JP6935882B2 - Inkjet recording method and manufacturing method of laminated printed matter - Google Patents

Description

The present disclosure relates to an inkjet recording method and a method for producing a laminated printed matter.

Examples of an image recording method for forming an image on a recording medium such as paper based on an image data signal include an electrophotographic method, a sublimation type and a molten type thermal transfer method, and an inkjet method.
In the inkjet method, the printing apparatus is inexpensive, a plate is not required at the time of printing, and the ink composition is ejected only to the required image portion to form an image directly on the recording medium. It can be used efficiently, and the running cost is low, especially in the case of small lot production. Furthermore, it has less noise and is excellent as an image recording method, and has been attracting attention in recent years.
Among them, the inkjet recording ink composition (radiocurable inkjet recording ink composition) that can be cured by irradiation with ultraviolet rays or the like cures most of the components of the ink composition by irradiation with radiation such as ultraviolet rays. It is an excellent method in that it can be printed on various recording media because it is excellent in drying property as compared with a solvent-based ink composition and the image is less likely to bleed.

Examples of the method using the conventional inkjet method include the methods described in Patent Documents 1 to 3.
Patent Document 1 includes a metal-based base material that forms an uneven pattern having a height difference of more than 1.5 mm, and a building board on which an ink receiving layer formed of a resin composition is arranged. After surface treatment with a flame generated by burning flammable gas injected from a burner flame port having a length of 1 to 8 mm at a ^{flow rate of 30 to 200 L / min per 1 cm 2 of the burner flame port, active photocuring} A method for manufacturing a decorative building board, including inkjet printing with a mold ink, is disclosed.

Patent Document 2 describes a method of imaging a flat plate printing member: (a) a soluble top layer having a first flat plate printing affinity and a underlying layer having a first flat plate printing affinity as well. In the step of providing the printing member including the above, the top layer responds to the imaging fluid to an insoluble state having a second plate printing affinity opposite to that of the first plate printing affinity. (B) A step of supplying an imaging fluid in an image pattern, in which the imaging fluid chemically reacts with the top layer to cause the phase change; (c). The step of exposing the printing member to a solvent, in which the solvent dissolves the soluble portion of the top layer; and (d) the step of removing the soluble portion of the top layer, thereby the step. A method is disclosed that includes a step in which an imaged flat plate printing pattern is generated on a printing member.

In Patent Document 3, as step a, an undercoat composition is applied to a recording medium to provide an undercoat layer, and as step b, an image forming step of ejecting an ink composition onto the undercoat layer to form an image is provided. And, as step c, a curing step of irradiating the undercoat layer and the ink composition with active light to cure them is included in this order, and the undercoat composition includes a compound having an isocyanate group, a radically polymerizable monomer, and a radical. An inkjet recording method is disclosed, which comprises a polymerization initiator, and the ink composition contains a radically polymerizable monomer, a radical polymerization initiator, and a colorant.

JP-A-2017-164685 Japanese Patent Application Laid-Open No. 2008-515687 Japanese Unexamined Patent Publication No. 2016-60049

An object to be solved by one embodiment of the present invention is to provide an inkjet recording method having excellent heat-resistant adhesion to the obtained printed matter.
Another problem to be solved by another embodiment of the present invention is to provide a method for producing a laminated printed matter using the printed matter obtained by the above-mentioned inkjet recording method.

Means for solving the above problems include the following aspects.
<1> A step of preparing a laminate having an aluminum foil base material and a first undercoat layer on the aluminum foil base material, a second undercoat composition on the first undercoat layer in the laminate. The step of forming the undercoat layer, the step of ejecting the ink composition onto the second undercoat layer by the inkjet method, and the ejected ink composition in an atmosphere having an oxygen concentration of 0.1% by volume or less. The first undercoat layer includes a heat-curable resin, an acrylic resin, and a fibrous radical resin, and includes a step of irradiating an ultraviolet light emitting diode with an integrated light amount of 400 mJ / cm ^{2 or more to cure the product.} The second undercoat composition contains a compound having an isocyanate group, a radically polymerizable monomer, and a radical polymerization initiator, and the ink composition is an inkjet containing a radically polymerizable monomer, a radical polymerization initiator, and a colorant. Recording method.
<2> In <1>, the thermosetting resin contained in the first undercoat layer contains a resin obtained by curing at least one resin selected from the group consisting of epoxy resins and melamine resins. The inkjet recording method described.
<3> The inkjet recording method according to <1> or <2>, wherein the thermosetting resin contained in the first undercoat layer contains a resin obtained by curing an epoxy resin and a melamine resin.
<4> The content of the polyfunctional ethylenically unsaturated compound with respect to the total content of the radically polymerizable monomer in the second undercoat composition is 70% by mass or more and is
The inkjet recording according to any one of <1> to <3>, wherein the content of the polyfunctional ethylenically unsaturated compound with respect to the total content of the radically polymerizable monomer in the ink composition is 70% by mass or more. Method.
<5> A step of irradiating the second undercoat layer with ultraviolet rays to semi-cure the second undercoat layer is included between the step of forming the second undercoat layer and the step of ejecting the ink composition <1> to <4>. The inkjet recording method according to any one of the above.
<6> In the step of curing, the steps of irradiating the ink composition with ultraviolet rays and semi-curing the ink composition are included between the steps of ejecting the ink composition and the step of irradiating with ultraviolet rays. The inkjet recording method according to any one.
<7> The inkjet recording method according to any one of <1> to <6>, which forms an image including a barcode in the step of ejecting the ink composition.
<8> The inkjet recording method according to any one of <1> to <7>, wherein the first undercoat layer further contains a colorant.
<9> A method for producing a laminated printed matter, which comprises a step of heat-bonding the printed matter obtained by the inkjet recording method according to any one of <1> to <8> and a resin base material.
<10> The method for producing a laminated printed matter according to <9>, wherein heat of 160 ° C. or higher is applied to the bonded portion in the bonding step.

According to one embodiment of the present invention, it is possible to provide an inkjet recording method having excellent heat-resistant adhesion to the obtained printed matter.
Further, according to another embodiment of the present invention, it is possible to provide a method for producing a laminated printed matter using the printed matter obtained by the above-mentioned inkjet recording method.

It is a schematic diagram which shows an example of the inkjet recording apparatus preferably used for this disclosure. It is a figure which shows the bar code drawn in an Example. It is a schematic diagram of the die of the lattice pattern used for the blister packaging in the Example.

The contents of the present disclosure will be described in detail below. The description of the constituent elements described below may be based on the representative embodiments of the present disclosure, but the present disclosure is not limited to such embodiments.
The description of the constituents described below may be based on typical embodiments of the present invention, but the disclosure is not limited to such embodiments.
Regarding the notation of a group (atomic group) in the present specification, the notation that does not describe substitution or non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Further, the "organic group" in the present specification means a group containing at least one carbon atom.
In the present specification, "~" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.

In the present specification, (meth) acrylate represents acrylate and methacrylate, and (meth) acrylic represents acrylic and methacryl.
In the present specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of the resin component are referred to as GPC (Gel Permeation Chromatography) apparatus (Tosoh Corporation). GPC measurement by HLC-8120 GPC (manufactured by HLC-8120 GPC) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Toso Co., Ltd., column temperature: 40 ° C., flow velocity: 1.0 mL / min, Detector: Defined as a polystyrene-equivalent value by a differential index detector.

In the present specification, the amount of each component in the composition is the total amount of the plurality of applicable substances present in the composition unless otherwise specified, when a plurality of the substances corresponding to each component are present in the composition. means.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
As used herein, the term "total solid content" refers to the total mass of the components excluding the solvent from the total composition of the composition. Further, the "solid content" is a component excluding the solvent as described above, and may be, for example, a solid or a liquid at 25 ° C.
In the present specification, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Further, in the present specification, a combination of two or more preferred embodiments is a more preferred embodiment.

(Inkjet recording method)
The inkjet recording method according to the present disclosure is a step of preparing a laminate having an aluminum foil base material and a first undercoat layer on the aluminum foil base material, and a second step on the first undercoat layer in the laminate. A step of forming a second undercoat layer with the undercoat composition, a step of ejecting the ink composition onto the second undercoat layer by an inkjet method, and an oxygen concentration of 0.1% by volume of the ejected ink composition. In the following atmosphere, the first undercoat layer includes a step of irradiating an ultraviolet light emitting diode with an integrated light amount of 400 mJ / cm ² or more to cure it, and the first undercoat layer is a heat-curable resin, an acrylic resin, and a fibrous element. The second undercoat composition contains a resin, the second undercoat composition contains a compound having an isocyanate group, a radical polymerizable monomer, and a radical polymerization initiator, and the ink composition contains a radical polymerizable monomer, a radical polymerization initiator, and a radical polymerization initiator. , Contains colorants.
In addition, the inkjet recording method according to the present disclosure is suitable for blister packaging printing, and is particularly suitable for printing including a barcode in blister packaging.

In particular, in blister packaging printing in which an aluminum foil base material is used and wrapped in a pocket of a tablet or the like, the present inventors have insufficient heat-resistant adhesion of the obtained printed matter when an image is formed by a conventional inkjet recording method. I found that there was a problem with. The present inventor has studied diligently to obtain a first undercoat layer containing a thermosetting resin, an acrylic resin, and a fibrous resin, as well as a compound having an isocyanate group, a radically polymerizable monomer, and radical polymerization. It has been found that the obtained printed matter is excellent in heat adhesion by providing a second undercoat layer formed by the second undercoat composition containing an initiator and ejecting the ink composition onto the second undercoat layer to form an image. rice field.
The detailed mechanism is unknown, but it is estimated as follows.
Adhesion to the aluminum foil base material cannot be obtained only with the undercoat layer formed by the radically polymerizable monomer and the undercoat composition containing the radical polymerization initiator.
A first undercoat layer containing a thermosetting resin, an acrylic resin, and a fibrous resin is provided, and the ink composition is further integrated by an ultraviolet light emitting diode in an atmosphere having an oxygen concentration of 0.1% by volume or less. By irradiating with ultraviolet rays having a light amount of 400 mJ / cm ² or more and curing the ink composition, the adhesion between the first undercoat layer and the cured ink composition is improved but insufficient, and bleeding of the ink composition occurs. Therefore, a compound having an isocyanate group is added to a second undercoat composition containing a radically polymerizable monomer and a radical polymerization initiator, and a second undercoat layer is provided, thereby passing through the second undercoat layer. The adhesion between the ink film and the first undercoat layer is improved and bleeding of the ink composition does not occur. Further, by curing the ink composition with the above oxygen concentration and integrated light amount, the adhesion of the ink film is improved. In order to improve it, it is estimated that the obtained printed matter has excellent heat-resistant adhesion.

Hereinafter, the present disclosure will be described in detail.

<Step of preparing a laminate having an aluminum foil base material and a first undercoat layer on the aluminum foil base material>
The inkjet recording method according to the present disclosure is a step of preparing a laminate having an aluminum foil base material and a first undercoat layer on the aluminum foil base material (also simply referred to as a “step of preparing a laminate”). The first undercoat layer contains a heat-curable resin, an acrylic resin, and a fibrous resin.

<< Aluminum foil base material >>
The aluminum foil base material used in the inkjet recording method according to the present disclosure may be a foil-like base material having an aluminum content of 50% by mass or more, preferably 90% by mass or more, and is a known aluminum foil base material. Can be used.
The material of the aluminum foil base material may be aluminum alone or an aluminum alloy.
Further, the aluminum foil base material may be surface-treated by a known method.
The thickness of the aluminum foil base material is preferably 1 μm to 100 μm, more preferably 5 μm to 60 μm, and particularly preferably 10 μm to 40 μm.
The material and thickness of the aluminum foil base material may be appropriately selected depending on the intended use of the printed matter to be produced.

