WO2019087807A1

WO2019087807A1 - Ink-jet recording method and laminated body

Info

Publication number: WO2019087807A1
Application number: PCT/JP2018/038893
Authority: WO
Inventors: 梅林　励
Original assignee: 富士フイルム株式会社
Priority date: 2017-11-02
Filing date: 2018-10-18
Publication date: 2019-05-09

Abstract

The present invention provides: an ink-jet recording method comprising a step for forming a colored image by imparting, by means of an ink-jet method, a colorant-containing coloring ink onto a recording medium that contains a urethane resin and/or a vinyl chloride resin, and a step for forming, at least on the colored image, a clear-ink layer by imparting a clear ink containing a vinyl chloride-vinyl acetate copolymer; and a laminated body.

Description

Ink jet recording method and laminate

The present disclosure relates to an inkjet recording method and a laminate.

Conventionally, various studies have been made on the ink jet recording method.
For example, in the following Patent Document 1, an image is formed by discharging an effect pigment ink onto a recording medium as an ink jet recording method in which an image excellent in metallic feeling (glint) and excellent in abrasivity is obtained. The image forming process, the transparent ink applying process for applying the transparent ink on the recording medium, and the curing process for curing the effect pigment ink and the transparent ink on the recording medium in this order, the image forming process and the transparent ink Between the application step, there is no step of curing the effect pigment ink, or, in the case of having the effect pigment ink curing rate is 85% or less, the transparent ink contains a polymerization initiator, and The effect pigment ink containing an organic compound and substantially free of a pigment is disclosed as an ink jet recording method containing an effect pigment, a polymerization initiator, and a polymerizable compound.

Further, Patent Document 2 below shows an image obtained by overlapping a plurality of inks, wherein water is used as a recording medium as an ink jet recording method capable of forming an image in which bleeding and cracking are suppressed. Forming a first ink layer by ejecting a first ink composition containing a water-soluble organic solvent and a solid content containing at least a coloring material by an inkjet method; and a first ink composition in the first ink layer Solid content containing at least water, a water-soluble organic solvent, and a coloring material on the first drying step of evaporating 80% by mass or more of the water contained in the ink, and the first ink layer subjected to the first drying step And a second drying step of evaporating volatile components on the recording medium after the steps of forming the second ink layer by discharging the second ink composition including the ink composition by an inkjet method, and forming the second ink layer. And [1] When “water-soluble organic solvent content / solid content” of the ink composition is “r1” and “water-soluble organic solvent content / solid content” of the second ink composition is “r2” An inkjet recording method is disclosed in which the value of “r2 / r1” is 2 or less.

Further, Patent Document 3 below discloses a composition set having high abrasion resistance and capable of providing a recorded matter excellent in odor reducing properties and image quality, and an ink jet recording method using the same.
Patent Document 3 discloses a radiation curable ink jet coloring composition containing a coloring material and a monomer A having a specific structure as a polymerizable compound as the above composition set; a heterocyclic group and a saturated fat as a polymerizable compound A radiation curable inkjet clear composition comprising (meth) acrylic acid esters B, which is a monofunctional polymerizable compound having an ether structure of at least one of a group ether group, is disclosed.

Patent Document 1: Japanese Unexamined Patent Application Publication No. 2012-210764 Patent Document 2: Japanese Unexamined Patent Application Publication No. 2017-109485 Patent Document 3: Japanese Unexamined Patent Application Publication No. 2017-078133

By the way, there are cases where a colored image is formed by an inkjet method for the purpose of decoration or the like on a recording medium such as a resin base material. In this case, for the purpose of protection of the formed colored image, etc., the laminate substrate may be heat-fused on the colored image. The heat-sealed body having a laminated structure of laminate base material / colored image / recording medium obtained by heat-sealing is, for example, a floor material or wall material of transportation equipment (railway, bus, etc.), floor material of building or It is used as a wall material, etc.
However, in the heat-sealed body, peeling between the recording medium and the laminate base (for example, interfacial peeling between the laminate base and the colored image) may be a problem.

An object of one aspect of the present disclosure is a laminate including, on a recording medium, a colored image which is an inkjet recording material and a clear ink layer disposed at least on the colored image, the clear ink layer An ink jet recording method capable of producing a laminate excellent in peel strength between a recording medium and a laminate substrate when the laminate substrate is heat-fused.
An object of another aspect of the present disclosure is a laminate including a colored image which is an ink jet recording material and a clear ink layer disposed at least on the colored image on a recording medium, and the clear ink layer An object of the present invention is to provide a laminate excellent in peel strength between a recording medium and a laminate base when the laminate base is heat-fused.

