 mass%, It is more preferable that it is 50-95 mass%, It is further more preferable that it is 70-90 mass%. Further, the second ink 2 preferably contains 5 to 50% by mass, more preferably 10 to 30% by mass of a tri- or higher functional radical polymerizable compound among the total mass of the polymerizable compound (b-2). More preferred. Furthermore, the second ink 2 preferably contains 5 to 50% by mass, more preferably 10 to 30% by mass of the trifunctional radical polymerizable compound in the total mass of the polymerizable compound (b-2).

When a radical polymerizable compound is used for the first ink 1, the first ink 1 preferably has a monofunctional radical polymerizable compound of 50 to 95% by mass in the total mass of the first ink 1. More preferably, it is 55-90 mass%, and it is further more preferable that it is 60-85 mass%. Within the above range, the printed layer 102 is rich in stretchability (flexibility).
When the radically polymerizable compound is used for the second ink 2, the second ink 2 is preferably such that the polyfunctional radically polymerizable compound is 50 to 98% by mass in the total mass of the second ink 2. More preferably, it is 55-95 mass%, and it is further more preferable that it is 60-90 mass%. Within the above range, the printed layer 102 is excellent in durability.

Below, a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound are demonstrated.
[Monofunctional radical polymerizable monomer]
As the radically polymerizable compound, a monofunctional radically polymerizable monomer can be used.
Preferred examples of the monofunctional radical polymerizable monomer include monofunctional acrylate compounds, monofunctional methacrylates, monofunctional N-vinyl compounds, monofunctional acrylamide compounds, and monofunctional methacrylamide compounds. More preferred examples include methacrylate compounds and monofunctional N-vinyl compounds.
When the first ink 1 contains a monofunctional radical polymerizable monomer, the monofunctional radical polymerizable monomer is a monofunctional acrylate compound and a monofunctional N-vinyl compound, or a monofunctional methacrylate compound and a monofunctional N-. It is preferable to use a vinyl compound in combination, and it is particularly preferable to use a monofunctional acrylate compound and a monofunctional N-vinyl compound in combination.

The monofunctional radical polymerizable monomer has only one ethylenically unsaturated double bond group selected from the group consisting of acryloyloxy group, methacryloyloxy group, acrylamide group, methacrylamide group and N-vinyl group, It is more preferable to use a monomer having a cyclic structure.
Moreover, an ethylenically unsaturated compound is mentioned as a radically polymerizable monomer which can be used suitably.

  Monofunctional acrylates, monofunctional methacrylates, monofunctional vinyloxy compounds, monofunctional acrylamides and monofunctional methacrylamides include phenyl group, naphthyl group, anthracenyl group, pyridinyl group, tetrahydrofurfuryl group, piperidinyl group, cyclohexyl group Monofunctional radical-polymerizable monomers having a group having a cyclic structure such as cyclopentyl group, cycloheptyl group, isobornyl group, tricyclodecanyl group and the like are preferable.

  Monofunctional radically polymerizable monomers are preferably norbornyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, cyclodecyl (Meth) acrylate, dicyclodecyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, acryloylmorpholine, 2-benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (Meth) acrylate, phenoxytriethylene glycol (meth) acrylate, EO-modified cresol (meth) acrelane , Tetrahydrofurfuryl (meth) acrylate, caprolactone modified tetrahydrofurfuryl acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, N-phthalimidoethyl (meta) ) Acrylate, pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, N-cyclohexylacrylamide, N- (1,1-dimethyl-2-phenyl) ethylacrylamide, N-diphenylmethylacrylamide, N-phthalimidomethyl Acrylamide, N- (1,1′-dimethyl-3- (1,2,4-triazol-1-yl)) propyl acrylic De, 5- (meth) acryloyloxy-methyl-5-ethyl-1,3-dioxacyclohexane like.

Moreover, it is preferable to use the radically polymerizable monomer which has an N-vinyl group and has a group which has a cyclic structure as a monofunctional radically polymerizable monomer. Of these, N-vinylcarbazole, 1-vinylimidazole, and N-vinyllactams are preferably used, and N-vinyllactams are more preferably used.
In the first ink 1, the monofunctional cyclic polymerizable monomer having an N-vinyl group is preferably contained in an amount of 1 to 40% by mass, more preferably 10 to 35% by mass, based on the entire first ink 1. It is more preferable to contain 12-30 mass%. In the above range, an ink exhibiting good copolymerizability with other polymerizable compound and excellent in curability and blocking resistance can be obtained.
Moreover, in the 1st ink 1, it is preferable to contain monofunctional N-vinyl lactam 1-40 mass% of the 1st ink 1 whole, It is more preferable to contain 10-35 mass%, 12- More preferably, the content is 30% by mass.

  When the use amount of the monofunctional N-vinyl lactam is within the above numerical range, the curability, the cured film flexibility, and the adhesion of the cured film to the support are excellent. N-vinyl lactams are compounds having a relatively high melting point. When the content of N-vinyl lactam is 40% by mass or less, good solubility is exhibited even at a low temperature of 0 ° C. or less, and the temperature range in which ink can be handled is widened.

  The following acyclic monofunctional monomer can also be used as the monofunctional radical polymerizable monomer. The acyclic monofunctional monomer has a relatively low viscosity, and can be preferably used, for example, for the purpose of reducing the viscosity of the ink. However, the ratio of the following acyclic monofunctional monomer to the whole ink is 20% by mass or less from the viewpoint of suppressing the stickiness of the cured film and providing a high film strength that does not cause scratches during molding. preferable. More preferably, it is 15 mass% or less.

  Specifically, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, 2 -Hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether, polypropylene glycol (meth) acrylate monomethyl ether, Examples include polytetraethylene glycol (meth) acrylate monomethyl ether.

  Besides these, (poly) ethylene glycol mono (meth) acrylate, (poly) ethylene glycol (meth) acrylate methyl ester, (poly) ethylene glycol (meth) acrylate ethyl ester, (poly) ethylene glycol (meta) ) Acrylate phenyl ester, (poly) propylene glycol mono (meth) acrylate, (poly) propylene glycol mono (meth) acrylate phenyl ester, (poly) propylene glycol (meth) acrylate methyl ester, (poly) propylene glycol (meth) acrylate Ethyl ester, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, n-decyl acrylate, isooctyl acrylate, n-lauryl acrylate N-tridecyl acrylate, n-cetyl acrylate, n-stearyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, oligoester acrylate, N-methylol acrylamide, diacetone acrylamide, epoxy Acrylate, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, n-decyl methacrylate, isooctyl methacrylate, n-lauryl methacrylate, n-tridecyl methacrylate, n-cetyl methacrylate, n-stearyl methacrylate, allyl methacrylate, glycidyl methacrylate, Jill methacrylate, dimethylaminomethyl methacrylate, and allyl glycidyl ether and the like.

  Further, 2-ethylhexyl-diglycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxybutyl acrylate, 2-acryloyloxyethylphthalic acid, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, ethoxy Examples thereof include phenyl acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, lactone-modified flexible acrylate, butoxyethyl acrylate, 2-hydroxyethyl acrylate, and methoxydipropylene glycol acrylate. .

[Polyfunctional radical polymerizable monomer]
A polyfunctional radically polymerizable monomer can be used as the radically polymerizable compound.
The polyfunctional radical polymerizable monomer includes two ethylenically unsaturated double bonds selected from the group consisting of acryloyloxy group, methacryloyloxy group, acrylamide group, methacrylamide group, vinyloxy group, and N-vinyl group. The polyfunctional polymerizable monomer which has the above can be illustrated preferably. By containing a polyfunctional polymerizable monomer, an ink having high cured film strength can be obtained.

  Examples of the polyfunctional radical polymerizable monomer having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and salts thereof, Anhydrides having ethylenically unsaturated groups, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated urethane (meth) acrylic monomers or prepolymers, epoxy monomers or prepolymers, A compound having two or more ethylenically unsaturated double bond groups, which is a (meth) acrylic ester such as a urethane monomer or a prepolymer, is preferably used.