<< First undercoat layer >>
The first undercoat layer contains a thermosetting resin, an acrylic resin, and a fibrin-based resin.
The thermosetting resin contained in the first undercoat layer may be any resin obtained by curing a thermosetting resin, and a resin obtained by curing a known thermosetting resin can be used.
Examples of the thermosetting resin include vinyl chloride-vinyl acetate copolymer resin, polyvinyl chloride resin, epoxy resin, urethane resin, melamine resin, ester resin and the like.
The thermosetting resin may be contained alone or in combination of two or more.
Among them, as the thermosetting resin, a mixed resin of an epoxy resin and a melamine resin is particularly preferable from the viewpoint of heat resistance and adhesion of the obtained printed matter.

The heat-curable resin preferably contains a resin obtained by curing at least one resin selected from the group consisting of epoxy-based resins and melamine-based resins from the viewpoint of heat-resistant adhesion of the obtained printed matter. It is particularly preferable to contain a resin obtained by curing an epoxy resin and a melamine resin.

Further, a matting agent such as thermosetting silicon oxide may be further contained, and the content thereof is preferably 3% by mass to 5% by mass with respect to the total mass of the first undercoat layer.

The content of the thermosetting resin contained in the first undercoat layer is 10% by mass to 90% by mass with respect to the total mass of the first undercoat layer from the viewpoint of heat resistance and adhesion of the obtained printed matter. It is preferable, it is more preferably 20% by mass to 80% by mass, and particularly preferably 30% by mass to 70% by mass.

The acrylic resin contained in the first undercoat layer is a resin mainly composed of a constituent unit formed of (meth) acrylic acid alkyl ester (containing 50% by mass or more with respect to the entire resin), and is a thermosetting acrylic. It may or may not be a resin.
Among them, the acrylic resin is particularly preferably a self-crosslinking type acrylic resin or a melamine resin crosslinked type acrylic resin from the viewpoint of heat resistance and adhesion of the obtained printed matter.
Examples of the acrylic resin include "Acrydic 54-172-60", "Acrydic A-322", "Acrydec A-405", and "Acrydic A-452" manufactured by DIC Corporation. "JONCRYL 500", "JONCRYL 512", "JONCRYL 901", "JONCRYL 906", "Dianar SE-5437", "Dianar SE-5102", "Dianar SE-192" manufactured by Mitsubishi Chemical Corporation , "Dianar SE-5179", "Dianar SE-5661", "Dianar SE-5377", "Dianar SE-5248", "Dianar SE-1466", "Dianar SE-5466", "Diamond""DianarSE-5456","DianarSE-5601","DianarSE-5650","DianarSE-5487","DianarSE-5649","DianarSE-5482","DianarSE" -5616 ”,“ Dianar SE-653 ”and the like.

The acrylic resin may be contained alone or in combination of two or more.
The content of the acrylic resin contained in the first undercoat layer is 5% by mass to 60% by mass with respect to the total mass of the first undercoat layer from the viewpoint of heat resistance and adhesion of the obtained printed matter. Is more preferable, and it is more preferably 10% by mass to 50% by mass, and particularly preferably 20% by mass to 40% by mass.

The fibrous resin in the present disclosure is a cellulosic resin, and preferably includes cellulose acetate such as cellulose acetate and cellulose acetate propionate, and nitrocellulose which is also referred to as nitrified cotton and is a nitrate ester of cellulose.
Of these, nitrocellulose is particularly preferable from the viewpoint of heat resistance and adhesion of the obtained printed matter.
Examples of nitrocellulose include DHX1-2, DHX3-5, DHX4-6, DHX5-10, DHX8-13, DHX11-16, and DHX30-50 manufactured by Nobel NC.
Examples of cellulose acetate using cotton acetate as a main raw material include Cellulose Actate (CA-320S NF / EP, CA-320S, CA-394-60LF, CA-398-10, CA-398-) manufactured by Eastman. 10NF / EP, CA-398-3, CA-398-30, CA-398-6), CAB-381-0.1, CAB-381-0.5, CAB-381-2 BP, CAB-381- 2. CAB-381-20, CAB-500-5, CAB-531-1, CAB-551-0.01, CAB-551-0.2, CAB-553-0.4) and the like.
Examples of the cellulose acetate propionate called CAP include Cellulose Acetate Propionate (CAP-482-0.5, CAP-482-20, CAP-504-0.2) manufactured by Eastman.

The fibrin-based resin may be contained alone or in combination of two or more.
The content of the fibrous resin contained in the first undercoat layer is 0.5% by mass to 30% by mass with respect to the total mass of the first undercoat layer from the viewpoint of heat resistance and adhesion of the obtained printed matter. It is preferably 1% by mass to 25% by mass, more preferably 5% by mass to 20% by mass.

Further, the first undercoat layer preferably contains a colorant, and more preferably a white pigment, in order to improve the readability of the barcode.

The colorant may be contained alone or in combination of two or more.
The content of the coloring contained in the first undercoat layer is preferably 1% by mass to 40% by mass with respect to the total mass of the first undercoat layer from the viewpoint of heat resistance and adhesion of the obtained printed matter. More preferably, it is 5% by mass to 35% by mass.

Further, a known coating agent can be used for forming the first undercoat layer, and for example, a PT VX-OP varnish manufactured by T & K TOKA can be preferably used.

The first undercoat layer is preferably formed in the same region as the region where the ink composition is ejected or in a region wider than the region where the ink composition is ejected, and is formed on one surface of the aluminum foil base material. It is more preferable that it is formed on the entire surface.
The formation of the first undercoating layer (coating amount) is not particularly limited, per unit ^area, more preferably from ^{0.5g / m 2 ~5.0g / m 2} , 1.0g more preferably / ^{m 2} ~3.0g / ^{m 2,} and particularly preferably ^{1.5g / m 2 ~2.5g / m 2} .

As a means for forming the first undercoat layer in the laminated body, for example, a coating device or an inkjet means can be used, and it is preferable to use a coating device.
The coating device is not particularly limited and may be appropriately selected from known coating devices according to the purpose and the like. For example, a gravure coater, an air doctor coater, a blade coater, a lot coater, a knife coater, and a squeeze coater. , Impregnation coater, reverse roll coater, transfer roll coater, gravure coater, kiss roll coater, cast coater, spray coater, curtain coater, extrusion coater and the like. For details, refer to "Coating Engineering" by Yuji Harasaki.
Above all, application using a gravure coater is preferable.
Further, as a means for forming the first undercoat layer, it is preferable to use a heating means.
The heating means is not particularly limited, and known means can be used.
Examples of the heating means include a heater, a hot air dryer, and the like.

The heating temperature at the time of forming the first undercoat layer is not particularly limited and may be appropriately selected depending on the material used, but is preferably 50 ° C to 300 ° C, preferably 100 ° C to 270 ° C. Is more preferable.

<Step of forming a second undercoat layer on the first undercoat layer in the above laminate with the second undercoat composition>
The inkjet recording method according to the present disclosure is a step of forming a second undercoat layer on the first undercoat layer of the laminate with a second undercoat composition (simply, a "step of forming a second undercoat layer"). The second undercoat composition also contains a compound having an isocyanate group, a radically polymerizable monomer, and a radical polymerization initiator.
Details of the second undercoat composition will be described later.

The second undercoat layer may be formed in the same region as the region where the ink composition is ejected or in a region wider than the region where the ink composition is ejected in the step of forming the second undercoat layer. It is preferable to form it on the entire surface of one surface of the aluminum foil base material.
Further, the second undercoat layer is preferably formed on the first undercoat layer, and is more than the same region where the first undercoat layer is formed or the region where the first undercoat layer is formed. Is more preferably formed in a narrow area.

That said formation of the second undercoating layer (coating amount) is, per unit area is preferably from ^{0.05g / m 2 ~5g / m 2} , a 0.06g ^{/ m 2} ~3g ^/ m 2 Is more preferable. When the amount of the undercoat composition applied is within the above range, a sufficient effect of improving adhesion can be obtained and a printed matter having excellent flexibility can be obtained, which is preferable.
The amount of the second undercoat layer formed (coating amount) per unit area is 0.05 to 5 when the maximum amount of the ink composition applied per unit area (per color) is 1. It is preferably in the range of 0.17 to 4, more preferably in the range of 0.07 to 4, and particularly preferably in the range of 0.1 to 3.

In the inkjet recording method of the present invention, a coating device, an inkjet means, or the like can be used as a means for applying the second undercoat composition, and it is preferable to use a coating device.
The coating device is not particularly limited and may be appropriately selected from known coating devices according to the purpose and the like. Examples thereof include the coating device described above.
Above all, in terms of equipment cost, it is preferable to apply the second undercoat composition using a relatively inexpensive bar coater or spin coater.

<Step of ejecting the ink composition onto the second undercoat layer by the inkjet method>
The inkjet recording method according to the present disclosure includes a step of ejecting an ink composition onto the second undercoat layer by an inkjet method (simply referred to as a "step of ejecting an ink composition"), and the ink composition. Includes a radically polymerizable monomer, a radical polymerization initiator, and a colorant.
Details of the ink composition will be described later.

It is preferable to use an inkjet head as a means for ejecting the ink composition by the inkjet method by the inkjet method. Inkjet heads include, for example, a charge control method that uses electrostatic attraction to eject ink, a drop-on-demand method that uses the vibration pressure of a piezo element (pressure pulse method), and an electric signal that is converted into an acoustic beam for ink. Heads such as an acoustic inkjet method that irradiates and ejects ink using radiation pressure, and a thermal inkjet (bubble jet (registered trademark)) method that heats ink to form bubbles and uses the generated pressure are suitable. be.

The inkjet recording device that can be used in the inkjet recording method according to the present disclosure is not particularly limited, and a known inkjet recording device that can achieve the desired resolution can be arbitrarily selected and used. That is, as the inkjet recording method according to the present disclosure, a known inkjet recording device including a commercially available product can be used.
Further, the means for forming the second undercoat layer may be provided in the inkjet recording device or may be provided as another device.

Examples of the inkjet recording device that can be used in the present disclosure include a device including an ink supply system, a temperature sensor, and an ultraviolet source.
The ink supply system includes, for example, a source tank containing an ink composition, a supply pipe, an ink supply tank immediately before the inkjet head, a filter, and a piezo-type inkjet head. The piezo type inkjet head preferably has multi-size dots of 1 pl (picolitre) to 100 pl, more preferably 8 pl to 30 pl, preferably 320 × 320 dpi to 4,000 × 4,000 dpi, more preferably 400 × 400 dpi. It can be driven so that it can be discharged at a resolution of 1,600 × 1,600 dpi, more preferably 1,200 × 1,200 dpi. The dpi referred to in the present disclosure represents the number of dots per 2.54 cm.

Since it is preferable for the ink composition to keep the ejected ink composition at a constant temperature, it is preferable that the inkjet recording apparatus is provided with means for stabilizing the ink composition temperature. The part to be kept at a constant temperature covers all the piping system and members from the ink tank (intermediate tank if there is an intermediate tank) to the nozzle injection surface. That is, heat insulation and heating can be performed from the ink supply tank to the inkjet head portion.
The temperature control method is not particularly limited, but for example, it is preferable to provide a plurality of temperature sensors at each piping portion and perform heating control according to the ink flow rate and the ambient temperature. The temperature sensor can be provided near the ink supply tank and the nozzle of the inkjet head. Further, it is preferable that the head unit to be heated is thermally shielded or insulated so that the main body of the apparatus is not affected by the temperature from the outside air. In order to shorten the printer start-up time required for heating or to reduce the loss of heat energy, it is preferable to insulate the printer from other parts and reduce the heat capacity of the entire heating unit.