Specific means for solving the problems include the following aspects.
<1> A step of forming a colored image by applying a coloring ink containing a coloring agent by an inkjet method on a recording medium containing at least one of a urethane resin and a vinyl chloride resin;
Applying a clear ink containing a vinyl chloride-vinyl acetate copolymer on at least a colored image to form a clear ink layer;
An inkjet recording method comprising:
<2> The inkjet recording method according to <1>, further comprising the step of thermally fusing a laminate substrate containing at least one of a urethane resin and a vinyl chloride resin on the clear ink layer.
<3> The ink jet recording method according to <2>, wherein the heat fusion temperature in the heat fusion step is 150 ° C. to 220 ° C.
The content of the vinyl chloride-vinyl acetate copolymer contained in <4> clear ink is 0.5% by mass to 10.0% by mass with respect to the total amount of clear ink <1> to <3> The inkjet recording method according to any one.
The total content mass of the non-volatile component contained in <5> clear ink is set to Mt1,
Assuming that the content mass of the vinyl chloride-vinyl acetate copolymer contained in the clear ink is Mt2.
The inkjet recording method according to any one of <1> to <4>, wherein Mt2 / Mt1 is 0.40 or more.
<6> The inkjet recording method according to any one of <1> to <5>, wherein the weight average molecular weight of the vinyl chloride-vinyl acetate copolymer contained in the clear ink is 13,000 to 30,000.
<7> The inkjet recording method according to any one of <1> to <6>, wherein the colored ink further contains at least one of a vinyl chloride-vinyl acetate copolymer and a polymerizable compound.
<8> The colored ink contains a vinyl chloride-vinyl acetate copolymer,
The ink jet recording method according to <7>, wherein the weight average molecular weight of the vinyl chloride-vinyl acetate copolymer contained in the colored ink is 13,000 to 30,000.
<9> The colored ink contains a vinyl chloride-vinyl acetate copolymer,
The total content of non-volatile components contained in the clear ink is Mt1
Let the content mass of the vinyl chloride-vinyl acetate copolymer contained in the clear ink be Mt2.
The total content mass of the non-volatile components contained in the colored ink is Mc1
When the content mass of the vinyl chloride-vinyl acetate copolymer contained in the colored ink is Mc2,
The inkjet recording method according to <7> or <8>, wherein Mt1, Mt2, Mc1 and Mc2 satisfy the following formula (1).
Mc2 / Mc1 ≦ Mt2 / Mt1 ... Formula (1)
<10> The inkjet recording method according to any one of <1> to <9>, wherein both the colored ink and the clear ink contain an organic solvent.
<11> A recording medium containing at least one of a urethane resin and a vinyl chloride resin,
A colored image which is disposed on a recording medium and is an inkjet recording material;
A clear ink layer disposed on at least a colored image on a recording medium and containing a vinyl chloride-vinyl acetate copolymer;
Stack comprising.
<12> The laminate according to <11>, further comprising a laminate substrate thermally fused on the clear ink layer and containing at least one of a urethane resin and a vinyl chloride resin.
The laminated body as described in <11> or <12> whose ratio of the content mass of a vinyl chloride-vinyl acetate copolymer with respect to the total mass of a <13> clear ink layer is 0.40 or more.

According to one aspect of the present disclosure, it is a laminate including, on a recording medium, a colored image, which is an inkjet recording material, and a clear ink layer disposed on at least a colored image, the clear ink layer There is provided an ink jet recording method capable of producing a laminate excellent in peel strength between a recording medium and a laminate substrate when the laminate substrate is heat-fused.
According to another aspect of the present disclosure, there is provided a laminate including, on a recording medium, a colored image which is an inkjet recording material and a clear ink layer disposed on at least a colored image, the clear ink layer When the laminate base is heat-fused onto the laminate, a laminate excellent in peel strength between the recording medium and the laminate base is provided.

It is a figure which shows notionally the grid | lattice-like image used for evaluation of the Example. It is a schematic sectional drawing which shows notionally the cross section parallel to the thickness direction and the longitudinal direction in the sample for peeling strength evaluation of an Example.

In the present specification, a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
In the present specification, the amount of each component in the composition is the total amount of the above-mentioned plurality of substances present in the composition unless a plurality of substances corresponding to each component are present in the composition. means.
In the numerical range described step by step in the specification, the upper limit or the lower limit described in a certain numerical range may be replaced with the upper limit or the lower limit in the numerical range described in the other stepwise Also, they may be replaced with the values shown in the embodiments.
In the present specification, the term "process" is included in the term if the intended purpose of the process is achieved, even if it can not be clearly distinguished from other processes, as well as independent processes. .
In the present specification, “(meth) acrylic” is a concept including acrylic and methacrylic, “(meth) acrylate” is a concept including acrylate and methacrylate, and “(meth) acryloyl” is acryloyl. And methacryloyl.
In the present specification, “(poly) alkylene glycol” is a concept including alkylene glycol and polyalkylene glycol, and “(poly) ethylene glycol” is a concept including ethylene glycol and polyethylene glycol, “( “Poly) propylene glycol” is a concept including propylene glycol and polypropylene glycol.
In the present specification, the combination of preferred embodiments is a more preferred embodiment.