Specific examples include neopentyl glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, (triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate. , Polypropylene glycol di (meth) acrylate, (poly) tetramethylene glycol di (meth) acrylate, propylene oxide (PO) adduct di (meth) acrylate of bisphenol A, ethoxylated neopentyl glycol di (meth) acrylate, propoxylation Neopentyl glycol di (meth) acrylate, bisphenol A ethylene oxide (EO) adduct di (meth) acrylate, EO-modified pentaerythritol tri (meth) acrylate , PO-modified pentaerythritol tri (meth) acrylate, EO-modified pentaerythritol tetra (meth) acrylate, PO-modified pentaerythritol tetra (meth) acrylate, EO-modified dipentaerythritol tetra (meth) acrylate, PO-modified dipentaerythritol tetra (Meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO-modified tetramethylolmethanetetra (meth) acrylate, PO-modified tetramethylolmethanetetra (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, tri Tyrolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, bis (4- (meth) acryloxypolyethoxyphenyl) propane, Diallyl phthalate, triallyl trimellitate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decandiol di (meth) acrylate, neopentyl hydroxypivalate Glycol di (meth) acrylate, tetramethylol methane tri (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, modified glycerin tri (meth) acrylate, bisphenol A diglycy Diether ether (meth) acrylic acid adduct, modified bisphenol A di (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate tolylene diisocyanate urethane Examples include prepolymers, pentaerythritol tri (meth) acrylate hexamethylene diisocyanate urethane prepolymers, ditrimethylolpropane tetra (meth) acrylate, and pentaerythritol tri (meth) acrylate hexamethylene diisocyanate urethane prepolymers. More specifically, Shinzo Yamashita “Cross-linking agent handbook” (1981, Taiseisha); Kato Kiyomi “UV / EB curing handbook (raw material)” (1985, Polymer publication society); Ed. "Application and Market of UV / EB Curing Technology", page 79 (1989, CMC); "Polyester Resin Handbook" by Eiichiro Takiyama (1988, Nikkan Kogyo Shimbun Co., Ltd.) Radical polymerizable or crosslinkable monomers, oligomers and polymers known in the industry can be used.
Among these, the following can be illustrated preferably as a polyfunctional radically polymerizable monomer.

Examples of the bifunctional radical polymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, ethoxylated neopentyl glycol diacrylate Propoxylated neopentyl glycol diacrylate can be preferably exemplified.
Furthermore, it is also preferable to use a vinyl ether compound as the radical polymerizable compound.
The monomers listed as the radically polymerizable compound described above have high reactivity, low viscosity, and excellent adhesion to the support.

<Cationically polymerizable compound>
As the cationic polymerizable compound, from the viewpoint of curability and scratch resistance, an oxetane ring-containing compound and an oxirane ring-containing compound are suitable, and an embodiment containing both an oxetane ring-containing compound and an oxirane ring-containing compound is more preferable.
Here, the oxirane ring-containing compound (hereinafter also referred to as “oxirane compound”) is a compound containing at least one oxirane ring (oxiranyl group, epoxy group) in the molecule, specifically, as an epoxy resin. It can select suitably from what is normally used, for example, a conventionally well-known aromatic epoxy resin, an alicyclic epoxy resin, and an aliphatic epoxy resin is mentioned. Any of a monomer, an oligomer, and a polymer may be sufficient.
An oxetane ring-containing compound (hereinafter also referred to as “oxetane compound”) is a compound containing at least one oxetane ring (oxetanyl group) in the molecule.

When a cationically polymerizable compound is used for the first ink 1, the first ink 1 has 65 to 95% by mass of the monofunctional cationically polymerizable compound in the total mass of the (b-1) polymerizable compound. It is preferably 65 to 85 mass%, more preferably 65 to 75 mass%. Within the above range, the printed layer 102 is rich in stretchability.
When a cationically polymerizable compound is used for the second ink 2, the second ink 2 has a polyfunctional cationically polymerizable compound of 50 to 90% by mass in the total mass of the (b-2) polymerizable compound. It is preferably 52 to 75% by mass, more preferably 55 to 65% by mass. Within the above range, the printed layer 102 is excellent in durability.

The cationically polymerizable compound may be monofunctional or polyfunctional.
The monofunctional cationically polymerizable compound is preferably a monofunctional oxirane compound and / or a monofunctional oxetane compound.
The polyfunctional cation polymerizable compound is preferably a bifunctional cation polymerizable compound. Moreover, as a polyfunctional radically polymerizable compound, it is preferable that they are a polyfunctional oxirane compound and / or a polyfunctional oxetane compound, and it is more preferable to use a polyfunctional oxirane compound and a polyfunctional oxetane compound together.

When a cationically polymerizable compound is used for the first ink 1, the first ink 1 preferably has a monofunctional cationically polymerizable compound of 40 to 95% by mass in the total mass of the first ink 1. More preferably, it is 45-80 mass%, and it is further more preferable that it is 45-65 mass%. Within the above range, the printed layer 102 is rich in stretchability.
When a cationically polymerizable compound is used for the second ink 2, the second ink 2 is preferably such that the polyfunctional cationically polymerizable compound is 35 to 90% by mass in the total mass of the second ink 2. 38 to 75% by mass is more preferable, and 40 to 60% by mass is even more preferable. Within the above range, the printed layer 102 is excellent in durability.

Hereinafter, the monofunctional cation polymerizable compound and the polyfunctional cation polymerizable compound will be described in detail.
Examples of the cationic polymerizable compound include JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, JP-A-2001-310938, JP-A-2001-310937, and JP-A-2001-2001. Examples thereof include epoxy compounds, vinyl ether compounds, oxetane compounds and the like described in each publication such as No. 220526.

  Examples of monofunctional epoxy compounds include, for example, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene. Monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, etc. Is mentioned.

Examples of polyfunctional epoxy compounds include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol. S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxy 2- (3,4-epoxycyclohexyl) -7,8-epoxy-1,3-dioxaspiro [5.5] undecane, bis (3,4-epoxycyclohexyl) Rumethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6 '-Methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate) , Epoxyhexahydrophthalate dioctyl, epoxyhexahydrophthalate di-2-ethylhexyl, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Resin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,13-tetradecadiene dioxide, limonene dioxide, 1,2,7,8-diepoxyoctane 1,2,5,6-diepoxycyclooctane and the like.
Among these epoxy compounds, aromatic epoxides and alicyclic epoxides are preferable from the viewpoint of excellent curing speed, and alicyclic epoxides are particularly preferable.

  Examples of monofunctional oxetane compounds include, for example, 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy) methylbenzene, 4- Fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [1- (3-ethyl-3- Oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ) Ether, 2-ethylhexyl (3-ethyl-3-oxe) Nylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, Dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxy Ethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether and the like.

Examples of the polyfunctional oxetane compound include, for example, 3,7-bis (3-oxetanyl) -5-oxanonane, 3,3 ′-(1,3- (2-methylenyl) propanediylbis (oxymethylene)) bis. (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3 -Bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethylene Glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl) Ru-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3 -Ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl- 3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl) 3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis ( 3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis ( 3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-e Le-oxetanylmethyl) ether, EO-modified bisphenol F (3- ethyl-3-oxetanylmethyl) include polyfunctional oxetanes such as ether.
In addition, these cationically polymerizable compounds may use only 1 type, or may use 2 or more types together.

Further, the total mass of the polymerizable compound in the ink is preferably 55 to 95% by mass and more preferably 60 to 90% by mass with respect to the total mass of the ink. Within the above range, the curability is excellent and the viscosity is moderate.
Moreover, there is no restriction | limiting in particular as a manufacturing method of a polymeric compound, It can synthesize | combine by a well-known method. Moreover, when available, you may use a commercial item.

(C) Colorant The first ink 1 contains a pigment as a colorant. The pigment is excellent in weather resistance and rich in color reproducibility. In addition, as a pigment (colorant) that can be suitably used for the ink, a compound that does not function as a polymerization inhibitor in a polymerization reaction that is a curing reaction can be selected from the viewpoint of not reducing the sensitivity of the curing reaction by actinic radiation. preferable.
Although it does not necessarily limit as a pigment, For example, the organic or inorganic pigment of the following number described in a color index can be used.