It is preferable to keep the temperature of the ink composition at the time of ejection as constant as possible. Therefore, in the present disclosure, it is appropriate that the temperature control range of the ink composition is preferably ± 5 ° C. of the set temperature, more preferably ± 2 ° C. of the set temperature, and further preferably ± 1 ° C. of the set temperature. ..

The drip interval from the application of the second undercoat composition to the first drip of the ink composition is not particularly limited, but may be within the range of 5 μs or more and 10 seconds or less. preferable. The ejection interval of the ink droplets is more preferably 10 μs or more and 5 seconds or less, and particularly preferably 20 μs or more and 5 seconds or less.

Further, in the inkjet recording method according to the present disclosure, one type of ink composition may be used alone, or two or more types of ink compositions may be used.
For example, when forming a color image, it is preferable to use at least each color ink composition of yellow, cyan, magenta and black, and it is more preferable to use each color ink composition of white, yellow, cyan, magenta and black. preferable.
Further, a light color ink composition such as light magenta or light cyan, a special color ink composition such as orange, green and violet, a clear ink composition, a metallic ink composition and the like may be used.

In the inkjet recording method according to the present disclosure, the order of each ink composition to be ejected is not particularly limited, but it is preferable to apply the ink composition having the lowest lightness onto the second undercoat layer, and yellow. , Cyan, magenta, and black are preferably applied on the second undercoat layer in the order of black, magenta, cyan, and yellow. When white is added to this, it is preferably applied on the second undercoat layer in the order of black, magenta, cyan, yellow, and white. Further, the present disclosure is not limited to this, and an ink set containing at least seven colors including a total of seven colors including yellow, light cyan, light magenta, cyan, magenta, black, and white ink compositions can also be preferably used. It is preferable to eject black, magenta, cyan, yellow, light magenta, light cyan, and white on the second undercoat layer by an inkjet method in this order.

The image to be formed in the step of ejecting the ink composition is not particularly limited, and a desired image may be formed. However, in many cases, the laminated printed matter described above is used, and it is considered that more heat-resistant adhesion is required. It is preferable to form an image containing a barcode.
The "image" in the present disclosure includes not only characters, symbols, figures, etc., which have individual meanings, but also patterns, wholly colored objects, and the like, which have no meaning.

<Step of curing the ejected ink composition by irradiating the ejected ink composition with ultraviolet rays having an integrated light amount of 400 mJ / cm ^{2 or more in an atmosphere of an oxygen concentration of 0.1% by volume or less with an ultraviolet light emitting diode>}
The inkjet recording method according to the present disclosure is a step of curing the ejected ink composition by irradiating the ejected ink composition with ultraviolet rays having an integrated light amount of 400 mJ / cm ² or more in an atmosphere of an oxygen concentration of 0.1% by volume or less by an ultraviolet light emitting diode (a step of curing the ejected ink composition. It simply includes "the process of irradiating with ultraviolet rays and curing").
This step completely cures the second undercoat layer and the entire ink composition. "Completely cured" in the present disclosure means a state in which the inside and the surface of the second undercoat layer and the ink composition are completely cured. Specifically, plain paper (for example, copy paper C2 manufactured by Fuji Xerox Co., Ltd., product code V436) is pressed against a uniform force (a constant value within the range of ^{500 mN / cm 2 to} 1,000 mN / cm ^2). Therefore, it can be judged by whether or not the liquid surface is transferred to plain paper. That is, the case where no transfer is performed is called a completely cured state.

In the above-mentioned step of irradiating with ultraviolet rays and curing, the step of irradiating with ultraviolet rays having an integrated light amount of 400 mJ / cm ² or more by an ultraviolet light emitting diode is performed and curing is performed.
Further, the integrated light quantity of the ultraviolet irradiation, is preferably 420 mJ / cm ² or more, and more preferably 440 mJ / cm ² or more. The upper limit of the integrated light quantity is not particularly limited, it is preferably 2,000 mJ / cm ² or less, and more preferably 1,000 mJ / cm ² or less.
Further, the integrated light amount of the ultraviolet irradiation includes the amount of light in the ultraviolet irradiation for semi-curing the ink composition described later. That is, the integrated light amount of the ultraviolet irradiation is the total light amount of the irradiated ultraviolet rays from the ejection of the first ink composition to the complete curing of the entire ink composition.
In the step of irradiating with ultraviolet rays and curing, the amount of light in one ultraviolet irradiation may be selected so as to satisfy the above integrated amount of light, and varies depending on the composition, particularly the type and content of the radical polymerization initiator. it is preferably 1mJ ^/ cm ² ~500mJ ^/ cm 2 approximately.
The ultraviolet (UV) exposure light source in the step of irradiating with ultraviolet rays and curing is an ultraviolet light emitting diode (UV-LED).
As a UV-LED, for example, Nichia Corporation has marketed a purple LED having a main emission spectrum having a wavelength between 365 nm and 420 nm. If even shorter wavelengths are required, US Pat. No. 6,084,250 discloses LEDs that can emit ultraviolet light centered between 300 nm and 370 nm. Other UV-LEDs are also available and can irradiate radiation in different UV bands. In the present disclosure, a particularly preferred source of ultraviolet light is a UV-LED having a peak wavelength in the range of 340 nm to 400 nm.

In the step of irradiating with ultraviolet rays and curing, the ejected ink composition is irradiated with ultraviolet rays and cured in an atmosphere having an oxygen concentration of 0.1% by volume or less.
As the oxygen concentration, the oxygen concentration is preferably 0.05% by volume or less, and the oxygen concentration is more preferably 0.01% by volume or less. The lower limit is 0% by volume, that is, an atmosphere containing no oxygen. Within the above range, the obtained printed matter is excellent in heat resistance and surface curability.
The method for adjusting the atmosphere of the oxygen concentration is not particularly limited, and a known method can be used, but it is preferably performed by nitrogen purging.
In the inkjet recording method according to the present disclosure, the ink composition may be described later in an atmosphere having an oxygen concentration of 0.1% by volume or less when irradiated with ultraviolet rays to completely cure the entire ink composition. Also in the step of irradiating with ultraviolet rays and semi-curing, it is preferable to irradiate with ultraviolet rays in an atmosphere having an oxygen concentration of 0.1% by volume or less.

<Step of irradiating the second undercoat layer with ultraviolet rays to semi-cure, and step of irradiating the ink composition with ultraviolet rays to semi-cure>
The inkjet recording method according to the present disclosure preferably includes a step of semi-curing the second undercoat layer between the step of forming the second undercoat layer and the step of ejecting the ink composition. It is more preferable to include a step of irradiating the second undercoat layer with ultraviolet rays to semi-cure it.
By having the step of semi-curing the second undercoat layer, it is possible to form an image having higher adhesion even when an undercoat composition having a low isocyanate compound content is used.
Further, the inkjet recording method according to the present disclosure preferably includes a step of irradiating the ink composition with ultraviolet rays to semi-cure the ink composition between the steps of ejecting the ink composition and the step of irradiating the ink composition with ultraviolet rays.
By having a step of irradiating the ink composition with ultraviolet rays to semi-cure the ink composition, the adhesion between the ink compositions is enhanced even if two or more kinds of ink compositions are used, and an image having higher adhesion can be formed. Become.
Hereinafter, these two semi-curing steps are collectively referred to as a "semi-curing step".
In the present disclosure, "semi-curing" means partially cured (partially cured), and a second undercoat layer or an ink composition described later (hereinafter, also simply referred to as "ink") is a portion. A state in which the ink is hardened but not completely hardened. When the ink composition ejected onto the second undercoat layer or the second undercoat layer is semi-cured, the degree of curing may be non-uniform. For example, it is preferable that the second undercoat layer, the ink composition, or both are cured in the depth direction.

Exposure of ultraviolet radiation necessary for the semi-curing the composition, in particular depends on the type and content of the radical polymerization initiator ^is preferably 1mJ / cm ² ~100mJ / cm 2 approximately.
Examples of the ultraviolet exposure means for semi-curing the ink composition include the above-mentioned ultraviolet light emitting diode (UV-LED).
Further, suitable ultraviolet exposure means for semi-curing the second undercoat layer include a metal halide lamp, a mercury lamp, and an LED light source. Among them, an LED light source is preferable.
In the step of semi-curing the second undercoat layer, ultraviolet irradiation may be performed in the above-mentioned atmosphere of an oxygen concentration of 0.1% by volume or less, but from the viewpoint of adhesion to the ink composition, the oxygen concentration is high. It is preferable to irradiate ultraviolet rays in an atmosphere of more than 0.1% by volume, and it is more preferable to irradiate ultraviolet rays in an atmosphere.

In the present disclosure, when the radically polymerizable second undercoat layer is partially UV-cured by using it in the presence of oxygen having a radical polymerization inhibitory effect, the undercoat layer is cured more internally than externally. proceed.
In particular, on the surface of the second undercoat layer, the polymerization reaction is more likely to be inhibited by the influence of oxygen in the air than the inside thereof. Therefore, the second undercoat layer can be semi-cured by controlling the conditions for applying ultraviolet rays.

Irradiation with ultraviolet rays promotes the generation of active species due to the decomposition of the radical polymerization initiator, and the increase in active species and the increase in temperature promote the curing reaction by polymerization or cross-linking of the polymerizable or cross-linkable material caused by the active species. Will be done.
Further, thickening (increased viscosity) can also be suitably performed by irradiation with ultraviolet rays.

In the semi-curing step, for example, in the case of a curing reaction based on an ethylenically unsaturated compound, the unpolymerization rate can be quantitatively measured by the reaction rate of the ethylenically unsaturated group.
When the semi-cured state of the second undercoat layer is realized by a polymerization reaction of an ethylenically unsaturated compound that starts polymerization by irradiation with ultraviolet rays, the unpolymerization rate (A (polymerization)) from the viewpoint of improving the scrapability of the printed matter. After) / A (before polymerization)) is preferably 0.2 or more and 0.9 or less, more preferably 0.3 or more and 0.9 or less, and 0.5 or more and 0.9 or less. Is particularly preferred.
Here, A (after polymerization) is the absorbance of the infrared absorption peak due to the ethylenically unsaturated group after the polymerization reaction, and A (before polymerization) is the absorbance of the infrared absorption peak due to the ethylenically unsaturated group before the polymerization reaction. The absorbance of. For example, when the ethylenically unsaturated compound contained in the undercoat liquid is an acrylate monomer or a methacrylate monomer, an absorption peak based on a polymerizable group (acrylate group, methacrylate group) can be observed in the vicinity of ^{810 cm -1, and the absorbance of the peak is observed.} Therefore, it is preferable to define the unpolymerization rate.
Further, as a means for measuring the infrared absorption spectrum, a commercially available infrared spectrophotometer can be used, and either a transmission type or a reflection type may be used, and it is preferable to appropriately select in the form of a sample. For example, it can be measured using an infrared spectrophotometer FTS-6000 manufactured by BIO-RAD.