[Ink jet recording method]
The ink jet recording method of the present disclosure (hereinafter, also referred to as “the recording method of the present disclosure”) is an ink jet method using a colored ink containing a colorant on a recording medium containing at least one of a urethane resin and a vinyl chloride resin. Forming a colored image, and applying a clear ink containing a vinyl chloride-vinyl acetate copolymer on at least a colored image to form a clear ink layer.

According to the recording method of the present disclosure, a laminate comprising a colored image which is an ink jet recorded matter and a clear ink layer disposed at least on the colored image on a recording medium (that is, clear ink layer / colored image And (laminate) having a layered structure of the recording medium can be manufactured.
When the laminate having the laminated structure of clear ink layer / colored image / recording medium manufactured is produced by heat-sealing the laminate base on the clear ink layer of this laminate (that is, laminate base / clear) When a heat-sealed body having a laminated structure of ink layer / colored image / recording medium is formed, the peel strength between the recording medium and the laminate base is excellent. That is, when the heat-sealed body is formed, peeling between the recording medium and the laminate base is suppressed.

The reason why the above effect is exhibited is presumed as follows. However, the recording method of the present disclosure is not limited by the following estimation reason.
For the above effects, the thermal melting point of the urethane resin and / or vinyl chloride resin contained in the recording medium and the thermal melting point of the vinyl chloride-vinyl acetate copolymer contained in the clear ink are relatively close. It is thought that temperature is related. Thus, a heat-sealed body having a laminated structure of laminate base / clear ink layer / colored image / recording medium obtained by heat-sealing the laminate base on the clear ink layer is laminated with the clear ink layer. If interfacial peeling with the substrate, cohesive failure of the clear ink layer, and interfacial peeling between the clear ink layer and the colored image are suppressed, and as a result, the peel strength between the laminate substrate and the recording medium is improved Conceivable.

According to the recording method of the present disclosure, for example, the problem of interfacial peeling between the laminate base and the colored image, which may be a problem in a laminate having a laminated structure of laminate base / colored image / recording medium, is eliminated. Be done.

As used herein, clear ink refers to an ink substantially free of colorant.
Here, not containing a colorant substantially means that the content of the colorant in the ink is less than 0.5% by mass (more preferably less than 0.1% by mass, particularly preferably 0% by mass). Means

In the present specification, "to thermally fuse a laminate substrate on a clear ink layer" means a laminate having a laminate structure of clear ink layer / colored image / recording medium, and a laminate substrate, It means that it heat-seals in the arrangement | positioning which a layer and a laminate base material contact | connect.

<Step of Forming a Colored Image>
In the recording method of the present disclosure, a step of forming a colored image by applying a coloring ink containing a colorant on a recording medium containing at least one of a urethane resin and a vinyl chloride resin by an inkjet method (hereinafter referred to as “coloring (Also referred to as “image forming step”).
In the colored image forming step, a single colored ink may be used to form a single colored image, or two or more colored inks may be used to form two or more colored images.
The colored ink will be described later.

(Recording medium)
The recording medium contains at least one of a urethane resin and a vinyl chloride resin.
In the recording medium, the total content of the urethane resin and the vinyl chloride resin is preferably 60% by mass, more preferably 80% by mass or more, still more preferably 90% by mass or more, based on the entire recording medium. .
In the recording medium, the total content of the urethane resin and the vinyl chloride resin may be 100% by mass.

The recording medium preferably contains a vinyl chloride resin, and the vinyl chloride resin is contained in an amount of 60% by mass (more preferably 80% by mass or more, still more preferably 90% by mass or more) based on the entire recording medium. Is particularly preferred.

The recording medium may contain other components (known additives for resin, etc.) other than the urethane resin and the vinyl chloride resin.

Further, the recording medium may be colored white, for example.
As a result, the appearance of the colored image formed on the recording medium is improved.
As a colored recording medium,
A recording medium containing at least one of a urethane resin and a vinyl chloride resin, and a colorant (for example, a white pigment);
A recording medium having a multilayer structure including a base material layer containing at least one of a urethane resin and a vinyl chloride resin, and a layer containing a colorant (for example, a white pigment);
Etc.