Examples of red or magenta pigments include Pigment Red 3, 5, 19, 22, 31, 38, 42, 43, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49: 1, 53. : 1, 57: 1, 57: 2, 58: 4, 63: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 88, 104, 108, 112, 122, 123, 144 , 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Orange 13, 16, 20, 36,
Pigment Blue 1,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,17-1,22,27,28,29,36,60 as a blue or cyan pigment ,
As a green pigment, Pigment Green 7, 26, 36, 50,
As yellow pigments, Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 120, 137 , 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193,
As the black pigment, Pigment Black 7, 28, 26,
As a white pigment, Pigment White 6, 18, 21
Etc. can be used according to the purpose.

Further, it is preferable that the colorant is appropriately dispersed in the ink after being added to the ink. For dispersing the colorant, for example, a dispersion device such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, or a paint shaker can be used.
The colorant may be blended directly with each component when preparing the ink. However, in order to improve dispersibility, the colorant is added in advance to a dispersion medium such as a solvent or a radical polymerizable compound, and uniformly dispersed or dissolved. It can also be blended later.

(D) Dispersant The ink preferably contains a dispersant in order to stably disperse the pigment in the ink.
As the dispersant, a polymer dispersant is preferable. The “polymer dispersant” means a dispersant having a mass average molecular weight of 1,000 or more.

Dispersor BYK-101, DisperBYK-102, DisperBYK-103, DisperBYK-106, DisperBYK-111, DisperBYK-161, DisperBYK-162, DisperBYK-164D, DisperBYK-164D, , DisperBYK-168, DisperBYK-170, DisperBYK-171, DisperBYK-174, DisperBYK-182 (manufactured by BYK Chemie), EFKA4010, EFKA4046, EFKA5080, EFKA5010, EFKA5010, EFKA5010, EFKA5010, EFKA5010, EFKA5010, EFKA5010 Polymers such as KA745, EFKA7462, EFKA7500, EFKA7570, EFKA7575, EFKA7580 (manufactured by Efka Additive), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (Sannopco) Dispersant: Solsperse (Solsperse) 3000, 5000, 9000, 12000, 13240, 13940, 17000, 22000, 24000, 26000, 28000, 32000, 36000, 39000, 41000, 71000, etc. Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P1 3, F108, L121, P-123 (manufactured by ADEKA Co., Ltd.) and Isonet S-20 (manufactured by Sanyo Kasei Kogyo Co., Ltd.), manufactured by Enomoto Kasei Co., Ltd. Agent), # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyether ester type) ”.
The content of the dispersant in the ink is appropriately selected depending on the purpose of use, but it is preferably 0.05 to 15% by mass with respect to the total mass of the ink.

(E) Other components Other components than the above components can be added to the ink as needed.
Examples of other components include sensitizers, co-sensitizers, surfactants, ultraviolet absorbers, antioxidants, anti-fading agents, conductive salts, solvents, polymer compounds, basic compounds, and the like. .
In addition to this, as necessary, for example, leveling additives, matting agents, waxes for adjusting film properties, polyolefins, PET, and the like to improve the adhesion to a support such as PET, do not inhibit the polymerization A tackifier or the like can be contained.

As the tackifier, specifically, a high molecular weight adhesive polymer described in JP-A-2001-49200, 5-6p (for example, (meth) acrylic acid and an alkyl group having 1 to 20 carbon atoms). An ester with an alcohol having, an ester of (meth) acrylic acid with an alicyclic alcohol having 3 to 14 carbon atoms, a copolymer comprising an ester of (meth) acrylic acid with an aromatic alcohol having 6 to 14 carbon atoms) And a low molecular weight tackifier resin having a polymerizable unsaturated bond.
The first ink 1 and the second ink 2 containing the components as described above have different characteristics after curing.

When the first ink 1 is cured to form a film 1 ′ having a thickness of t _{1 of} 5 μm, the first ink 1 is stretched by 70% or more when the film 1 ′ is stretched in an environment of 150 ° C. (See FIG. 5). Hereinafter, this characteristic is referred to as a “first characteristic”. On the other hand, in the second ink 2, the glass transition point Tg ₂ of the second cured product obtained by curing the second ink 2 is the glass transition point Tg of the first cured product obtained by curing the first ink 1. _It has a characteristic higher than ₁ . Hereinafter, this characteristic is referred to as “second characteristic”. When the first cured product (film 1 ′) and the second cured product are compared, the first cured product is superior to the second cured product and has high elasticity.

The first characteristic, that is, the stretch ratio (stretchability) of the film 1 ′ is defined as follows.
As shown in FIG. 5A, a resin-made base material 300 having a length L ₃ , a thickness t ₃ , and a width w ₃ is prepared. Examples of the resin material constituting the substrate 300 include various thermoplastic elastomers such as polyethylene terephthalate (PET) and polycarbonate.
Then, the first ink 1 is applied onto the substrate 300 by an inkjet method.

Next, as shown in FIG. 5B, the first ink 1 on the substrate 300 is irradiated with ultraviolet rays from the ultraviolet irradiation device 500. The peak wavelength of ultraviolet rays at this time is about 390 nm, and the total irradiation time of ultraviolet rays is 0.05 to 5 seconds.
Thereby, as shown in FIG. 5C, a film 1 ′ formed by curing the first ink 1 is formed on the substrate 300. This film 1 ′ has a substantially circular shape with a diameter φd _{1 in} plan view. The thickness t ₁ of the film 1 ′ is 5 μm.

Next, as shown in FIG. 5D, the base material 300 on which the film 1 ′ is formed is accommodated in, for example, a chamber (not shown), and the inside of the chamber is heated to 150 ° C. by the electric heater 600. Maintain that state.
And the base material 300 is pulled until the full length becomes 2L. The pulling speed at this time is 1.0 mm / sec.
Further, the film 1 ′ follows the tensile deformation of the base material 300 and extends in the same direction as the base material 300. Drawing amount of time (stretched length) becomes △ d _1.
The stretching ratio is defined by (Δd ₁ / d) × 100, and the value is 70% or more.

In the second characteristic, the glass transition point Tg ₂ is higher than the glass transition point Tg _{1. In} this case, the glass transition point Tg ₁ is less than 100 ° C., and the glass transition point Tg ₂ is 100 ° C. or more. The glass transition point Tg ₁ is 50 to 90 ° C., and the glass transition point Tg ₂ is more preferably 100 to 150 ° C.
Further, the difference (Tg ₂ −Tg ₁ ) between the glass transition point Tg ₁ and the glass transition point Tg ₂ is preferably 300 ° C. or less, more preferably 10 to 200 ° C., and more preferably 50 to 100 ° C. More preferably.
The glass transition points Tg ₁ and Tg ₂ can be adjusted, for example, by adjusting the wavelength and irradiation time of ultraviolet rays that are irradiated when the ink is cured.

The first ink 1 and the second ink 2 having the above characteristics are applied to a part or all of the substrate 101 when the printed material 100 is manufactured. At this time, the first ink 1 and the second ink 2 are applied so as to overlap and partly mix (see FIGS. 7 to 13). Thereafter, the ink (first ink 1 and second ink 2) on the substrate 101 is cured by irradiating with ultraviolet rays from the ultraviolet irradiation means 12a and 12b. Thereby, the printing layer 102 is formed. As will be described later, the printing layer 102 is reliably prevented from being cracked or peeled off, and the printing layer 102 is rich in durability.
Since the second ink 2 is substantially colorless and transparent as described above, even if the first ink 1 and the second ink 2 are mixed, the original ink of the first ink 1 is used. It is possible to suppress or prevent discoloration of the color.

Further, the first ink 1 and the second ink 2 can be collectively cured with ultraviolet rays having the same peak wavelength (see FIG. 9). The peak wavelength of the ultraviolet light is not particularly limited, and is preferably 350 nm or more and 450 nm or less, for example, and more preferably 380 nm or more and 420 nm or less.
On the other hand, when the peak wavelength at which the first ink 1 is cured differs from the peak wavelength at which the second ink 2 is cured, that is, when the curing wavelength range is different, ultraviolet rays having respective peak wavelengths must be irradiated. I must. However, since ultraviolet rays having the same peak wavelength can be used, the process of forming the printed layer 102 by curing the first ink 1 and the second ink 2 when the printed material 100 is manufactured can be easily and quickly performed. Can be done.
In order to cure the first ink 1 and the second ink 2 with ultraviolet rays having the same peak wavelength, for example, a method in which the same kind (common) polymerization initiator is contained in each ink may be mentioned.