In the inkjet recording method according to the present disclosure, when two or more kinds of ink compositions are ejected, one ink composition is ejected and then the next other ink composition is ejected before being ejected. It is preferable to include a step of semi-curing the ink composition. That is, in the inkjet recording method according to the present disclosure, for each ink composition used, a step of ejecting the ink composition onto the second undercoat layer and a step of semi-curing the ejected ink composition. Is preferably included. In the above aspect, the effect of the present disclosure can be more exerted.
When two or more kinds of ink compositions are applied, the steps of semi-curing each ink composition after ejection of each ink composition are the same as the steps of irradiating the above ink compositions with ultraviolet rays to semi-curing the ink compositions. The same applies to the exposure apparatus and exposure conditions used, and the preferred embodiments.
Further, when the step of irradiating with ultraviolet rays to be cured immediately afterwards is performed, the inkjet recording method according to the present disclosure may include or may include a step of semi-curing the ink composition ejected last. It is not necessary, but it is preferable not to include it from the viewpoint of cost and convenience.
When ejecting two or more kinds of ink compositions, each ink composition may be ejected onto the second undercoat layer, the ejected ink composition, or the semi-cured ink composition. preferable. That is, it is preferable that any ink composition is directly in contact with the ink composition or is ejected onto the second undercoat layer via another ink composition layer. At that time, it is preferable that the second undercoat layer is semi-cured from the viewpoint of adhesion.

In addition, the inkjet recording method according to the present disclosure may include steps (other steps) other than the above.
Other steps can include known steps.

<Inkjet recording device>
The inkjet recording apparatus used particularly preferably in the present disclosure will be described in more detail. The inkjet recording method according to the present disclosure described above is preferably carried out by the inkjet recording apparatus used in the present disclosure described below.
The inkjet recording apparatus used in the present disclosure includes a transport means for transporting the laminate, an imparting means for forming a second undercoat layer on the laminate, and an ink composition on the second undercoat layer. It is preferable to have a ejection means for discharging and a complete curing means for completely curing the undercoat liquid and the ink composition, and a semi-curing means for semi-curing the applied undercoat composition may be further provided.
Further, the inkjet recording apparatus used in the present disclosure is preferably a so-called single-pass type inkjet recording apparatus.
FIG. 1 is a schematic view showing an example of an inkjet recording apparatus preferably used in the present disclosure. The device below has an exposure light source 17 for semi-curing the undercoat composition, but even a device that does not have such a semi-curing light source can be suitably used in the present disclosure.
The laminate 12 stretched by the feeding roller 24 and the take-up roller 26, which are the means for conveying the laminate 12, is conveyed in the direction of arrow A, and the undercoat composition is applied by the second undercoat layer coating roller 14. A second undercoat layer is formed. Subsequently, the second undercoat composition is semi-cured by the exposure light source 17 for semi-curing the second undercoat composition. Subsequently, the ink composition of each color (K: black, Y: yellow, M: magenta, C: cyan, W: white) is used in the inkjet heads 18K, 18C, 18M, 18Y, and 18W for ejecting the ink composition of each color. ) Is ejected, and the ejected black, yellow, magenta and cyan ink compositions are semi-cured by the semi-curing exposure light sources 20K, 20C, 20M and 20Y installed immediately after the inkjet heads 18K, 18C, 18M and 18Y. Will be done. Finally, the nitrogen purge exposure light source unit 22 is irradiated with ultraviolet rays in an atmosphere having an oxygen concentration of 0.1% by volume or less, and the semi-cured second undercoat layer and the entire ink composition are cured. The integrated amount of ultraviolet irradiation of the ink composition is 400 mJ / cm ² or more.
In the nitrogen purge exposure light source unit 22, for example, when the LED light source is surrounded by an inert gas blanket and is connected to the inert gas generator via an inert gas pipe, the inert gas generator is operated. , The mode in which the air in the blanket is replaced with an inert gas is preferably mentioned. As the inert gas, nitrogen or the like can be used as described above.
In FIG. 1, a nip roll 28 is provided in order to improve the transport system. By completely curing the undercoat composition, in the inkjet recording method according to the present disclosure, a nip roll can be used, more accurate transportability is realized, and misregistration (misalignment of landing position) is suppressed. The nip roll 28 is not essential, and an image forming apparatus that does not have a nip roll may be used.

The transport speed of the laminated body or the like in the inkjet recording method according to the present disclosure is not particularly limited, but is preferably 50 m / min to 150 m / min.
Further, the transport means in the inkjet recording method according to the present disclosure is not particularly limited, and any known transport means may be used.

<< Second Undercoat Composition >>
The second undercoat composition used in the inkjet recording method according to the present disclosure contains a compound having an isocyanate group, a radically polymerizable monomer, and a radical polymerization initiator.
The second undercoat composition used in the present disclosure is an oily liquid composition that can be cured by irradiation with ultraviolet rays.

-Compounds with isocyanate groups-
The compound having an isocyanate group used in the second undercoat composition is not particularly limited, and a known isocyanate compound can be used. Either an aliphatic or aromatic isocyanate may be used, but an aliphatic isocyanate is preferable from the viewpoint of safety and stability.
In addition, as the isocyanate compound used in the present disclosure, a commercially available product can also be used.
For example, Takenate series (manufactured by Mitsui Chemicals, Inc.) such as Takenate D103H, D204, D160N, D170N, D165N, D178NL, D110N, Coronate HX, HXR, HXL, HXLV, HK, HK-T, HL, 2096 (Japan). Polyurethane Industry Co., Ltd.) is preferably mentioned. In addition, TM-550 and CAT-RT-37-2K (manufactured by Toyo Morton Co., Ltd.), and X-series solvent-free adhesives such as XC233-2 and XA126-1 It is also possible to use a commercially available two-component mixed adhesive of an isocyanate compound and a polyol compound described later, such as (manufactured by Dainichi Seika Kogyo Co., Ltd.).
The amount of the isocyanate compound added is preferably 2% by mass to 90% by mass, more preferably 5% by mass to 80% by mass, and 10% by mass to the total mass of the second undercoat composition. 75% by mass is more preferable.

-Radical polymerizable monomer-
As the radically polymerizable monomer used in the second undercoat composition, an ethylenically unsaturated compound is preferable, and a known ethylenic compound can be used, and a (meth) acrylate compound, a vinyl ether compound, an allyl compound, N- Examples thereof include vinyl compounds and unsaturated carboxylic acids. Examples thereof include radically polymerizable monomers described in JP-A-2009-22414, polymerizable compounds described in JP-A-2009-209289, and ethylenically unsaturated compounds described in JP-A-2009-191183.
The ethylenically unsaturated compound is preferably a (meth) acrylate compound, more preferably an acrylate compound.
The second undercoat composition preferably contains a polyfunctional ethylenically unsaturated compound in an amount of 70% by mass or more based on the total content of the radically polymerizable monomer. Within the above range, the generation of odor can be suppressed.
The second undercoat composition preferably contains a polyfunctional ethylenically unsaturated compound from the viewpoint of curability and flexibility.

In the present disclosure, the second undercoat composition preferably contains a polyfunctional (meth) acrylate compound as the polyfunctional ethylenically unsaturated compound, and more preferably contains a bifunctional (meth) acrylate compound. It is more preferable to contain a bifunctional acrylate compound, and it is particularly preferable to contain a diacrylate monomer because it has a low viscosity and is excellent in reactivity.
In the present disclosure, the monomer means a radically polymerizable compound having a viscosity of less than 0.1 Pa · s at room temperature (25 ° C.). The monomer preferably has a molecular weight (weight average molecular weight when having a molecular weight distribution) of less than 1,000, and the oligomer is generally a polymer in which a finite number (preferably 5 to 100) of monomers are bonded. The weight average molecular weight is preferably 1,000 or more.

As the polyfunctional ethylenically unsaturated compound, a di (meth) acrylic acid ester (bifunctional (meth) acrylate compound) of an aliphatic hydrocarbon diol having 6 to 12 carbon atoms is preferably exemplified. The hydrocarbon diol may be any of a linear hydrocarbon diol, a branched hydrocarbon diol and a cyclic hydrocarbon diol, and the linear hydrocarbon diol and the branched hydrocarbon diol are preferably exemplified.
Di (meth) acrylic acid esters of aliphatic hydrocarbon diols having 6 to 12 carbon atoms are preferable because they have a low viscosity and a relatively low odor of themselves.
Examples of the di (meth) acrylic acid ester of the aliphatic hydrocarbon diol having 6 to 12 carbon atoms include 1,6-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, and 1,8-. Octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 3-methyl-1, 5-Pentanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, tricyclodecanedimethanol di (meth) Acrylate is preferably exemplified.
Among these, decanediol diacrylate, dodecanediol diacrylate, 3-methyl-1,5-pentanediol dimethacrylate are more preferable, and 3-methyl-1,5-pentanediol diacrylate is even more preferable.
Further, in the present disclosure, the (meth) acrylate monomer means a compound containing one or more (meth) acryloyloxy groups in the molecule and having a viscosity of less than 0.1 Pa · s at room temperature (25 ° C.). do. When the viscosity is within the above range, migration of printed matter, suppression of odor, and reactivity can be achieved at the same time.

Specific examples of other bifunctional (meth) acrylate compounds include dipropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and ethylene oxide (EO) modification. Neopentyl glycol di (meth) acrylate, propylene oxide (PO) -modified neopentyl glycol di (meth) acrylate, EO-modified hexanediol di (meth) acrylate, PO-modified hexanediol di (meth) acrylate, tripropylene glycol di (meth) ) Acrylate and triethylene glycol di (meth) acrylate are preferable.

Examples of the trifunctional or higher functional (meth) acrylate compound include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, trimethylolethanetri (meth) acrylate, and trimethylol. Examples thereof include propanetri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, and oligoester (meth) acrylate.

[Monofunctional ethylenically unsaturated compound]
The second undercoat composition may contain a monofunctional ethylenically unsaturated compound as a radically polymerizable monomer. Examples of the monofunctional ethylenically unsaturated compound include a monofunctional (meth) acrylate compound, a monofunctional (meth) acrylamide compound, a monofunctional aromatic vinyl compound, a monofunctional vinyl ether compound (triethylene glycol divinyl ether, etc.), and a monofunctional N-. Examples include vinyl compounds (N-vinyl caprolactam, etc.).

Examples of the monofunctional (meth) acrylate compound include hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, and isodecyl (meth). Acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-Ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate, cyanoethyl (meth) acrylate, benzyl (meth) acrylate, butoxymethyl (meth) Acrylate, 3-methoxybutyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2- (2-butoxyethoxy) ethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meth) ) Acrylate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4-butylphenyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, 4- Chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, glycidyloxypropyl (meth) ) Acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate,

4-Hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, trimethoxy Cyrilpropyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, polyethylene oxide monomethyl ether (meth) acrylate, oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, oligoethylene Oxide monoalkyl ether (meth) acrylate, polyethylene oxide monoalkyl ether (meth) acrylate, dipropylene glycol (meth) acrylate, polypropylene oxide monoalkyl ether (meth) acrylate, oligopropylene oxide monoalkyl ether (meth) acrylate, 2- Methacryloxytyl succinic acid, 2-methacryloyloxyhexahydrophthalic acid, 2-methacryloyloxyethyl-2-hydroxypropylphthalate, butoxydiethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl ( Meta) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, ethylene oxide (EO) modified phenol (meth) acrylate, EO modified cresol (meth) acrylate, EO modified nonylphenol (meth) acrylate, propylene oxide (PO) Modified nonylphenol (meth) acrylate, EO-modified -2-ethylhexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (3-ethyl- Examples thereof include 3-oxetanylmethyl) (meth) acrylate and phenoxyethylene glycol (meth) acrylate.

Examples of the (meth) acrylamide compound include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, Nn-butyl (meth) acrylamide, and N. -T-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl ( Examples include (meth) acrylamide and (meth) acryloylmorpholin.