The shape of the recording medium is not particularly limited, but from the viewpoint of workability of heat fusion when forming a heat fusion body having a laminated structure of laminate base material / clear ink layer / colored image / recording medium And preferably in the form of a sheet.
The thickness of the recording medium in the form of a sheet is not particularly limited, but is preferably 0.1 mm to 20 mm, more preferably 0.2 mm to 10 mm, and particularly preferably 0.5 m to 5 mm.

A commercial item may be used as the recording medium.
As a commercial item of the recording medium, a polyvinyl chloride base “PVC 35 phr” manufactured by Okamoto Corp., a polyurethane leather “Elna (YP 528)” manufactured by Yamaplus Corp., etc. may be mentioned.

In the colored image forming step, a colored ink containing a coloring agent is applied onto the recording medium by an inkjet method to form a colored image.
Needless to say, the application of the colored ink by the inkjet method is performed by discharging the colored ink toward the recording medium from an inkjet head provided in the inkjet recording apparatus.
The ejection conditions such as the ejection amount of the colored ink are not particularly limited, and can be appropriately selected according to the composition, physical properties, and the like of the colored ink to be used.
The ink jet recording apparatus is not particularly limited, and any known ink jet recording apparatus capable of achieving the target resolution can be selected and used. That is, as long as it is a known inkjet recording apparatus including commercial products, any colored ink can be applied by the inkjet method.

The ink supply system provided in the ink jet recording apparatus includes, for example, a source tank containing colored ink, a supply pipe, an ink supply tank immediately before the ink jet head, a filter, and a piezoelectric ink jet head.
The piezo-type ink jet head is preferably 1 pl to 100 pl, more preferably 8 pl to 30 pl multi-size dots, preferably 320 × 320 dpi to 4,000 × 4,000 dpi, more preferably 400 × 400 dpi to 1,600 × It can be driven to be able to eject at a resolution of 1,600 dpi, more preferably 720 × 720 dpi.
The term "dpi (dot per inch)" as used herein refers to the number of dots per 2.54 cm.

In the colored image forming step, preferably, the colored ink applied on the recording medium is dried to form a colored image.
Drying of the colored ink applied onto the recording medium may be air drying or drying by heating, but drying by heating is preferable.
For example, when the colored ink contains an organic solvent described later, it is preferable to dry the colored ink applied on the recording medium by heating (that is, to remove at least a part of the organic solvent from the colored ink) .
The heating temperature in heating is preferably 30 ° C. to 90 ° C., more preferably 50 ° C. to 80 ° C., as the temperature of the recording medium.

When the colored ink contains a polymerizable compound described later, it is preferable to irradiate actinic radiation to the colored ink applied on the recording medium. Irradiation with actinic radiation polymerizes the polymerizable compound in the colored ink on the recording medium, and the colored ink is cured to form an image. Thereby, a colored image excellent in strength is obtained.

As actinic radiation, α rays, γ rays, electron beams, X rays, ultraviolet rays (UV), visible light, infrared light and the like can be used.
The peak wavelength of the actinic radiation is preferably 200 nm to 600 nm, more preferably 300 nm to 450 nm, still more preferably 320 nm to 420 nm, and still more preferably 340 nm to 400 nm.

As an actinic radiation source, a mercury lamp, a metal halide lamp, a gas laser, a solid state laser and the like are widely known.
However, at present there is a strong demand for mercury-free from the viewpoint of environmental protection, and the replacement of the active radiation source exemplified above with a GaN-based semiconductor ultraviolet light emitting device is very useful industrially and environmentally. is there. Furthermore, light emitting diodes (LEDs) and laser diodes (LDs) are small in size, long in life, high in efficiency, low in cost, and are expected as light sources for light curing type inkjets.
It is also possible to use light emitting diodes (LEDs) and laser diodes (LDs) as actinic radiation sources. In particular, when an ultraviolet light source is required, ultraviolet LEDs (hereinafter also referred to as UV-LEDs) and ultraviolet LDs (hereinafter also referred to as UV-LDs) can be used. For example, Nichia Corporation has marketed UV-LEDs whose main emission spectrum has a wavelength between 365 nm and 420 nm. Also, US Pat. No. 6,084,250 discloses a UV-LED capable of emitting actinic radiation centered between 300 nm and 370 nm. Other UV-LEDs are also available that can emit ultraviolet light of a wavelength different from these wavelengths.
The preferred actinic radiation source is a UV-LED. Particularly preferred actinic radiation sources are UV-LEDs having a peak wavelength between 340 nm and 400 nm.