The first ink 1 and the second ink 2 each preferably have a viscosity of about 1 mPa · s to 1000 mPa · s in the vicinity of 25 ° C., which is room temperature, and is preferably 1 mPa · s to 50 mPa · s. More preferably, it is s or less. Further, when the droplet discharge head 9 is heated to 40 ° C., the viscosity of the first ink 1 at 40 ° C. is μ ₁ , and the viscosity of the second ink 2 at 40 ° C. is μ ₂ . It is preferable that ((μ ₁ −μ ₂ ) / μ ₁ ) × 100 = ± 10 [%] is satisfied.
Within the above range, when the first ink 1 and the second ink 2 are each ejected by the ink jet method, the ejection is stably performed.

Further, each of the first ink 1 and the second ink 2 preferably has a surface tension of about 5 mN / m or more and 200 mN / m or less in the vicinity of 25 degrees which is normal temperature, and is 10 mN / m or more and 40 mN or less. / M or less is more preferable. Further, when the droplet discharge head 9 is heated to 40 ° C., the surface tension of the first ink 1 at 40 ° C. is f ₁ , and the surface tension of the second ink 2 at 40 ° C. is f ₂ . It is preferable that ((f ₁ −f ₂ ) / f ₁ ) × 100 = ± 10 [%] is satisfied.

Within the above range, when the first ink 1 and the second ink 2 are each ejected by the ink jet method, the ejection is stably performed. Further, the wetting and spreading methods of the first ink 1 and the second ink 2 on the base material 101 exhibit the same behavior, and each ink spreads uniformly, resulting in uneven color in one printing layer 102. Can be prevented.
The ink viscosity and surface tension can be adjusted, for example, by adjusting the content of an additive such as a surfactant.

Next, the printing apparatus 700 loaded with the ink set 10 will be described.
[Printer]
As shown in FIGS. 7 to 13, the printing apparatus 700 discharges ultraviolet curable ink (first ink 1, second ink 2) in a loaded state and then applies ultraviolet light to the discharged ultraviolet curable ink. Irradiation is performed to cure the ultraviolet curable ink, and letters, numbers, various patterns, etc. are drawn on the substrate 101.

  As shown in FIGS. 1 to 3, the printing apparatus 700 includes a base 720 on which the base material 101 is placed, a transport device 730 that transports the base material 101 on the base 720 in the X direction in FIG. 1, A droplet discharge head 9 that discharges ink, a carriage 740 that supports the droplet discharge head 9, and a feeding device 750 that moves the carriage 740 in the Y direction orthogonal to the X direction are provided. In this embodiment, the substrate 101 and the carriage 740 (droplet ejection head 9) are moved relatively (reciprocated) in the X direction and the Y direction by the transport device 730 and the feeding device 750, respectively. An apparatus (moving means) is configured.

  The transfer device 730 includes a work stage 760 and a stage moving device 770 provided on a base 720. The work stage 760 is provided on the base 720 so as to be movable in the X direction by a stage moving device 770, and is conveyed from a conveying device (not shown) arranged on the upstream side of the printing device 700 in the manufacturing process. The base material 101 is held on the XY plane by, for example, a vacuum suction mechanism. The stage moving device 770 includes a mechanism such as a ball screw or a linear guide. The stage moving device 770 moves the work stage 760 in the X direction based on a stage position control signal indicating the X coordinate of the work stage 760 input from the control device 780. It is configured to move.

  The feeding device 750 that moves the carriage 740 has, for example, a bridge structure straddling the base 720, and includes a ball screw or linear guide mechanism in the Y direction and the Z direction orthogonal to the XY plane. Based on such a configuration, the feeding device 750 moves the carriage 740 in the Y direction based on the carriage position control signal indicating the Y coordinate and the Z coordinate of the carriage 740 input from the control device 780, and at the same time, Z It is also designed to move in the direction.

  As shown in FIGS. 2 and 3, the carriage 740 has a rectangular plate shape that is movably attached to the feeding device 750, and a plurality (six in this embodiment) of droplet discharge heads 9 are provided on the bottom surface 741 side. (9Y, 9C, 9M, 9K, 9Wa, 9Wb) are held in a state of being arranged along the Y direction. In this embodiment, the droplet discharge heads 9Wa, 9Y, 9C, 9M, 9K, and 9Wb are arranged in order from the left side in FIGS.

  The plurality of droplet discharge heads 9 (9Y, 9C, 9M, 9K, 9Wa, 9Wb) include a large number (plurality) of nozzles N (first nozzle N1, second nozzle N2), as will be described later. Ink is ejected as droplets L from each nozzle N based on drawing data and drive control signals input from the control device 780. The droplet discharge head 9Y discharges the first ink 1Y corresponding to Y (yellow), and the droplet discharge head 9C discharges the first ink 1C corresponding to C (cyan). The droplet discharge head 9M discharges the first ink 1M corresponding to M (magenta), and the droplet discharge head 9K discharges the first ink 1K corresponding to K (black). The second ink 2a corresponding to the droplet discharge head 9Wb and the transparent color (W) is discharged, and the second ink 2a corresponding to the transparent color (W) is discharged. 2b is discharged.

  A droplet discharge head 9Y corresponding to Y (yellow) is connected to a tank 11Y filled and stored with a first ink 1Y for Y (yellow) via a tube 710. Thus, the first ink 1Y for Y (yellow) is supplied from the tank 11Y to the droplet discharge head 9Y. The supplied first ink 1Y is ejected as droplets L from a plurality of first nozzles N1 provided on the lower surface of the droplet ejection head 9Y.

  Similarly, a tank 11C filled and stored with C (cyan) first ink 1C is connected to a droplet discharge head 9C corresponding to C (cyan) via a tube 710. Thus, the C (cyan) first ink 1C is supplied from the tank 11C to the droplet discharge head 9C. The supplied first ink 1C is discharged as a droplet L from a plurality of first nozzles N1 provided on the lower surface of the droplet discharge head 9C.

  Further, a tank 11M filled and stored with the first ink 1M for M (magenta) is connected to the droplet discharge head 9M corresponding to M (magenta) via a tube 710. As a result, the first ink 1M for M (magenta) is supplied from the tank 11M to the droplet discharge head 9M. The supplied first ink 1M is ejected as droplets L from a plurality of first nozzles N1 provided on the lower surface of the droplet ejection head 9M.

  Further, a tank 11K filled and stored with the first ink 1K for K (black) is connected to the droplet discharge head 9K corresponding to K (black) via a tube 710. Thus, the first ink 1K for K (black) is supplied from the tank 11K to the droplet discharge head 9K. The supplied first ink 1K is ejected as droplets L from a plurality of first nozzles N1 provided on the lower surface of the droplet ejection head 9K.

  Further, a tank 11Wa filled and stored with W (transparent) second ink 2a is connected to the droplet discharge head 9Wa corresponding to W (transparent) via a tube 710. Accordingly, the second ink 2a for W (transparent) is supplied from the tank 11Wa to the droplet discharge head 9Wa. The supplied second ink 2a is discharged as a droplet L from a plurality of second nozzles N2 provided on the lower surface of the droplet discharge head 9Wa.

  Further, a tank 11Wb filled and stored with W (transparent) second ink 2b is connected to the droplet discharge head 9Wb corresponding to W (transparent) via a tube 710. Accordingly, the second ink 2b for W (transparent) is supplied from the tank 11Wb to the droplet discharge head 9Wb. The supplied second ink 2b is discharged as a droplet L from a plurality of second nozzles N2 provided on the lower surface of the droplet discharge head 9Wb.

As described above, the droplet discharge heads 9Wa, 9Y, 9C, 9M, 9K, and 9Wb are arranged in this order along the Y direction. Accordingly, the first nozzles N1 corresponding to the respective colors are also arranged along the Y direction, and the second nozzles N2 are arranged on both sides thereof along the arrangement direction of the first nozzles N1.
With such an arrangement, as shown in FIGS. 7 to 13, when the droplet discharge heads 9Wa, 9Y, 9C, 9M, 9K, and 9Wb travel along the Y direction, that is, when they reciprocate, their forward paths Then, the first ink 1K is ejected from the first nozzle N1 of the droplet ejection head 9K onto the substrate 101, and then the droplet ejection head 9Wa located behind the droplet ejection head 9K in the traveling direction. The second ink 2a can be ejected from the second nozzle N2. Also in the return path, the first ink 1K is ejected from the first nozzle N1 of the droplet ejection head 9K onto the substrate 101, and then the droplet ejection located behind the droplet ejection head 9K in the traveling direction. The second ink 2b can be ejected from the second nozzle N2 of the head 9Wb.