Examples of the aromatic vinyl compound include styrene, dimethylstyrene, trimethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, vinyl benzoic acid methyl ester, 3-methylstyrene, and the like. 4-Methyl styrene, 3-ethyl styrene, 4-ethyl styrene, 3-propyl styrene, 4-propyl styrene, 3-butyl styrene, 4-butyl styrene, 3-hexyl styrene, 4-hexyl styrene, 3-octyl styrene, 4-octyl styrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allyl styrene, isopropenyl styrene, butenyl styrene, octenyl styrene, 4-t-butoxycarbonyl styrene, 4-t- Butoxystyrene and the like can be mentioned.

More specifically, Shinzo Yamashita, "Handbook of Crosslinking Agents" (1981, Taiseisha); Kiyomi Kato, "UV / EB Curing Handbook (Raw Materials)" (1985, Polymer Publishing Association); Edited by "Application and Market of UV / EB Curing Technology", p. 79 (1989, CMC Publishing Co., Ltd.); "Polyester Resin Handbook" by Eiichiro Takiyama (1988, Nikkan Kogyo Shimbun Co., Ltd.), etc. Commercially available products or industry-known radically polymerizable or crosslinkable monomers, oligomers and polymers can be used.

The radically polymerizable monomer may be used alone or in combination of two or more.
The total content of the radically polymerizable monomer in the second undercoat composition is preferably 10% by mass to 80% by mass, and 15% by mass to 75% by mass, from the viewpoint of both adhesion and blocking suppression. It is preferably by mass%, more preferably 60% by mass to 72% by mass.
Further, from the viewpoint of curability and heat resistance, the content of the polyfunctional monomer with respect to the total content of the radically polymerizable monomer in the second undercoat composition is preferably 70% by mass or more, preferably 70% by mass. It is more preferably% to 100% by mass, and more preferably 80% by mass to 100% by mass.

-Binder polymer-
The second undercoat composition may include a binder polymer. As the binder polymer, an inert resin having no radically polymerizable group is preferable.
As the binder polymer, known binder polymers such as polyester resin, polyurethane resin, vinyl resin, acrylic resin, and rubber resin can be used, but acrylic resin is preferable, and an inert methyl methacrylate homopolymer and / or co-polymer can be used. Polymers are more preferred. For example, Aldrich polymethylmethacrylate (molecular weight 10,000, catalog number 81497; molecular weight 20,000, catalog number 81498; molecular weight 50,000, catalog number 81501), methyl methacrylate / n-butyl methacrylate copolymer (mass). Ratio 85/15, molecular weight 75,000; catalog number 474029), etc .; ELVACITE 2013 (methyl methacrylate / n-butyl methacrylate copolymer, mass ratio 36/64, molecular weight 37,000), 2021, 2614, manufactured by Lucite International. 4025, 4026, 4028, etc .; Paraloid DM55, B66, etc. manufactured by Rohm and Haas; BR113, 115, etc. manufactured by Dianal Polymer, etc. may be mentioned.
The weight average molecular weight (Mw) of the binder polymer is preferably 1,000 or more, more preferably 1,000 to 1,000,000, and even more preferably 5,000 to 200,000. , 8,000-100,000 is particularly preferable.
The binder polymer may be used alone or in combination of two or more.
The content of the binder polymer is preferably 0.2% by mass to 15% by mass, and more preferably 1% by mass to 10% by mass of the entire second undercoat composition.
When the content of the binder polymer is within the above range, a printed matter excellent in blocking inhibition can be obtained.

-Radical polymerization initiator-
In the present disclosure, the second undercoat composition contains a radical polymerization initiator.
The radical polymerization initiator is more preferably a radical photopolymerization initiator.
Examples of the radical polymerization initiator include (a) aromatic ketones, (b) acylphosphine compounds, (c) aromatic onium salt compounds, (d) organic peroxides, (e) thio compounds, and (f) hexaally. Rubiimidazole compound, (g) ketooxime ester compound, (h) borate compound, (i) azinium compound, (j) metallocene compound, (k) active ester compound, (l) compound having carbon halogen bond, and (m) ) Alkylamine compounds and the like can be mentioned. As these radical polymerization initiators, the compounds (a) to (m) above may be used alone or in combination. As for the details of the radical polymerization initiator, for example, those described in paragraphs 0090 to 0116 of JP2009-185186A can be exemplified.
The radical polymerization initiator in the present disclosure may be used alone or in combination of two or more.
Preferred examples of the radical polymerization initiator include an acylphosphine compound, an α-hydroxyketone compound and / or an α-aminoketone compound. Among them, the acylphosphine compound and / or the α-aminoketone compound is more preferable, and the acylphosphine compound is further preferable.

Preferable examples of acylphosphine compounds are bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethylbenzoyl) phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl)-. 2-methoxyphenylphosphine oxide, bis (2,6-dimethylbenzoyl) -2-methoxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-dimethoxyphenylphosphine oxide, bis (2,6) -Dimethylbenzoyl) -2,4-dimethoxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-dipentyloxyphenylphosphine oxide, bis (2,6-dimethylbenzoyl) -2,4- Dipentyloxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,6-dimethylbenzoylethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2,6-dimethoxy) Benzoyl) -2,4,4-trimethylpentylphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (LUCIRIN TPO, manufactured by BASF), 2,6-dimethylbenzoylmethoxyphenylphosphine oxide, 2,4 Examples thereof include 6-trimethylbenzoyl (4-pentyloxyphenyl) phenylphosphine oxide and 2,6-dimethylbenzoyl (4-pentyloxyphenyl) phenylphosphine oxide.

Among these, as the acylphosphine oxide compound, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (IRGACURE 819, manufactured by BASF), bis (2,6-dimethoxybenzoyl) -2,4,4- Trimethylpentylphenylphosphine oxide is preferable, and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide is particularly preferable.

Further, as the radical polymerization initiator, aromatic ketones are preferable from the viewpoint of curability.
As the aromatic ketones, α-hydroxyketone compounds and / or α-aminoketone compounds are preferable.
As the α-hydroxyketone compound, known ones can be used, and for example, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, Examples thereof include 2-hydroxy-2-methyl-1-phenylpropane-1-one and 1-hydroxycyclohexylphenylketone, and among them, 1-hydroxycyclohexylphenylketone compound is preferable. In the present disclosure, the 1-hydroxycyclohexylphenyl ketone compound also includes a compound in which 1-hydroxycyclohexylphenyl ketone is substituted with an arbitrary substituent. The substituent can be arbitrarily selected as long as it can exhibit its ability as a radical polymerization initiator, and specifically, an alkyl group having 1 to 4 carbon atoms can be exemplified.
Further, as the α-aminoketone compound, known ones can be used, and specifically, for example, 2-methyl-1-phenyl-2-morpholinopropane-1-one and 2-methyl-1- [4. -(Hexyl) Phenyl] -2-morpholinopropan-1-one, 2-ethyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one And so on. Commercially available products include IRGACURE907 (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one) and IRGACURE369 (2-benzyl-2-dimethylamino-1- (4-morpholino)). Phenyl) -1-butanone), IRGACURE379 (2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone) (above, BASF (Manufactured by the company) and the like can be preferably exemplified.

In the present disclosure, a radical polymerization initiator having a weight average molecular weight of 500 to 3,000 may be used in combination from the viewpoint of suppressing migration and odor. The weight average molecular weight is more preferably 800 to 2,500, and even more preferably 1,000 to 2,000. When the molecular weight is 500 or more, elution of the compound from the cured film is suppressed, and an ink composition in which migration, odor and blocking are suppressed can be obtained. On the other hand, when it is 3,000 or less, the steric hindrance of the molecule is small, the degree of freedom of the molecule in the liquid / membrane is maintained, and high sensitivity can be obtained.
The weight average molecular weight is measured by the GPC method (gel permeation chromatography method) and converted into standard polystyrene to obtain the weight average molecular weight. For example, as GPC, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and three columns, TSKgeL SuperHZM-H, TSKgeL SuperHZ4000, and TSKgeL SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID x 15 cm) are used and eluted. THF (tetrahydrofuran) is used as the liquid. The conditions are as follows: the sample concentration is 0.35% by mass, the flow rate is 0.35 ml / min, the sample injection amount is 10 μl, the measurement temperature is 40 ° C., and an RI (differential refractive index) detector is used. The calibration curve is "Standard sample TSK standard, polystyrene" manufactured by Tosoh Corporation: "F-40", "F-20", "F-4", "F-1", "A-5000", It is prepared from 8 samples of "A-2500", "A-1000" and "n-propylbenzene".
As a radical polymerization initiator having a molecular weight having a weight average molecular weight of 500 to 3,000, SPEEDCURE 7010 (1,3-di ({α-[1-chloro-9-oxo-9H-thioxanthen-4-yl]] oxy} acetylpoly [oxy (1-methylethylene)]) oxy) -2,2-bis ({α-[1-chloro-9-oxo-9H-thioxanthen-4-yl] oxy} acetylpoly [oxy (1-methylethylene)] )]) Oxymethyl) propane, CAS No. 1003567-83-6), OMNIPOL TX (Polybutyleneglycol bis (9-oxo-9H-thioxanthenyloxy) acetate, CAS No. 813452-37-8), OMNIPOL BP (Polybutyleneglycol bis (4) -benzoylphenoxy) acetate, CAS No. 515136-48-8), etc. can be exemplified. The radical polymerization initiator having a molecular weight having a weight average molecular weight of 500 to 3,000 is preferably 0.01% by mass to 10% by mass, and 0.05% by mass to 8% by mass of the entire second undercoat composition. It is more preferably 0.0% by mass, further preferably 0.1% by mass to 5.0% by mass, and particularly preferably 0.1% by mass to 2.4% by mass. When it is within the above range, the curability is excellent.

The content of the radical polymerization initiator having a molecular weight of less than 340 in the second undercoat composition is not contained from the viewpoint of suppressing migration, odor and blocking, or is 0% by mass of the entire second undercoat composition. It is preferably more than 1.0% by mass and not contained, or more preferably more than 0% by mass and not more than 0.5% by mass, and it is not contained or more than 0% by mass and 0. It is more preferably 3% by mass or less, and particularly preferably not contained.

In addition, the second undercoat composition is a compound that functions as a sensitizer as a radical polymerization initiator by absorbing specific active energy rays and accelerating the decomposition of the radical polymerization initiator (hereinafter, simply "sensitizing"). It may also contain "agent").
Examples of the sensitizer include polynuclear aromatics (eg, pyrene, perylene, triphenylene, 2-ethyl-9,10-dimethoxyanthracene, etc.), xanthenes (eg, fluoressein, eosin, erythrosin, rhodamine B, etc.). Rose Bengal, etc.), cyanines (eg, thiacarbocyanine, oxacarbocyanine, etc.), merocyanines (eg, merocyanine, carbomerocyanine, etc.), thiadins (eg, thionin, methylene blue, toluidine blue, etc.), acridines (eg, erythinine, etc.) , Acridine orange, chloroflavin, acryflabin, etc.), anthracenes (eg, anthracene, etc.), squaliums (eg, squalium, etc.), coumarins (eg, 7-diethylamino-4-methylcoumarin, etc.), thioxanthones (eg, 7-diethylamino-4-methylcoumarin, etc.) , Isopropylthioxanthone, etc.), thiochromanones (for example, thiochromanone, etc.) and the like.
Among them, as the sensitizer, thioxanthones are preferable, and isopropylthioxanthone is more preferable.
Further, the sensitizer may be used alone or in combination of two or more.

The total content of the radical polymerization initiator with respect to the total mass of the second undercoat composition is preferably 1.0% by mass to 15.0% by mass, preferably 1.5% by mass to 10.0% by mass. More preferably, it is more preferably 2.0% by mass to 8.0% by mass. Within the above range, the curability is excellent.