The maximum illumination intensity of the LED on a recording medium ^is preferably 10mW / cm 2 ~ 2000mW / cm 2, more preferably 20mW / cm 2 ~ 1000mW / cm 2, 50mW / cm 2 ~ Particularly preferred is 800 mW / cm ² .
The colored ink of the embodiment containing the polymerizable compound is suitably irradiated with such actinic radiation preferably for 0.01 seconds to 120 seconds, more preferably for 0.1 seconds to 90 seconds.
The irradiation conditions and the basic irradiation method of actinic radiation are disclosed in Japanese Patent Application Laid-Open No. 60-132767.

When curing of the colored ink is performed by irradiation with actinic radiation, curing may be completed by another light source without driving.
WO 99/54415 discloses a method of using an optical fiber as a method of irradiation, and a method of irradiating a UV light to a recording unit by applying a collimated light source to a mirror provided on the side of the head unit. Such curing methods can also be applied to the colored image forming process.

When performing irradiation with actinic radiation in the colored image forming process, an exposure dose of the actinic radiation is ^preferably ^{10mJ / m 2 ~ 1000mJ / m} 2, more preferably ^{100mJ / m 2 ~ 500mJ / m} 2, 200mJ / m 2 ~ 400 mJ / m ² is more preferred.

When the colored ink contains an organic solvent and a polymerizable compound, it is preferable that both heating and actinic radiation be applied to the colored ink applied on the recording medium in the colored image forming step. And actinic radiation is more preferably applied in this order.

<Step of Forming Clear Ink Layer>
In the recording method of the present disclosure, a step of applying a clear ink containing a vinyl chloride-vinyl acetate copolymer on at least a colored image to form a clear ink layer (hereinafter, also referred to as a “clear ink layer forming step”) Have.
In the clear ink layer forming step, the clear ink layer may be formed only on the colored image, or may be formed over the colored image and the non-image forming area.
Here, the non-image forming area refers to an area in which a colored image is not formed in the colored image forming process (that is, an area in which the colored ink is not applied).

The clear ink contains a vinyl chloride-vinyl acetate copolymer.
Thus, the clear ink layer formed by the application of the clear ink also contains a vinyl chloride-vinyl acetate copolymer. Thus, as described above, when a heat-sealed body having a laminated structure of laminate base / clear ink layer / colored image / recording medium is formed, the peel strength between the laminate base and the recording medium is improved. be able to.
Details of the clear ink will be described later.

The application of the clear ink can be performed by applying a known method such as a coating method, an inkjet method, or an immersion method.
As a coating method, a known bar coater (for example, wire bar coater), extrusion die coater, air doctor coater, blade coater, rod coater, knife coater, squeeze coater, reverse roll coater, gravure coater, flexo coater, etc. The application method is mentioned.
The details of the ink jet method are the same as those of the ink jet method in the above-described color image forming step.
The application of the clear ink is preferably performed by an inkjet method from the viewpoint of simplifying the manufacturing apparatus for manufacturing a laminate having a laminated structure of clear ink layer / colored image / recording medium.

When the clear ink contains an organic solvent, in the clear ink layer forming step, preferably, the clear ink applied on the recording medium is heated to form a clear ink layer.
The heating can efficiently dry the clear ink (that is, remove the organic solvent from the clear ink).
The preferable heating temperature in heating the clear ink on the recording medium is the same as the preferable heating temperature in heating the colored ink on the recording medium.

When the clear ink contains a polymerizable compound described later, it is preferable to irradiate actinic radiation to the clear ink applied on the recording medium. Irradiation with actinic radiation polymerizes the polymerizable compound in the clear ink on the recording medium, and as a result, a cured clear ink layer is obtained.
Preferred embodiments of the actinic radiation and the actinic radiation irradiation conditions are the same as the preferred embodiments in the case of irradiating the colored ink on the recording medium with actinic radiation.

When the clear ink contains an organic solvent and a polymerizable compound, in the clear ink layer forming step, preferably, both the heating and the actinic radiation are preferably applied to the clear ink applied on the recording medium, It is more preferable to apply heating and actinic radiation in this order.

The clear ink layer formed in the clear ink layer forming step preferably has transparency. As a result, a heat-sealed body having a laminated structure of laminate base / clear ink layer / colored image / recording medium is formed, and the clearness of the colored image when the colored image is viewed from the laminate base side is excellent.
Here, having transparency means that the transmittance of visible light having a wavelength of 400 nm to 700 nm is 80% or more (preferably 90% or more).

<Step of heat-sealing laminated base material>
The recording method of the present disclosure preferably further includes the step of heat-fusing the laminate substrate on the clear ink layer (hereinafter, also referred to as “heat-fusing step”). By this heat sealing step, a heat sealed body having a laminated structure of laminate base material / clear ink layer / colored image / recording medium is formed. The heat-sealed body thus formed is excellent in peel strength between the laminate substrate and the recording medium as described above.