  As described above, in the printing apparatus 700, the colored first ink 1 is reliably supplied in advance of the colorless and transparent second ink 2 in the progress in one direction, that is, in both the forward path and the return path. It can be discharged. This makes it possible to make the time from when the second ink 2 overlaps the first ink 1 on the substrate 101 until the ink is cured by the ultraviolet irradiation means 12a or 12b. Further, the time during which the first ink 1 remains in the liquid state and continues to contact the second ink 2 can be shortened as much as possible.

Next, the internal configuration of the droplet discharge head 9 (9Y, 9C, 9M, 9K, 9Wa, 9Wb) will be described with reference to FIG. The internal configurations of the droplet discharge heads 9Y, 9C, 9M, 9K, 9Wa, and 9Wb are the same.
FIG. 4 is a schematic configuration diagram of the droplet discharge head 9. 4A is a plan view of the droplet discharge head 9 as viewed from the work stage 760 side, FIG. 4B is a partial perspective view of the droplet discharge head 9, and FIG. It is a fragmentary sectional view for 1 nozzle.

  As shown in FIG. 4A, the droplet discharge head 9 has a plurality (for example, 180) of nozzles N arranged in a direction crossing the Y direction, in this embodiment, the X direction. N forms a nozzle array NA. In the figure, the nozzles N for one row are shown, but the number of nozzles and the number of nozzle rows provided in the droplet discharge head 9 can be arbitrarily changed. For example, a plurality of nozzle rows NA arranged in the X direction are arranged in the Y direction. A row may be provided.

  4B, the diaphragm 20 provided with the material supply hole 20a connected to the tube 710, the nozzle plate 21 provided with the nozzle N, the diaphragm 20 and the nozzle plate 21 A reservoir (liquid reservoir) 22, a plurality of partition walls 23, and a plurality of cavities (liquid chambers) 24 are provided. The surface (bottom surface) of the nozzle plate 21 is a nozzle surface 21 a on which a plurality of nozzles N are formed. On the vibration plate 20, piezoelectric elements (drive elements) PZ are arranged corresponding to the respective nozzles N. The piezoelectric element PZ is made of a piezo element, for example.

  The reservoir 22 is filled with ink supplied through the material supply hole 20a. The cavities 24 are formed so as to be surrounded by the diaphragm 20, the nozzle plate 21, and the pair of partition walls 23, and are provided in a one-to-one correspondence with the nozzles N. In addition, ink is introduced into each cavity 24 from the reservoir 22 through a supply port 24 a provided between the pair of partition walls 23.

  Further, as shown in FIG. 4C, the piezoelectric element PZ is obtained by sandwiching the piezoelectric material 25 between a pair of electrodes 26. When a drive signal is applied to the pair of electrodes 26, the piezoelectric material 25 contracts. It is comprised so that it may do. Therefore, the diaphragm 20 on which such a piezoelectric element PZ is disposed is integrally bent with the piezoelectric element PZ and bends outward (opposite the cavity 24) at the same time. The volume of 24 is increased.

  Therefore, the ink corresponding to the increased volume in the cavity 24 flows from the reservoir 22 through the supply port 24a. Further, when the application of the drive signal to the piezoelectric element PZ is stopped from such a state, both the piezoelectric element PZ and the diaphragm 20 return to the original shape, and the cavity 24 also returns to the original volume. As a result, the pressure of the ink in the cavity 24 rises, and the ink droplet L is ejected from the nozzle N toward the substrate 101.

In the droplet discharge head 9 having such a configuration, the bottom surface of the nozzle plate 21, that is, the formation surface (nozzle surface) NS of the nozzle N is lower than the bottom surface 741 of the carriage 740 as shown in FIG. As shown in FIG.
The droplet discharge heads 9Y, 9C, 9M, 9K, 9Wa, 9Wb, the tube 710, and the tanks 11Y, 11C, 11M, 11K, 11Wa, 11Wb are each provided with heating means (not shown) such as a heater. It has been. By the operation of the heating means, the ink is adjusted so that the ejection property from the droplet ejection head 9 is good.

As shown in FIGS. 2 and 3, on the carriage 740, the ultraviolet irradiation means 12a and the ultraviolet irradiation means 12b are arranged adjacent to each other across the six droplet discharge heads 9 arranged. That is, the ultraviolet irradiation means 12a and 12b are respectively arranged on both sides along the arrangement direction of the droplet discharge heads 9 arranged in the Y direction.
These ultraviolet irradiation means 12a and 12b are for curing ink, and in this embodiment, are constituted by a light source that emits ultraviolet rays. This light source emits ultraviolet light having a peak wavelength in the above-described range.

The control device 780 outputs a stage position control signal to the stage moving device 770, outputs a carriage position control signal to the feeding device 750, and further draws drawing data and data on a drive circuit board (not shown) of the droplet discharge head 9. A drive control signal is output. Accordingly, the control device 780 performs synchronous control of the positioning operation of the base material 101 by the movement of the work stage 760 and the positioning operation of the droplet discharge head 9 by the movement of the carriage 740 in order to move the base material 101 and the carriage 740 relative to each other. In addition, by causing the droplet discharge head 9 to perform a droplet discharge operation, the droplets of the radiation curable ink are arranged at predetermined positions on the substrate 101. The control device 780 also causes the ultraviolet irradiation means 12a and 12b to perform the ultraviolet irradiation operation separately from causing the droplet discharge head 9 to perform the droplet discharging operation.
The printing apparatus 700 is configured as described above.

Next, a method of manufacturing the printed material 100 using the loaded printing apparatus 700 and manufacturing a molded body from the printed material 100 will be described with reference to FIGS.
In the printing apparatus 700, when the colored print layer 102 is formed, the droplet discharge heads 9Y, 9C, 9M, and 9K are appropriately selected and used, but here, as an example, the droplet discharge head 9K is representative. Select and use.

[Manufacturing method (printing method)]
As shown in FIG. 7, the base material 101 is placed on a work stage 760. Then, the droplet discharge heads 9Y, 9C, 9M, 9K, 9Wa, 9Wb and the ultraviolet irradiation means 12a, 12b supported by the carriage 740 move together on the base material 101 in the right direction. .
Moreover, the ultraviolet irradiation means 12a is operating and irradiating with ultraviolet rays. This operating state is maintained while the ultraviolet irradiation means 12a is moving in the right direction, that is, during the forward path. On the other hand, the ultraviolet irradiation means 12b is stopped.

  As shown in FIG. 8, the droplet discharge head 9 </ b> K discharges the first ink 1 </ b> K as droplets L to a portion where the printing layer 102 of the substrate 101 is to be formed, and applies the droplets onto the substrate 101. At this time, as shown in FIG. 15A, a large number of first dots D1 formed by the landing of the droplets L of the first ink 1K are formed on the substrate 101, but are adjacent in the Y direction. The first dots D1 to be overlapped with each other while being slightly shifted in the direction.

Further, the first dots D1 adjacent in the X direction also overlap each other while being slightly shifted in that direction (see FIG. 15A). This is possible by appropriately setting the interval between the first nozzles N1 in the droplet discharge head 9K.
There is no particular limitation on the amount of misalignment between the first dots D1 in the X direction and the Y direction (inter-center distance p ₁ ). it can.
By applying the first ink 1K as described above, a layered first ink layer 111 composed of the first ink 1K is formed on the substrate 101.

As shown in FIG. 9, the first ink layer 111 is gradually cured from the left portion by the ultraviolet rays from the ultraviolet irradiation means 12a.
Further, when the droplet discharge head 9Wa approaches the first ink layer 111, the droplet discharge head 9W discharges and applies the second ink 2a as the droplet L onto the first ink layer 111. At this time, as shown in FIG. 15B, a large number of second dots D2 formed by the droplets L of the second ink 2a landing are formed in a staggered pattern (regular), but in the Y direction. The second dots D2 adjacent to each other are spaced apart in that direction. The separation distance in the Y direction (center distance p _2Y ) is not particularly limited, and is preferably twice the center distance p ₁ , for example, and the diameter of the second dot D2 is 50 μm. In this case, it can be set to 70 μm.