-Polyol compound-
The second undercoat composition used in the present disclosure may contain a polyol compound.
The polyol compound is preferably a diol compound.
The polyol compound is not particularly limited, but when the isocyanate compound is TM-550, it is CAT-RT-37-2K (manufactured by Toyo Morton Co., Ltd.), and when the isocyanate compound is XC233-2, it is It is possible to use a commercially available product as a two-component mixed adhesive of an isocyanate compound and a polyol compound, such as an X-series useless adhesive (manufactured by Dainichi Seika Kogyo Co., Ltd.) such as XA126-1. ..
When the second undercoat composition used in the present disclosure contains a polyol compound, the content of the polyol compound with respect to the total mass of the second undercoat composition is preferably 5% by mass to 50% by mass, and 10% by mass. More preferably, it is from mass% to 40% by mass.

-Colorant-
The second undercoat composition that can be used in the present disclosure may contain a colorant, but preferably contains or does not contain a white colorant, and more preferably does not.
As the white pigment, Pigment White 6, 18, 21, and the like can be used depending on the purpose.
When the second undercoat composition contains a colorant, the content of the colorant in the composition is appropriately selected depending on the color and the purpose of use, but is 0.01 with respect to the total mass of the undercoat liquid. It is preferably mass% to 30% by mass.

-Dispersant-
In the present disclosure, the second undercoat composition may contain a dispersant.
In particular, when the second undercoat composition contains the above-mentioned colorant, it is preferable to include the dispersant in order to disperse the colorant.
As the dispersant, a polymer dispersant is preferable. The "polymer dispersant" in the present disclosure means a dispersant having a weight average molecular weight of 1,000 or more.

Examples of the polymer dispersant include DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-111, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-166. , DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-182 (manufactured by BYK Chemie); , EFKA7570, EFKA7575, EFKA7580 (manufactured by Fuka Additive); Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by San Nopco Ltd.); 12000, 13240, 13940, 17000, 22000, 24000, 26000, 28000, 32000, 36000, 39000, 41000, 71000 and other various polymer dispersants (manufactured by Noveon); ADEKA PLRONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by ADEKA Corporation), Ionet S-20 (manufactured by Sanyo Chemical Industries, Ltd.); Disparon Examples thereof include KS-860, 873SN, 874 (polymer dispersant), # 2150 (aliphatic polyvalent carboxylic acid), and # 7004 (polyether ester type) (manufactured by Kusumoto Kasei Co., Ltd.).
The content of the dispersant in the second undercoat composition is appropriately selected depending on the intended use, but is preferably 0.05% by mass to 15% by mass with respect to the total mass of the composition.

-Surfactant-
A surfactant may be added to the second undercoat composition in order to impart stable ejection properties for a long period of time.
Examples of the surfactant include those described in JP-A-62-173463 and JP-A-62-183457. For example, anionic surfactants such as dialkyl sulfosuccinates, alkylnaphthalene sulfonates, fatty acid salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene blocks. Examples thereof include nonionic surfactants such as copolymers, and cationic surfactants such as alkylamine salts and quaternary ammonium salts. Further, as the above-mentioned surfactant, a fluorine-based surfactant (for example, an organic fluoro compound or the like) or a silicone-based surfactant (for example, a polysiloxane compound or the like) may be used. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluorocompound include a fluorine-based surfactant, an oil-like fluorine-based compound (eg, fluorine oil), and a solid fluorine compound resin (eg, tetrafluoride ethylene resin). Nos. 8 to 17 and those described in JP-A-62-135826 can be mentioned.

The polysiloxane compound is preferably a modified polysiloxane compound in which an organic group is introduced into a part of the methyl group of dimethylpolysiloxane. Examples of denaturation include, but are particularly limited to, denaturation of polyether, methylstyrene, alcohol, alkyl, aralkyl, fatty acid ester, epoxy, amine, amino, mercapto and the like. is not it. These degeneration methods may be used in combination. Further, among them, a polyether-modified polysiloxane compound is preferable from the viewpoint of improving ejection stability in inkjet.
Examples of the polyether-modified polysiloxane compound include SILWET L-7604, SILWET L-7607N, SILWET FZ-2104, SILWET FZ-2161 (manufactured by Nippon Unicar Co., Ltd.), BYK306, BYK307, BYK331, BYK333, BYK347. , BYK348, etc. (manufactured by BYK Chemie), KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, Examples thereof include KF-6020, X-22-6191, X-22-4515, KF-6011, KF-6012, KF-6015, and KF-6017 (manufactured by Shin-Etsu Chemical Co., Ltd.).
Among these, a silicone-based surfactant is preferably mentioned as the surfactant.
The content of the surfactant in the second undercoat composition is appropriately selected depending on the purpose of use, but is preferably 0.0001% by mass to 5% by mass, preferably 0.001% by mass, based on the total mass of the composition. More preferably, it is by mass% to 2% by mass.

-Other ingredients-
In the present disclosure, the second undercoat composition is, if necessary, a cosensitizer, an ultraviolet absorber, an antioxidant, an antioxidant, a conductive salt, a solvent, a polymer compound, in addition to the above components. It may contain a basic compound or the like. As these other components, known components can be used, and examples thereof include those described in JP-A-2009-22416.

In addition, the second undercoat composition may contain a polymerization inhibitor from the viewpoint of storage stability and suppression of clogging of the inkjet head.
The content of the polymerization inhibitor is preferably 200 ppm to 20,000 ppm with respect to the total mass of the composition.
Polymerization inhibitors include nitroso-based polymerization inhibitors, hindered amine-based polymerization inhibitors, hydroquinone, benzoquinone, p-methoxyphenol, 2,2,6,6-tetramethylpiperidin 1-oxyl (TEMPO), 4-hydroxy-. 2,2,6,6-tetramethylpiperidin 1-oxyl (TEMPOL), cuperon Al and the like can be mentioned.

-Physical characteristics of the second undercoat composition-
In the present disclosure, when the second undercoat layer is provided by the inkjet method, the viscosity of the second undercoat composition at 25 ° C. is preferably 40 mPa · s or less, preferably 5 to 40 mPa · s, in consideration of ejection properties. s, more preferably 7 to 30 mPa · s. Further, the viscosity at the discharge temperature (preferably 25 to 80 ° C., more preferably 25 to 50 ° C.) is preferably 3 to 15 mPa · s, and more preferably 3 to 13 mPa · s. It is preferable to appropriately adjust the composition ratio of the second undercoat composition so that the viscosity is within the above range. By setting the viscosity at room temperature (25 ° C.) high, even when a porous recording medium (support) is used, the penetration of the second undercoat composition into the recording medium is avoided, and the uncured monomer is prevented. Can be reduced.
The viscosity of the second undercoat composition is measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.).

The surface tension of the second undercoat composition at 25 ° C. is preferably 15 mN / m to 40 mN / m, more preferably 20 mN / m to 35 mN / m, and 20 mN / m to 30 mN / m. Is even more preferable.
As a method for measuring the surface tension of the second undercoat composition at 25 ° C., a known method can be used, but it is preferable to measure the surface tension by the ring method or the Wilhelmy method. For example, a method of measuring using an automatic surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd. or a method of measuring using SIGMA702 manufactured by KSV INSTRUMENTS LTD is preferable.

-Preparation of second undercoat composition-
As the method for preparing the second undercoat composition, each component can be prepared by stirring and mixing.
Here, when preparing the undercoat solution, all the components contained in the undercoat solution may be stirred and mixed at the same time, or a solution in which each component other than the isocyanate compound and / or the radical polymerization initiator is stirred and mixed is stored. , Isocyanate compounds and / or radical polymerization initiators may be added before use to prepare an undercoat solution.
In the inkjet recording method according to the present disclosure, it is preferable that the second undercoat composition is applied to a recording medium within one day after preparation from the viewpoint of coatability.

<< Ink composition >>
The ink composition used in the inkjet recording method according to the present disclosure contains a radically polymerizable monomer, a radical polymerization initiator, and a colorant.
From the viewpoint of curability, the total content of the radically polymerizable monomer in the ink composition is preferably 70% by mass to 98% by mass, and more preferably 70% by mass to 95% by mass. , 80% by mass to 93% by mass, more preferably.
Further, from the viewpoint of curability and heat resistance, the content of the polyfunctional ethylenically unsaturated compound with respect to the total content of the radically polymerizable monomer in the ink composition is preferably 70% by mass or more, and is 70. It is more preferably from mass% to 100% by mass, and more preferably from 80% by mass to 100% by mass.
In addition, the radically polymerizable monomer and the radical polymerization initiator are synonymous with the radically polymerizable monomer and the radical polymerization initiator in the second undercoat composition, and the preferred embodiments are also the same. Further, it is preferable to contain a polyalkylene glycol diacrylate as the polyfunctional ethylenically unsaturated compound (more preferably, the polyfunctional ethylenically unsaturated monomer).
The polyalkylene glycol diacrylate is preferably polyethylene glycol diacrylate or polypropylene glycol diacrylate.
Further, the number of repetitions of the alkylene glycol unit in the polyalkylene glycol diacrylate, that is, the number of repetitions of the alkyleneoxy group is 2 or more, preferably 2 to 100, and more preferably 2 to 20.
The second undercoat composition and the ink composition each preferably contain a bifunctional (meth) acrylate compound.
Further, in the present disclosure, the ink composition is an active photocurable ink composition, which is different from the water-based ink composition and the solvent ink composition. The ink composition preferably contains as little water and a volatile solvent as possible, and even if it does, it preferably contains 1% by mass or less, and 0.5% by mass or less, based on the total mass of the ink composition. It is more preferable that it is 0.1% by mass or less.

-Colorant-
In the present disclosure, the ink composition contains a colorant in order to improve the visibility of the formed image portion.
The colorant is not particularly limited, but pigments and oil-soluble dyes having excellent weather resistance and excellent color reproducibility are preferable, and known colorants such as soluble dyes can be arbitrarily selected and used. As the colorant, it is preferable to select a compound that does not function as a polymerization inhibitor from the viewpoint of not lowering the sensitivity of the curing reaction by active radiation.

The pigments that can be used in the present disclosure are not particularly limited, but for example, organic or inorganic pigments having the following numbers described in the color index can be used.
Pigment Red 3,5,19,22,31,38,42,43,48: 1,48: 2,48: 3,48: 4,48: 5,49: 1,53 as red or magenta pigments : 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, as a blue or cyan pigment, Pigment Blue 1,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,17-1,22 27,28,29,36,60, Pigment Green 7,26,36,50 for green pigments, Pigment Yellow 1,3,12,13,14,17,34,35,37, for yellow pigments, 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, Pigment Black 7, 28, 26 can be used as the black pigment, and Pigment White 6, 18, 21 and the like can be used as the white pigment, depending on the purpose.
In the present disclosure, disperse dyes can also be used as long as they are soluble in water-immiscible organic solvents. The disperse dye generally includes a water-soluble dye, but in the present disclosure, it is preferable to use the disperse dye as long as it is soluble in a water-immiscible organic solvent.
Preferred specific examples of the disperse dye include C.I. I. (Color Index) Disperse Yellow 5,42,54,64,79,82,83,93,99,100,119,122,124,126,160,184: 1,186,198,199,201,204 , 224 and 237; C.I. I. Dispers Orange 13,29,31: 1,33,49,54,55,66,73,118,119 and 163; C.I. I. Dispers Red 54,60,72,73,86,88,91,92,93,111,126,127,134,135,143,145,152,153,154,159,164,167: 1,177 , 181,204,206,207,221,239,240,258,277,278,283,311,323,343,348,356 and 362; C.I. I. Dispers Violet 33; C.I. I. Disperse Blue 56,60,73,87,113,128,143,148,154,158,165,165: 1,165: 2,176,183,185,197,198,201,214,224,225 , 257, 266, 267, 287, 354, 358, 365 and 368; and C.I. I. Disperse greens 6: 1 and 9; and the like.