(Laminated substrate)
As a laminate base, a laminate base containing at least one of a urethane resin and a vinyl chloride resin is preferable. As a result, in the heat-sealed body, the peel strength between the laminate base and the recording medium is further improved.
In the laminate substrate, the total content of the urethane resin and the vinyl chloride resin is preferably 60% by mass, more preferably 80% by mass or more, still more preferably 90% by mass or more, based on the entire laminate substrate. It is.
In the laminate substrate, the total content of the urethane resin and the vinyl chloride resin may be 100% by mass.

The laminate substrate preferably contains a vinyl chloride resin, and the vinyl chloride resin is contained in an amount of 60% by mass (more preferably 80% by mass or more, still more preferably 90% by mass or more) with respect to the entire recording medium. Is particularly preferred.

The laminate substrate may contain other components (known additives for resin, etc.) other than urethane resin and vinyl chloride resin.

The laminate substrate preferably has transparency. As a result, a heat-sealed body having a laminated structure of laminate base / clear ink layer / colored image / recording medium is formed, and the clearness of the colored image when the colored image is viewed from the laminate base side is excellent.
The meaning of "having transparency" is as described above.
The thickness of the laminate substrate is not particularly limited, but is preferably 30 μm to 200 μm, more preferably 40 μm to 150 μm, and particularly preferably 50 μm to 100 μm.

A commercial item may be used as a laminate base.
Examples of commercially available laminate base materials include polymeric vinyl chloride laminate film “SG 800” manufactured by KN Trading Co., Ltd., urethane sheet “Higress HIGRESS (registered trademark)” manufactured by NTW Co., Ltd., and the like.

The heat fusion temperature in the heat fusion step is preferably 140 ° C. to 230 ° C., more preferably 150 ° C. to 220 ° C., still more preferably 170 ° C. to 190 ° C.
When the heat sealing temperature is 140 ° C. or higher, the peel strength between the laminate substrate and the recording medium is further improved.
When the heat sealing temperature is 230 ° C. or less, the disturbance of the colored image due to the heat sealing is further suppressed.
Here, the heat fusion temperature means the surface temperature of the laminate substrate at the time of heat fusion.

Heat-sealing pressure in thermal bonding step is ^preferably 1.0N / cm 2 ~ 10.0N / cm 2, 2.0N / cm 2 ~ 6.0N / cm 2 is more preferable.
The heat sealing time in the heat sealing step is preferably 2 seconds to 60 seconds, and more preferably 3 seconds to 20 seconds.

In the recording method of the present disclosure, from the viewpoint of further improving the peel strength described above, a combination of a recording medium containing a vinyl chloride resin and a laminate substrate containing a vinyl chloride resin, or a recording containing a urethane resin. It is preferable to use a combination of a medium and a laminate base containing a urethane resin, and more preferable to use a combination of a recording medium containing a vinyl chloride resin and a laminate base containing a vinyl chloride resin.
The combination of the recording medium containing the vinyl chloride resin and the laminate base containing the vinyl chloride resin is advantageous also from the viewpoint of being able to further suppress the disorder of the colored image due to the thermal fusion.

When a combination of a recording medium containing a vinyl chloride resin and a laminate substrate containing a vinyl chloride resin is used in the recording method of the present disclosure, the thermal fusion temperature is preferably 150 ° C. to 220 ° C. The temperature is more preferably 170 ° C. to 190 ° C. In the case of using a combination of a recording medium containing a vinyl chloride resin and a laminate base containing a vinyl chloride resin, when the thermal fusion temperature is 150 ° C. to 220 ° C., the above-mentioned peel strength is more Thus, the disturbance of the colored image due to the heat fusion is further suppressed.
When a combination of a recording medium containing a urethane resin and a laminate base containing a urethane resin is used in the recording method of the present disclosure, the thermal fusion temperature is preferably 150 ° C. to 190 ° C., and more preferably Is 150.degree. C. to 170.degree. In the case of using a combination of a recording medium containing a urethane resin and a laminate base containing a urethane resin, when the heat sealing temperature is 150 ° C. to 190 ° C., the above-mentioned peel strength is further improved. And, the disorder of the colored image due to the heat fusion is further suppressed.

Next, preferred embodiments of the clear ink and the colored ink used in the recording method of the present disclosure will be described.

<Clear ink>
The clear ink contains an organic solvent and a vinyl chloride-vinyl acetate copolymer as described above. The clear ink may contain other components.