Further, the second dots D2 adjacent in the X direction are also separated from each other in the direction (see FIG. 15B). This is possible by appropriately setting the interval between the second nozzles N2 in the droplet discharge head 9Wa. The separation distance in the X direction (center distance p _2X ) is not particularly limited, and is preferably, for example, four times the center distance p ₁ , and the diameter of the second dot D2 is 50 μm. In this case, it can be 140 μm.

Then, as shown in FIG. 15C, the second dots D2 arranged in a staggered pattern in this way are in contact with the first ink layer 111 (first dots D1) from vertically above, respectively. Will be.
Further, as shown in FIG. 9, the second dots D2 arranged in a staggered pattern are cured by the ultraviolet rays from the ultraviolet irradiation means 12a in order from the one located on the left side.
The ink application and curing in the outward path are thus completed.

As shown in FIG. 10, in the return path, the droplet discharge heads 9Y, 9C, 9M, 9K, 9Wa, and 9Wb supported by the carriage 740 and the ultraviolet irradiation means 12a and 12b are collectively placed on the substrate 101. Move to the left.
Moreover, the ultraviolet irradiation means 12b is operating and irradiating ultraviolet rays. This operating state is maintained while the ultraviolet irradiation means 12b is traveling. On the other hand, the ultraviolet irradiation means 12a is stopped.

As shown in FIG. 11, the droplet discharge head 9 </ b> K discharges and applies the first ink 1 </ b> K as droplets L on the cured first ink layer 111. At this time, as in the forward path, a large number of first dots D1 are formed, but the first dots D1 adjacent in the Y direction overlap each other while being slightly shifted in that direction (FIG. 15A). reference). Further, the first dots D1 adjacent in the X direction also overlap each other while being slightly shifted in that direction (see FIG. 15A).
By such application of the first ink 1K, a layered first ink layer 112 composed of the first ink 1K is further formed on the first ink layer 111 formed in the forward path. The first ink layer 112 also covers the cured second dots D2 on the first ink layer 111.

As shown in FIG. 12, the first ink layer 112 is gradually cured from the right portion by the ultraviolet rays from the ultraviolet irradiation means 12b.
Further, when the droplet discharge head 9Wb reaches the first ink layer 112, the droplet discharge head 9Wb discharges and applies the second ink 2b as the droplet L onto the first ink layer 112. In this case as well, as in the forward path, a large number of second dots D2 are formed in a staggered pattern, but the second dots D2 adjacent in the Y direction are separated from each other in the direction (FIG. 15). (See (b)). Further, the second dots D2 adjacent in the X direction are also separated from each other in the direction (see FIG. 15B). The second dots D2 arranged in a staggered pattern in this way come into contact with the first ink layer 112 from vertically above (see FIGS. 12 and 15C).
Also, as shown in FIG. 12, the second dots D2 arranged in a staggered pattern are cured by the ultraviolet rays from the ultraviolet irradiation means 12b in order from the one located on the right side.
Then, as shown in FIG. 13, the application and curing of the ink in the return path are completed, and the printed matter 100 is obtained.

As shown in FIG. 14, the printed material 100 is machined as described above to obtain a molded body 200.
Through such a process, on the base material 101, the first dots D1 are arranged “densely” and the second dots D2 are arranged “sparsely”. As a result, in the printing layer 102, the total amount of the first ink 1 is larger than the total amount of the second ink 2. The total amount of the second ink 2 is preferably 3 to 25% of the total amount of the first ink 1, and more preferably 5 to 10%.

  As described above, the first cured product obtained by curing the first ink 1 is superior in stretchability to the second cured product obtained by curing the second ink 2. For example, when the second ink 2 is excessively applied, that is, when the magnitude relationship between the total amount of the first ink 1 and the total amount of the second ink 2 is reversed, the stretchability may be impaired. . As a result, it is considered that the printed layer 102 has poor stretchability. However, such a problem can be reliably prevented by the magnitude relationship of the total amount.

  Further, through the above process, in the forward path, the first ink layer 111 and each of the second dots D2 are partially mixed with each other before the ink is cured at the boundary portion, but the remaining portion. So no mixing is done. Even in the return pass, the first ink layer 112 and each of the second dots D2 are partially mixed before the ink is cured at the boundary portion, but not mixed in the remaining portion. That is, a part of the second ink 2 is mixed with the first ink 1 in both the forward path and the return path, but the remaining part is prevented from being mixed with the first ink 1.

  By the way, in manufacturing the molded body 200, when the printed material 100 is machined, a change occurs in the internal stress due to the processing in the portion of the printed layer 102 where the processing is performed and its peripheral portion, There is concern that problems such as cracks and peeling will occur. However, such a problem is prevented from occurring in the molded body 200. This will be described below.

As described above, the print layer 102 is a layer formed by curing the first ink 1 containing a pigment as a colorant and the colorless and transparent second ink 2. The printed layer 102 after the ink curing has a first characteristic and a second characteristic.
Here, let us consider a first case where only the first ink 1 in which the print layer 102 is cured and a second case where only the second ink 2 in which the print layer 102 is cured are considered.

  In the first case, using a TMA device, a constant pressure is applied to the printing layer 102 in an environment of 30 ° C., and the maximum displacement amount (dent amount) at that time and the displacement recovery when the pressure is released The amount (recovery amount) was measured several times. The recovery rate was calculated by dividing the displacement recovery amount by the maximum displacement amount. As a result, it was found that the recovery rate averaged 30% (error range ± 5%) although it depends on the test conditions such as the pressure level (see FIG. 6). From this, in the first case, it can be said that the printed layer 102 is a layer that is easily plastically deformed, and when machining is performed, problems such as cracking and peeling occur.

  On the other hand, in the second case, it was found that the average recovery rate was 80% (error range ± 10%) (see FIG. 6). From this, it can be said that in the second case, the print layer 102 is a layer that is easily elastically deformed. Note that the second ink 2 is colorless and transparent, and is not used alone, so the evaluation when the printing layer 102 is machined is omitted.

  However, in the present invention, unlike the second case, the first case is composed of the first ink 1 and the second ink 2 in which the printing layer 102 is cured, and the recovery rate depends on the mixing ratio and the density. Was found to have an average of 55% (error range ± 3%) (see FIG. 6). As is apparent from FIG. 6, in the present invention, it can be said that the printed layer 102 is a layer having intermediate properties between the first case and the second case. In the printing layer 102, even if the printing layer 102 is subjected to machining due to a synergistic effect of the effect of being excellent in stretchability (by the first property) and the effect of being rich in elasticity (by the second property). It is possible to reliably prevent problems such as cracks and peeling.

  In this way, the colored first ink 1 is mixed (superposed) with the colorless and transparent second ink 2 in which the color change of the first ink 1 is prevented or suppressed, and the ink has the first characteristic. And the second characteristic, the durability of the printing layer 102 is improved. Thereby, when processing the printed matter 100 which has the printing layer 102 (application surface) and manufacturing the molded object 200, it is excellent in the workability. For example, when the molded body 200 is a speedometer of an automobile, the printing layer 102 can be stored for a long period of time in various environments such as an internal temperature of 50 ° C. or more under a hot summer sun, while maintaining high quality. .

  In the printing layer 102, the total mass of the (b-1) polymerizable compound contained in the first ink 1 is equal to the total mass of the (b-2) polymerizable compound contained in the second ink 2. It is preferable that it is the same or larger (for example, 1.1 times or more). Thereby, when the printed material 100 is machined (manufactured the molded body 200), the printed layer 102 is more reliably prevented from being cracked or peeled, and the printed layer 102 is further enhanced in durability.

Further, unlike the present invention, a case will be considered where these inks are mixed in advance and applied to the substrate 101 before the first ink 1 and the second ink 2 are applied to the substrate 101.
In this case, as a result, the printed layer 102 does not exhibit a synergistic effect between the effect due to the first characteristic and the effect due to the second characteristic, and problems such as cracking and peeling occur. It is expected that the cause of the former is that if the inks are mixed in advance, the dispersion stability of the pigment in the ink is destroyed.
Thus, the first ink 1 and the second ink 2 are mixed for the first time on the substrate 101, the first ink 1 has the first characteristic, and the second characteristic has the second ink. 2 must have.