It is preferable that the colorant is appropriately dispersed in the ink composition after being added to the ink composition. For the dispersion of the colorant, for example, each dispersing 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, and a paint shaker can be used.

The colorant may be added directly together with each component in the preparation of the ink composition. Further, in order to improve dispersibility, it may be added to a solvent or a dispersion medium such as the polymerizable compound used in the present disclosure in advance, uniformly dispersed or dissolved, and then blended.
In the present disclosure, the colorant is polymerizable in order to avoid deterioration of solvent resistance when the solvent remains in the cured image and the problem of VOC (Volatile Organic Compound) of the remaining solvent. It is preferable to add it in advance to a dispersion medium such as a compound and blend it. From the viewpoint of dispersion suitability only, it is preferable to select a monomer having a low viscosity as the polymerizable compound used for adding the colorant. As the colorant, one kind or two or more kinds may be appropriately selected and used depending on the purpose of use of the ink composition.

When a colorant such as a pigment that remains solid in the ink composition is used, the average particle size of the colorant particles is preferably 0.005 μm to 0.5 μm, more preferably 0.01 μm to. It is preferable to set the colorant, the dispersant, the dispersion medium, the dispersion conditions, and the filtration conditions so that the thickness is 0.45 μm, more preferably 0.015 μm to 0.4 μm. This particle size control is preferable because clogging of the head nozzle can be suppressed and the storage stability, transparency and curing sensitivity of the ink composition can be maintained.
The content of the colorant in the ink composition is appropriately selected depending on the color and the purpose of use, but is preferably 0.01% by mass to 30% by mass with respect to the total mass of the ink composition.

-Other ingredients-
The ink composition used in the present disclosure may contain a dispersant, a surfactant, and other components.
The dispersant, surfactant, and other components in the ink composition are synonymous with the dispersant, surfactant, and other components in the second undercoat composition, as are preferred embodiments.

-Physical characteristics of the ink composition-
In the present disclosure, it is preferable to use an ink composition having a viscosity at 25 ° C. of 40 mPa · s or less in consideration of ejection property. It is more preferably 5 mPa · s to 40 mPa · s, and even more preferably 7 mPa · s to 30 mPa · s. Further, the viscosity at the discharge temperature (preferably 25 ° C to 80 ° C, more preferably 25 ° C to 50 ° C) is preferably 3 Pa · s to 15 mPa · s, and is preferably 3 Pa · s to 13 mPa · s. More preferred. It is preferable to appropriately adjust the composition ratio of the ink composition so that the viscosity is within the above range. By setting the viscosity at room temperature (25 ° C.) high, it is possible to reduce the amount of uncured monomers. Further, it is possible to suppress ink bleeding when the ink composition is landed by droplets, and as a result, the image quality is improved, which is preferable.

The surface tension of the ink composition at 25 ° C. is preferably 20 mN / m or more and 40 mN / m or less, more preferably 20.5 mN / m or more and 35.0 mN / m or less, and 21 mN / m or more and 30. It is more preferably 0 mN / m or less, and particularly preferably 21.5 mN / m or more and 28.0 mN / m or less. Within the above range, a printed matter having excellent blocking suppression can be obtained.

(Printed matter)
The printed matter according to the present disclosure is preferably a printed matter obtained by the inkjet recording method according to the present disclosure.
Further, since the printed matter according to the present disclosure is excellent in heat resistance and adhesion, it can be suitably used in the method for producing a laminated printed matter according to the present disclosure, which will be described later.
The shape of the printed matter and the image to be formed according to the present disclosure are not particularly limited and may be appropriately selected as desired.
Further, the printed matter according to the present disclosure may be a printed matter having an image including a barcode.

(Manufacturing method of laminated printed matter and laminated printed matter)
The method for producing a laminated printed matter according to the present disclosure includes a step of heat-bonding the printed matter obtained by the inkjet recording method according to the present disclosure and a resin base material.
In addition, the laminated printed matter according to the present disclosure is manufactured by the method for manufacturing the laminated printed matter according to the present disclosure.
As the laminated printed matter, a packaged printed matter is preferably mentioned, and a blister package (blister pack) is more preferably mentioned. Further, as the blister package, PTP (press through pack), which allows the drug to be easily taken out, is preferably mentioned.

The size and thickness of the resin base material are not particularly limited, and may be appropriately selected according to the intended use of the laminated printed matter to be produced and the printed matter to be used.
The material of the resin base material is not particularly limited, and examples thereof include polyester resin, polyvinyl chloride, and polystyrene.
Further, the resin base material can form pockets by heat-treating the resin base material using a mold in a blister packaging machine, for example. The size and shape of the pocket are not particularly limited and may be appropriately selected as desired.
The content of the blister package is preferably a product that can be deteriorated by contact with the outside air, and is preferably a pharmaceutical product. In addition to pharmaceutical products, foods, cosmetics, medical devices, electronic components and the like can also be mentioned. In addition, the above-mentioned preparations include detergents, pesticides and the like in addition to pharmaceutical preparations (pharmaceuticals).

Further, the resin base material may have an adhesive layer, if necessary.
The adhesive layer is not particularly limited and can be formed by applying a known adhesive by a known method.

Regarding the heat applied in the bonding step, from the viewpoint of adhesion, it is preferable to apply heat of 160 ° C. or higher to the bonding portion, and heat of 160 ° C. or higher and 280 ° C. or lower may be applied to the bonding portion. More preferred.
Further, in the above-mentioned bonding step, it is preferable to crimp. The pressure applied at the time of crimping is not particularly limited, and may be appropriately selected depending on the printed matter, the resin base material, and the like to be used.
The time for applying heat is also not particularly limited and may be appropriately selected depending on the printed matter and the resin base material to be used, but is preferably 0.5 seconds to 10 seconds.
The bonding means and heating means used in the bonding step are not particularly limited, and known bonding means and known heating means can be used.

Further, the method for producing a laminated printed matter according to the present disclosure is such that after the laminating step, for example, in the blister package, it can be easily separated in a region including one or a plurality of pockets (blisters). It may have a step of forming a separation line in the obtained laminated printed matter.
The shape of the separating line is not particularly limited and may be any known shape.

Hereinafter, the present disclosure will be described in detail by way of examples, but the present disclosure is not limited thereto. In this embodiment, "%" and "parts" mean "mass%" and "parts by mass", respectively, unless otherwise specified.

The materials used in this disclosure are as shown below.

<Colorant>
・ IRGALITE BLUE GLVO (cyan pigment, manufactured by BASF Japan Ltd.)
・ CINQUASIA MAGENTA RT-355-D (magenta pigment, manufactured by BASF Japan Ltd.)
・ NOVOPERM YELLOW H2G (yellow pigment, manufactured by Clariant)
・ SPECIAL BLACK 250 (black pigment, manufactured by BASF Japan Ltd.)
・ Typake CR60-2 (white pigment, manufactured by Ishihara Sangyo Co., Ltd.)

<Dispersant>
・ SOLSERSE32000 (Noveon dispersant)

<Radical polymerizable monomer>
SR9003: Propoxylation (2) Neopentyl glycol diacrylate (manufactured by Sartomer)
SR341: 3-Methyl-1,5-pentanediol diacrylate (manufactured by Sartomer)
-SR489D: Tridecyl acrylate (manufactured by Sartomer)
-DVE-3: Triethylene glycol divinyl ether (manufactured by BASF)
SR344: Polyethylene glycol (400) diacrylate (manufactured by Sartomer)

<Radical polymerization initiator>
-IRGACURE 819 (bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, manufactured by BASF, molecular weight 419)
-Speedcure 7010L (manufactured by Rambson, molecular weight 1,899)

<Isocyanate compound>
・ TM550 (NCO type urethane ester resin, manufactured by Toyo Morton Co., Ltd.)
-Takenate D160N (Adduct of hexamethylene diisocyanate and trimethylolpropane, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.)
-Takenate D170N (isocyanurate of hexamethylene diisocyanate, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.)
-Takenate D178NL (alofanate of hexamethylene diisocyanate, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.)
-Takenate D110N (Adduct of xylylene diisocyanate and trimethylolpropane, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.)

<Urethane oligomer>
-UV7630B (urethane acrylate, purple light UV-7630B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)

<Polymerization inhibitor>
UV-22 (Irgastab® UV-22, Poly [oxy (methyl-1,2-ethanediyl)]-α, α', α ”-1,2,3-propanetriyltris [ω-[(1-) oxo-2-propen-1-yl) oxy] -2,6-bis (1,1-dimethylethyl) -4- (phenylenemethylene) cyclohexa-2,5-dien-1-one, manufactured by BASF)

<Surfactant>
BYK-307 (Silicone-based surfactant (polyether-modified polydimethylsiloxane), manufactured by BYK Chemie)

<Mixed resin of epoxy resin and melamine resin (epoxy / melamine mixed resin)>
・ PT-OP varnish (containing epoxy resin and melamine resin, manufactured by T & K TOKA Co., Ltd.)
・ OP20 # H Clear (containing epoxy resin and melamine resin, manufactured by Osaka Printing Ink Mfg. Co., Ltd.)
・ ADZ Clear (containing epoxy resin and melamine resin, manufactured by T & K TOKA Co., Ltd.)
・ YL432 PTP OP varnish (containing epoxy resin and melamine resin, manufactured by Toyo Ink Co., Ltd.)

<Acrylic resin>
・ Acrydic A-322 (Acrylic resin, manufactured by DIC Corporation)
・ JONCRYL 901 (Acrylic resin, manufactured by DIC Corporation)
・ Dianar SE-5650 (Acrylic resin, manufactured by DIC Corporation)

<Fiber resin>
・ DHX4-6 (nitrocellulose, manufactured by Nobel NC)
-CAB-381-2 (Cellulose Acetate, manufactured by Eastman)
-CAP-482-20 (Cellulose Acetate Propionate, manufactured by Eastman)

<Pigment>
-Titanium oxide (CR-Super 70, manufactured by Ishihara Sangyo Co., Ltd., average particle size: 0.25 μm to 0.30 μm)

<Organic solvent>
・ Methyl ethyl ketone (MEK, manufactured by Daishin Chemical Co., Ltd.)
・ Toluene (manufactured by Daishin Chemical Co., Ltd.)
・ Propylene glycol monomethyl ether (PM, manufactured by Daishin Chemical Co., Ltd.)

<Preparation of Cyan Mill Base A>
300 parts by mass of IRGALITE BLUE GLVO, 620 parts by mass of SR9003, and 80 parts by mass of SOLPERSE32000 were stirred and mixed to obtain a cyan mill base A. The cyan mill base A was prepared by putting it in a disperser motor mill M50 (manufactured by Eiger) and dispersing it at a peripheral speed of 9 m / s for 4 hours using zirconia beads having a diameter of 0.65 mm.

<Preparation of magenta mill base B, yellow mill base C, black mill base D and white mill base E>
In the same manner as the cyan mill base A, magenta mill base B, yellow mill base C, black mill base D and white mill base E were prepared under the composition and dispersion conditions shown in Table 1.