(Vinyl chloride-vinyl acetate copolymer)
The clear ink contains at least one vinyl chloride-vinyl acetate copolymer.
The content of the vinyl chloride-vinyl acetate copolymer contained in the clear ink is preferably 0.5% by mass to 10.0% by mass with respect to the total amount of the clear ink.
When the content of the vinyl chloride-vinyl acetate copolymer is 0.5% by mass or more, the above-described effect, that is, the heat having a laminated structure of laminate base / clear ink layer / colored image / recording medium The effect of improving the peel strength between the laminate substrate and the recording medium in the fused body is more effectively exhibited.
When the content of the vinyl chloride-vinyl acetate copolymer is 10.0% by mass or less, the formability of the clear ink layer is more suitably secured. For example, the dischargeability at the time of discharging the clear ink from the ink jet head, the coatability at the time of applying the clear ink by the coating method, and the like are secured.
The content of the vinyl chloride-vinyl acetate copolymer with respect to the total amount of the clear ink is more preferably 1.0% by mass to 6.0% by mass, still more preferably 1.5% by mass to 5.0% by mass It is more preferably 1.5% by mass to 4.5% by mass.

The copolymerization ratio in the vinyl chloride-vinyl acetate copolymer is not particularly limited, but
Preferably, the copolymerization amount of vinyl chloride is 70% by mass to 95% by mass, and the copolymerization amount of vinyl acetate is 5% by mass to 30% by mass,
More preferably, the copolymerization amount of vinyl chloride is 80% by mass to 93% by mass, and the copolymerization amount of vinyl acetate is 7% by mass to 20% by mass,
More preferably, the copolymerization amount of vinyl chloride is 80% by mass to 90% by mass, and the copolymerization amount of vinyl acetate is 10% by mass to 20% by mass.

The weight average molecular weight (Mw) of the vinyl chloride-vinyl acetate copolymer is preferably 13,000 to 30,000.
When the weight average molecular weight (Mw) of the vinyl chloride-vinyl acetate copolymer is 13,000 or more, the peel strength between the laminate substrate and the recording medium in the heat-sealed product is further improved.
When the weight average molecular weight (Mw) of the vinyl chloride-vinyl acetate copolymer is 30,000 or less, the dischargeability of the colored ink is further improved.
The Mw of the vinyl chloride-vinyl acetate copolymer is preferably 13,000 to 20,000.

In the present specification, weight average molecular weight (Mw) means a value measured by gel permeation chromatography (GPC).
The above GPC was eluted using three columns of TSKgel (registered trademark) and Super Multipore HZ-H (manufactured by Tosoh Corp., 4.6 mm ID × 15 cm) as columns using HLC-8020GPC (manufactured by Tosoh Corp.) It is carried out using THF (tetrahydrofuran) as a solution.
In addition, GPC is performed using a differential refractive index (RI) detector with a sample concentration of 0.45 mass%, a flow rate of 0.35 ml / min, a sample injection amount of 10 μl, and a measurement temperature of 40 ° C.
The standard curve is the standard sample TSK standard, polystyrene from Tosoh Corp .: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A It is prepared from eight samples of "-2500", "A-1000" and "n-propylbenzene".

Commercially available vinyl chloride-vinyl acetate copolymers may be used.
Examples of commercially available products include vinyl chloride-vinyl acetate copolymer manufactured by Wacker Chemie, Solvaine CL manufactured by Nisshin Chemical Co., Ltd., CNL, C5R, TA3 and TA5R.

The clear ink has a total content mass of non-volatile components contained in the clear ink as Mt1, and a content mass of the vinyl chloride-vinyl acetate copolymer contained in the clear ink as Mt2, Mt2 / Mt1 Is preferably 0.40 or more, more preferably 0.45 or more.
When Mt2 / Mt1 is 0.40 or more, the peel strength between the laminate base and the recording medium in the heat-sealed body is further improved.
From the viewpoint of achieving such an effect more effectively, Mt2 / Mt1 is preferably 0.45 or more, and more preferably 0.50 or more.
Here, the vinyl chloride-vinyl acetate copolymer is included in the non-volatile component.
Therefore, Mt2 / Mt1 is 1.00 or less in principle. Mt2 / Mt1 may be 0.98 or less.

Here, with the non-volatile component contained in the clear ink, the clear ink is applied from an ink jet head at an application amount of 15 g / m ² on a glass of 10 cm × 10 cm size to form a solid image, and a solid image Means a component remaining on the glass when the formed glass is heated for 5 minutes in a thermostatic chamber at a temperature of 60 ° C., a pressure of 1 atm (101325 Pa), and the atmosphere.
In the clear ink applied as described above, the total content mass Mt1 of the non-volatile components contained in the clear ink means the mass of the remaining components, and the vinyl chloride-vinyl acetate copolymer contained in the clear ink The content mass of Mt2 means the mass of the vinyl chloride-vinyl acetate copolymer contained in the remaining components.