Second Embodiment
FIG. 16 is a plan view showing a state (second embodiment) in which the first ink and the second ink are respectively applied to the print medium using the printing apparatus of the present invention.
Hereinafter, the second embodiment of the printing method, printing apparatus, printed matter, and molded body of the present invention will be described with reference to this figure. Description is omitted.
This embodiment is the same as the first embodiment except that the application state of the second ink is different.

As shown in FIG. 16B, a large number of second dots D2 are arranged in a matrix, that is, in a lattice shape (periodic), and the second dots D2 adjacent in the Y direction are Separated in the direction. The second dots D2 adjacent in the X direction are also separated from each other in that direction.
Note that the arrangement of the first dots D1 shown in FIG. 16A is the same as the arrangement of the first dots D1 shown in FIG.
Then, as shown in FIG. 16C, each second dot D2 comes into contact with the first ink layer 111 (first dot D1) from vertically above.
Even when the printing layer 102 having such an arrangement of ink is machined, it is possible to reliably prevent problems such as cracks and peeling from occurring in the printing layer 102.

<Third Embodiment>
FIG. 17 is a plan view showing a state (third embodiment) in which the first ink and the second ink are respectively applied to the print medium using the printing apparatus of the present invention.
Hereinafter, the third embodiment of the printing method, printing apparatus, printed matter, and molded product of the present invention will be described with reference to this drawing. Description is omitted.

This embodiment is the same as the first embodiment except that the application state of the second ink is different.
As shown in FIG. 17B, a large number of second dots D2 are randomly arranged, and adjacent second dots D2 are separated from each other.
The arrangement of the first dots D1 shown in FIG. 17A is the same as the arrangement of the first dots D1 shown in FIG.

Then, as shown in FIG. 17C, each second dot D2 comes into contact with the first ink layer 111 (first dot D1) from vertically above.
Even when the printing layer 102 having such an arrangement of ink is machined, it is possible to reliably prevent problems such as cracks and peeling from occurring in the printing layer 102.
Also, with such an arrangement, the second dots D2 are difficult to visually recognize, i.e., become inconspicuous, and the aesthetics of the printed layer 102 are improved.

<Fourth embodiment>
FIG. 18 is a plan view showing a state (fourth embodiment) in which the first ink and the second ink are respectively applied to the print medium using the printing apparatus of the present invention.
Hereinafter, the fourth embodiment of the printing method, printing apparatus, printed matter, and molded body of the present invention will be described with reference to this figure. Description is omitted.
The present embodiment is the same as the first embodiment except that the application states of the first ink and the second ink are different.

As shown in FIG. 18, in the portion to be the printing layer 102, that is, in the region to be printed on the substrate 101, the first ink 1 of four colors (Y: C: M: K = 20 in the illustrated configuration). : 50: 100: 30) and a certain amount of colorless and transparent second ink 2 is mixed with the first ink 1 of each color.
As a result, the ratio between the first ink 1 (1Y, 1C, 1M, 1K) and the second ink 2 is constant at a plurality of different locations on the printing layer 102 (on the base material 101). . Thereby, the influence of the 2nd ink 2 with respect to the 1st ink 1 of each color can be made constant, and the extreme discoloration by the 2nd ink 2 of the 1st ink 1 of each color can be prevented reliably.

<Fifth Embodiment>
FIG. 19 is a plan view showing a state (fifth embodiment) in which the first ink and the second ink are respectively applied to the print medium using the printing apparatus of the present invention.
Hereinafter, the fifth embodiment of the printing method, printing apparatus, printed matter, and molded body of the present invention will be described with reference to this drawing. Description is omitted.
This embodiment is the same as the first embodiment except that the application state of the second ink is different.

For example, when forming the printing layer 102 having a desired stretchability, the total amount of the second ink 2 may be known in advance.
In such a case, as shown in FIG. 19, in the portion that becomes the printing layer 102, the first ink 1 of four colors (Y: C: M: K = 20: 50: 100: 30 in the illustrated configuration). A predetermined amount (50% in the illustrated configuration) of colorless and transparent second ink 2 can be mixed in advance with the first ink 1 of each color.
Thereby, the printing layer 102 which has desired stretchability can be obtained reliably.

<Sixth Embodiment>
FIG. 20 is a plan view showing a state (sixth embodiment) in which the first ink and the second ink are respectively applied to the print medium using the printing apparatus of the present invention.
Hereinafter, the sixth embodiment of the printing method, printing apparatus, printed matter, and molded product according to the present invention will be described with reference to this drawing. Description is omitted.
This embodiment is the same as the fourth embodiment except that the application state of the second ink is different.

As shown in FIG. 20, in the portion that becomes the printing layer 102, the first ink 1 of four colors (Y: C: M: K = 20: 50: 100: 30 in the illustrated configuration) and three colors of A certain amount of colorless and transparent second ink 2 is mixed with the first ink 1 (1C, 1M, 1K).
Thereby, in the printing layer 102 in which the second ink 2 is mixed, that is, in a plurality of different locations of the local printing layer 102, the first ink 1C, 1M, 1K and the second ink 2 are all present. The ratio to is constant. Accordingly, the influence of the second ink 2 on the first inks 1C, 1M, and 1K is made constant, and the extreme discoloration of the first inks 1C, 1M, and 1K by the second ink 2 is surely prevented. Can do.

<Seventh embodiment>
FIG. 21 is a plan view showing a state (seventh embodiment) in which the first ink and the second ink are respectively applied to the print medium using the printing apparatus of the present invention.
Hereinafter, the seventh embodiment of the printing method, printing apparatus, printed matter, and molded body of the present invention will be described with reference to this drawing. However, the difference from the above-described embodiment will be mainly described, and the same matters will be described. Description is omitted.
This embodiment is the same as the fifth embodiment except that the application state of the second ink is different.

For example, there is a case where the total amount of the second ink 2 can be grasped in advance when part of the print layer 102 having a desired stretchability is formed.
In such a case, as shown in FIG. 21, in the portion that becomes the printing layer 102, the first ink 1 of four colors (Y: C: M: K = 20: 50: 100: 30 in the illustrated configuration). In addition, a predetermined amount (50% in the illustrated configuration) of the colorless and transparent second ink 2 can be mixed in advance with the first ink 1 (1C, 1M, 1K) of the three colors.
As a result, it is possible to reliably obtain the printed layer 102 that partially has the desired stretchability.

<Eighth Embodiment>
FIG. 22 is a table as a calibration curve stored in the printing apparatus (eighth embodiment) of the present invention.
Hereinafter, the eighth embodiment of the printing method, the printing apparatus, the printed matter, and the molded body of the present invention will be described with reference to this drawing. However, the difference from the above-described embodiment will be mainly described, and the same matters will be described. Description is omitted.
The present embodiment is the same as the first embodiment except that the configuration of the printing apparatus is different.

In the present embodiment, the control device 780 of the printing apparatus 700 stores a table shown in FIG. 22 as a calibration curve. This table shows the relationship between input information and output information. The input information is displayed by the material of the base material 101 (material 1, material 2, material 3,...) And the first ink 1 and the second ink 2 mixed on the base material 101. Color (display color 1, display color 2, display color 3,...). The output information is the mixing ratio (Y: C: M: K: W) between the first ink 1 and the second ink 2. A plurality of such tables are prepared according to the color of the base material 101.
And the control apparatus 780 can determine output information from input information based on this table. Depending on the material and color of the base material 101, the print layer 102 formed on the base material 101 can be reliably reproduced in a desired color.
In addition to the table, for example, an arithmetic expression can be used as the calibration curve.

The printing method, the printing apparatus, the printed material, and the molded body of the present invention have been described above with respect to the illustrated embodiment. It can be replaced with any structure capable of performing the same function. Moreover, arbitrary components may be added.
In addition, the printing method, printing apparatus, printed matter, and molded body of the present invention may be a combination of any two or more configurations (features) of the above embodiments.

In each of the above embodiments, the first ink of the first ink and the second ink contains the pigment as the colorant. However, the present invention is not limited to this, and for example, the second ink The ink may contain a pigment as a colorant.
In addition, the ink set has the first ink of four colors in each of the embodiments described above, but is not limited to this. For example, the first ink of one color, two colors, three colors, or five colors is used. It may have.
Further, when machining a printed material, the printed material may be processed while being heated.