(Examples 1 to 25 and Comparative Examples 1 to 8)
<Preparation of the first undercoat composition>
Each material was stirred and mixed at the ratios shown in Tables 2 to 4 to prepare the first undercoat compositions used in Examples 1 to 25 and Comparative Examples 1 to 8, respectively. The unit of the content of each component in Tables 2 to 4 is parts by mass. Further, the description of "-" in Tables 2 to 4 means that the above-mentioned component is not contained. The amount of the epoxy / melamine mixed resin shown in Tables 2 to 4 is the total content of the epoxy resin and the melamine resin. For example, in Example 1, the epoxy / melamine mixed resin contained in the PT-OP varnish. The amount as.

<Preparation of second undercoat composition and ink composition>
Each material was stirred and mixed at room temperature (25 ° C.) at 5,000 rpm for 20 minutes using a mixer (L4R manufactured by Silberson) at the ratios shown in Tables 2 to 4, and Examples 1 to 25. The second undercoat composition and the ink composition used in Comparative Examples 1 to 8 were prepared. The second undercoat composition used in Comparative Example 2 was stored at room temperature (25 ° C.) for one day until it was used in the experiment. The unit of the content of each component in Tables 2 to 4 is parts by mass. Further, the description of "-" in Tables 2 to 4 means that the above-mentioned component is not contained.

<Manufacturing of laminated body>
The first undercoat composition is applied onto the aluminum foil base material shown below under the conditions shown below, and is thermoset under the drying conditions shown below to have the first undercoat layer on the aluminum foil base material. Laminates were prepared respectively.

-Aluminum foil base material-
Base material thickness: 20 μm
Base material number: 1N30 (JIS H 4000)
Quality: H18 (JIS H 4000)

-Manufacturing conditions for a laminate having a first undercoat layer on an aluminum foil substrate-
Coating method: Gravure Coating amount: 2g / m ²
Drying method: Hot air drying furnace: A three-zone drying furnace having a furnace length of 3 m at 100 ° C., 180 ° C., and 270 ° C. was used.
Processing speed: 100 m / min

<Inkjet recording method>
As shown in FIG. 1, a roller coating machine (coating amount of the second undercoat composition: 2 g / m ² (coating film thickness 2 μm)) is arranged at the most upstream portion of the roll transport system, and an LED light source is provided downstream thereof. A black head, an LED light source, a cyan head, an LED light source, a magenta head, an LED light source, a W head, and a nitrogen purge LED exposure machine were arranged.
As inkjet heads, four CA3 heads manufactured by TOSHIBA TEC CORPORATION were arranged in parallel for each color, the heads were heated to 45 ° C., and the frequency was controlled so that drawing could be performed with a droplet size of 42 pL. As the LED light source, an LED light source unit having a peak wavelength of 385 nm (LED Zero Solidcure, manufactured by Integration Technology Co., Ltd.) was used. Nitrogen purge, as the inert gas source, a compressor with _{N 2} gas generating apparatus Maxi-Flow30 the (Inhouse Gas Co., Ltd.) connected with a pressure of 0.2 MPa · s, the nitrogen concentration in the blanket 99.9 vol% Nitrogen was flown at a flow rate of 2 L / min to 10 L / min so that the oxygen concentration was 0.1% by volume or less, and the nitrogen concentration was set.
Scanning was performed at a speed of 50 m / min, and a second undercoat layer was formed on a laminate having the first undercoat layer on the obtained aluminum foil base material, and an LED light source (light amount 30 mJ / cm ² for semi-curing) was formed. The second undercoat layer was semi-cured using. The ink composition was ejected onto the ink composition, and the ink composition was further semi-cured ^{using an LED light source (light amount 10 mJ / cm 2} for semi-curing), and the image shown below was drawn. Then, the image was completely cured by the LED light source so that the integrated light amount was shown in Tables 2 to 4. The following performance tests were performed.
The amount of light of the LED light source before the nitrogen purge exposure was adjusted so that the second undercoat layer and the ink composition could be kept in a semi-cured state.
The term "completely cured" in the present disclosure means a state in which the inside and the surface of the second undercoat layer and the ink composition are completely cured. Specifically, plain paper (for example, copy paper C2 manufactured by Fuji Xerox Co., Ltd., product code V436) is pressed against a uniform force (a constant value within the range of ^{500 mN / cm 2 to} 1,000 mN / cm ^2). Therefore, it can be judged by whether or not the liquid surface is transferred to plain paper. That is, the case where no transfer is performed is called a completely cured state.

-Drawn image-
〔letter〕
The characters "on-demand PTP" with a character height of 3 mm and the characters "extrude" with a character height of 1.5 mm were drawn.
〔barcode〕
The GSI data bar (minimum element width: 0.254 mm), which is the barcode shown in FIG. 2, has a character height of 1 mm for the number of the barcode, a height of 3 mm for the black line portion of the barcode, and the entire horizontal direction of the barcode. It was drawn with a width of 18.5 mm.

<Heat resistance evaluation>
Using an FBP-300E manufactured by CKD, which is a blister packaging machine that wraps medicines one by one in a pocket, the unit of the numerical value of the length in FIG. 3 is mm. A mold with a lattice pattern of about 8 mm (width of the mold part forming the lattice: 0.1 mm to 0.3 mm) is pressed, the temperature is 190 ° C to 280 ° C, the maximum machine pressure is 0.48 MPa, 0.2 m / sec. Sealing was performed under (filling low speed condition 100 shots) to obtain a laminated printed matter. A cellophane tape of 2.4 mm was strongly attached to the character portion and the barcode portion formed above on the printed surface of the obtained laminated printed matter, and the cells were peeled off at once to determine the quality of adhesion. If the ink film does not adhere to the peeled tape, it is passed.
Of the conditions that can be achieved by the machine, the harshest conditions were implemented. The evaluation was made as follows according to the highest temperature (heat resistant temperature (filling temperature)) among the passed temperatures.
Even if the above evaluation was performed at 5: 280 ° C., it was acceptable.
4: The heat resistant temperature was 250 ° C. or higher and lower than 280 ° C.
3: The heat resistant temperature was 220 ° C. or higher and lower than 250 ° C.
2: The heat resistant temperature was 190 ° C. or higher and lower than 220 ° C.
1: The heat resistant temperature was less than 190 ° C.

<Barcode readability>
In the heat-resistant adhesion evaluation, the laminated printed matter sealed at 280 ° C. was evaluated based on the ISO / IEC 15416/15415 standard (step evaluation of A to D and F according to the following eight judgment items). Bar code readability was evaluated. If the comprehensive judgments described later are A to D, there is no problem in practicality.

-Judgment item-
1: Element / Edge
2: Decode
3: Decodability
4: Reflectance Minimum
5: Symbol Control
6: Ecmin
7: Modulation
8: Defects

-Laser barcode reading evaluation-
The above-mentioned determination items were evaluated for each of the obtained laminated printed matter under the following laser code reading conditions.
Measuring device: TruCheck TC-843 manufactured by WEBSCAN
Measuring method: The laminated printed matter was placed on a flat surface so as not to cause wrinkles, and the measuring instrument was measured on it.
Judgment items: The above eight types of judgment items were evaluated.
Measurement aperture diameter: 6 mil
Evaluation of each judgment item: Read 10 times, average the obtained numerical results, and judge by A to F according to the standard of IEC 15416/15415.

-Camera-type barcode reading evaluation-
The above-mentioned determination items were evaluated for the obtained laminated printed matter under the following camera-type barcode reading conditions.
Measuring device: LVS INTEGRA 9510
Measuring method: The laminated printed matter was measured by closing the lid on the measuring machine so as not to cause wrinkles.
Judgment items: The above eight types of judgment items were evaluated.
Evaluation of each judgment item: Read 10 times, average the obtained numerical results, and judge by A to F according to the standard of IEC 15416/15415.

-Comprehensive judgment-
Of the laser type and camera type evaluation results, the worst judgment result was adopted as the comprehensive judgment.
A: Best B: Excellent C: Good D: Possible F: Not possible

The evaluation results are summarized in Tables 2 to 4.

As is clear from the results in Tables 2 to 4, the inkjet recording method according to the present disclosure shown in Examples 1 to 25 provides a printed matter having excellent heat resistance and adhesion as compared with the inkjet recording method in Comparative Examples 1 to 8. It turns out that it can be done.
Further, as is clear from the results of Tables 2 to 4, the inkjet recording method according to the present disclosure shown in Examples 1 to 25 is excellent in barcode readability even when a laminated printed matter is formed.

Since the aluminum base material has high reflectance and diffuse reflection, as shown in Examples 1, 21 and 22 of Tables 2 and 3, when the first undercoat layer contains a colorant, the hiding property is improved and the difference in brightness is improved. Is large, and the barcode is excellent in readability.
As shown in Examples 23 to 25 of Table 3, in the step of irradiating with ultraviolet rays and curing, a printed matter obtained when the ^{integrated light amount is preferably 420 mJ / cm 2} or more, more preferably 440 mJ / cm ^{2 or more.} Excellent in heat and adhesion.

12: Recording medium, 14: Second undercoat composition coating roller, 17: Second undercoat composition semi-curing exposure light source, 18K, 18C, 18M, 18Y, 18W: Inkjet head, 20K, 20C, 20M, 20Y : Semi-curing exposure light source, 22: Nitrogen purge exposure light source unit, 24: Feeding roller, 26: Winding roller, 28: Nip roll

Claims (10)

A step of preparing a laminate having an aluminum foil base material and a first undercoat layer on the aluminum foil base material,
A step of forming a second undercoat layer on the first undercoat layer in the laminate with a second undercoat composition,
A step of ejecting an ink composition onto the second undercoat layer by an inkjet method, and
The ejected ink composition is cured by irradiating the ^{ejected ink composition with ultraviolet rays having an integrated light intensity of 400 mJ / cm 2} or more in an atmosphere of an oxygen concentration of 0.1% by volume or less by an ultraviolet light emitting diode.
The first undercoat layer contains a thermosetting resin, an acrylic resin, and a fibrin-based resin.
The second undercoat composition comprises a compound having an isocyanate group, a radically polymerizable monomer, and a radical polymerization initiator.
An inkjet recording method in which the ink composition contains a radically polymerizable monomer, a radical polymerization initiator, and a colorant. The inkjet according to claim 1, wherein the thermosetting resin contained in the first undercoat layer contains a resin obtained by curing at least one resin selected from the group consisting of an epoxy resin and a melamine resin. Recording method. The inkjet recording method according to claim 1 or 2, wherein the thermosetting resin contained in the first undercoat layer contains a resin obtained by curing an epoxy resin and a melamine resin. The content of the polyfunctional ethylenically unsaturated compound with respect to the total content of the radically polymerizable monomer in the second undercoat composition is 70% by mass or more and is
The inkjet recording according to any one of claims 1 to 3, wherein the content of the polyfunctional ethylenically unsaturated compound with respect to the total content of the radically polymerizable monomer in the ink composition is 70% by mass or more. Method. Any of claims 1 to 4, which includes a step of irradiating the second undercoat layer with ultraviolet rays to semi-cure the second undercoat layer between the step of forming the second undercoat layer and the step of ejecting the ink composition. The inkjet recording method according to item 1. Claims 1 to 5 include a step of irradiating the ink composition with ultraviolet rays to semi-cure the ink composition between the step of ejecting the ink composition and the step of irradiating the ink composition with the curing step. The inkjet recording method according to any one item. The inkjet recording method according to any one of claims 1 to 6, wherein an image including a barcode is formed in the step of ejecting the ink composition. The inkjet recording method according to any one of claims 1 to 7, wherein the first undercoat layer further contains a colorant. A method for producing a laminated printed matter, which comprises a step of heat-bonding the printed matter obtained by the inkjet recording method according to any one of claims 1 to 8 and a resin base material. The method for producing a laminated printed matter according to claim 9, wherein heat of 160 ° C. or higher is applied to the bonded portion in the bonding step.

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