1, 1Y, 1C, 1M, 1K... First ink 1 '... Film 111, 112... First ink layer 2, 2a, 2b... Second ink 9, 9Y, 9C, 9M, 9K , 9Wa, 9Wb: Droplet ejection head 10: Ink set 11Y, 11C, 11M, 11K, 11Wa, 11Wb ... Tank 12a, 12b ... Ultraviolet irradiation means 20 ... Vibrating plate 20a ... Material supply hole 21 ... Nozzle Plate 21a: Nozzle surface 22 ... Reservoir 23 ... Bulkhead 24 ... Cavity 24a ... Supply port 25 ... Piezoelectric material 26 ... Electrode 100 ... Printed material 101 ... Base material (substrate) 102 ... Printed layer 103 ... Bottomed cylinder 104 ... Opening 200 ... Molded body 300 ... Base material 500 ... UV irradiation device 600 ... Electric heater 700 ... Printing device 710 ... Tube 720 ... Base 730 ... Conveying device 740 ... Carriage 741 ... Bottom 750 ... Feeding device 760 ... Work stage 770 ... Stage moving device 780 ... Control device D1 ... First dot D2 ... Second dot L ... ... Droplet N ... Nozzle N1 ... First nozzle N2 ... Second nozzle NA ... Nozzle array NS ... Formation surface (nozzle surface) PZ ... Piezoelectric element (drive element) φd ₁ ... Diameter △ d ₁ ... Stretching amount (stretching length) L ₃ ... Length p ₁ , p _2X , p _2Y ... Center distance t ₁ , t ₃ ... Thickness w ₃ ... Width

Claims (21)

Drops of a first ink containing a first polymerization initiator and a first polymerizable compound and a second ink containing a second polymerization initiator and a second polymerizable compound onto a print medium A printing method for applying and printing on the print medium after being cured,
When the first ink is cured to form a film having a thickness of 5 μm, the first ink is stretched by 70% or more when the film is stretched in an environment of 150 ° C.,
The glass transition point of the cured product obtained by curing the second ink is higher than the glass transition point of the cured product obtained by curing the first ink.
When applying the first ink and the second ink onto the print medium, the first dots formed by the droplets of the first ink landing on the print medium; and the second dots Applying each of the droplets such that a plurality of droplets of ink are in contact with a plurality of second dots formed on the print medium, but are adjacent to each other. A printing method characterized by the above.   The printing method according to claim 1, wherein the total amount of the first ink is larger than the total amount of the second ink on the print medium.   The glass transition point of the cured product obtained by curing the first ink is less than 100 ° C, and the glass transition point of the cured product obtained by curing the second ink is 100 ° C or higher. The printing method as described in.   4. The difference between the glass transition point of a cured product obtained by curing the first ink and the glass transition point of a cured product obtained by curing the second ink is 300 ° C. or less. 5. The printing method as described in.   Of the total mass of the first polymerizable compound, the monofunctional polymerizable compound is 65% by mass or more, and among the total mass of the second polymerizable compound, the polyfunctional polymerizable compound is 50% by mass or more. The printing method according to any one of claims 1 to 4.   The printing method according to claim 1, wherein the first ink and the second ink are each cured by being irradiated with ultraviolet rays having the same wavelength.   The first ink and the second ink are each cured by being irradiated with ultraviolet rays, and the wavelength of the ultraviolet rays is 350 nm or more and 450 nm or less. The printing method described.   The printing method according to claim 1, wherein each of the first ink and the second ink has a viscosity at room temperature of 1 mPa · s to 1000 mPa · s. When the viscosity of the first ink in a 40 ° C. environment is μ ₁ and the viscosity of the second ink in a 40 ° C. environment is μ ₂ , ((μ ₁ −μ ₂ ) / μ ₁ 9) The printing method according to any one of claims 1 to 8, wherein x100 = ± 10 [%] is satisfied.   10. The printing method according to claim 1, wherein each of the first ink and the second ink has a surface tension at room temperature of 5 mN / m or more and 200 mN / m or less. When the surface tension of the first ink at 40 ° C. is f ₁ and the surface tension of the second ink at 40 ° C. is f ₂ , ((f ₁ −f ₂ ) / f ₁ ) × 100 = The printing method according to claim 1, wherein ± 10 [%] is satisfied.   The printing method according to claim 1, wherein the first ink or the second ink contains a pigment as a colorant.   The printing method according to claim 1, wherein the second ink is substantially colorless.   The printing method according to claim 1, wherein a ratio of the first ink to the second ink is constant at a plurality of different locations on the print medium.   The printing method according to claim 1, wherein the amount of the second ink is constant and the amount of the first ink changes at a plurality of different locations on the print medium. Drops of a first ink containing a first polymerization initiator and a first polymerizable compound and a second ink containing a second polymerization initiator and a second polymerizable compound onto a print medium Is a printing apparatus that applies and then cures and prints on the print medium,
When the first ink is cured to form a film having a thickness of 5 μm, the first ink is stretched by 70% or more when the film is stretched in an environment of 150 ° C.,
The glass transition point of the cured product obtained by curing the second ink is higher than the glass transition point of the cured product obtained by curing the first ink.
When applying the first ink and the second ink onto the print medium, the first dots formed by the droplets of the first ink landing on the print medium; and the second dots Applying each of the droplets such that a plurality of droplets of ink are in contact with a plurality of second dots formed on the print medium, but are adjacent to each other. A printing apparatus characterized by the above. A droplet discharge head having at least one first nozzle that discharges the first ink as droplets, and at least one second nozzle that discharges the second ink as droplets;
A moving means for relatively reciprocating the droplet discharge head and the printing medium,
The droplet discharge head is configured such that the second nozzle is positioned behind the first nozzle in the direction of travel, and the first nozzle is placed on the print medium from the first nozzle when the head is advanced. The printing apparatus according to claim 16, wherein ink is ejected, and further, the second ink is ejected from the second nozzle onto the first ink on the print medium. The first ink contains a pigment as a colorant,
The droplet discharge head discharges the plurality of first inks having different colors of the pigment, respectively, and a plurality of the first nozzles arranged along the traveling direction of the droplet discharge head;
18. The printing apparatus according to claim 17, further comprising two second nozzles disposed on a front side and a rear side in a traveling direction of the droplet discharge head with respect to the plurality of first nozzles.   Input information having color and material of the print medium and display colors displayed by the first ink and the second ink mixed on the print medium; the first ink and the second 19. The printing according to claim 18, further comprising: a calibration curve indicating a relationship with output information having a mixing ratio with the ink, wherein the output information is determined from the input information based on the calibration curve. apparatus. Print media;
Drops of a first ink containing a first polymerization initiator and a first polymerizable compound and a second ink containing a second polymerization initiator and a second polymerizable compound onto a print medium And having a printed layer obtained by curing as
When the first ink is cured to form a film having a thickness of 5 μm, the first ink is stretched by 70% or more when the film is stretched in an environment of 150 ° C.,
The glass transition point of the cured product obtained by curing the second ink is higher than the glass transition point of the cured product obtained by curing the first ink.
When applying the first ink and the second ink onto the print medium, the first dots formed by the droplets of the first ink landing on the print medium; and the second dots Applying each of the droplets such that a plurality of droplets of ink are in contact with a plurality of second dots formed on the print medium, but are adjacent to each other. Printed matter characterized by. A printing medium, a first ink containing a first polymerization initiator and a first polymerizable compound, and a second ink containing a second polymerization initiator and a second polymerizable compound A molded product obtained by applying machining to a printed matter having a printed layer that is applied as droplets and then cured.
When the first ink is cured to form a film having a thickness of 5 μm, the first ink is stretched by 70% or more when the film is stretched in an environment of 150 ° C.,
The glass transition point of the cured product obtained by curing the second ink is higher than the glass transition point of the cured product obtained by curing the first ink.
When the first ink and the second ink are applied on the print medium, the first dots formed by the droplets of the first ink landing on the print medium, and the second Each of the droplets is applied so that the plurality of droplets of ink contact with the plurality of second dots formed on the print medium, but the adjacent second dots are separated from each other. A molded product characterized by that.

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