When the clear ink contains an organic solvent, the total content mass (Mt1) of the non-volatile components contained in the clear ink corresponds to the total mass excluding the organic solvent from the clear ink.

(Organic solvent)
The clear ink preferably contains at least one organic solvent.
This further improves the stability of the clear ink containing the vinyl chloride-vinyl acetate copolymer. Further, when the clear ink contains an organic solvent, the dischargeability of the clear ink from the ink jet head (hereinafter, also simply referred to as the "clear ink dischargeability") when the clear ink is applied by the ink jet method is It improves more.

As the organic solvent, known organic solvents that can be used for the ink composition can be used. Examples of known organic solvents include organic solvents described in New Edition Solvent Pocket Book (edited by Association of Synthetic Organic Chemistry, published in 1994) and the like.
The organic solvent is preferably an organic solvent having a boiling point of 150 ° C. or more and 250 ° C. or less, more preferably an organic solvent having a boiling point of 150 ° C. or more and 200 ° C. or less, from the viewpoint of further improving the dischargeability of the clear ink.
Hereinafter, the boiling point may be described as "BP".

As an organic solvent, for example,
(Poly) alkylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether;
(Poly) alkylene glycol dialkyl ethers such as ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol diethyl ether, tetraethylene glycol dimethyl ether;
(Poly) alkylene glycol acetates such as diethylene glycol acetate;
(Poly) alkylene glycol diacetates such as ethylene glycol diacetate and propylene glycol diacetate;
(Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monobutyl ether acetate and propylene glycol monomethyl ether acetate; ketones such as methyl ethyl ketone and cyclohexanone;
lactones such as γ-butyrolactone;
Esters such as ethyl acetate, propyl acetate, butyl acetate, 3-methoxybutyl acetate, methyl propionate, and ethyl propionate;
Cyclic ethers such as tetrahydrofuran and dioxane;
Amides such as dimethylformamide, dimethylacetamide and the like;
Etc.
The (poly) alkylene glycol is preferably (poly) ethylene glycol and / or (poly) propylene glycol.

As the organic solvent, from the viewpoint of dischargeability of clear ink, etc.,
Alkylene glycol monoalkyl ether acetates, alkylene glycol monoalkyl ethers, alkylene glycol dialkyl ethers, alkylene glycol acetates, polyalkylene glycol monoalkyl ether acetates, polyalkylene glycol monoalkyl ethers, polyalkylene glycol dialkyl ethers, At least one selected from the group consisting of polyalkylene glycol acetates, ketones, lactones, and esters is preferred,
Alkylene glycol monoalkyl ether acetates, alkylene glycol dialkyl ethers, polyalkylene glycol monoalkyl ether acetates, polyalkylene glycol dialkyl ethers, ketones, lactones, and at least one selected from the group consisting of esters Is more preferable,
Further preferred is at least one selected from the group consisting of polyalkylene glycol dialkyl ethers and esters.
It is particularly preferable that the organic solvent contains at least one of diethylene glycol diethyl ether (DEGDEE) and 3-methoxybutyl acetate.

The content of the organic solvent in the clear ink is preferably 50% by mass to 99.5% by mass, more preferably 80% by mass to 99% by mass, and 90% by mass to 98.5% by mass with respect to the total amount of the clear ink. More preferable.

(Surfactant)
The clear ink may contain at least one surfactant.
As the surfactant, those described in JP-A-62-173463 and JP-A-62-183457 can be mentioned.

As a surfactant, for example,
Anionic surfactants such as dialkyl sulfosuccinates, alkyl naphthalene sulfonates, fatty acid salts and the like;
Nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, acetylene glycols, polyoxyethylene / polyoxypropylene block copolymers;
Cationic surfactants such as alkylamine salts and quaternary ammonium salts;
Etc.

Moreover, as surfactant, a fluorine-type surfactant (for example, organic fluoro compound etc.) and silicone type surfactant (for example, polysiloxane compound etc.) are also mentioned.

The organic fluoro compound is preferably hydrophobic.
As the organic fluoro compound, for example, a fluorine-based surfactant, an oil-like fluorine-based compound (eg, fluorine oil) and a solid fluorine compound resin (eg, tetrafluoroethylene resin) are included, and JP-B-57-9053 Those described in each of JP-A-62-135826 and JP-A-62-135826 can be mentioned.
As a polysiloxane compound, it is preferable that it is a modified polysiloxane compound which introduce | transduced the organic group into a part of methyl group of dimethylpolysiloxane. Examples of modification include polyether modification, methylstyrene modification, alcohol modification, alkyl modification, alkyl modification, aralkyl modification, fatty acid ester modification, epoxy modification, amine modification, amino modification, mercapto modification and the like, but are particularly limited thereto is not. These methods of modification may be used in combination.

As a polysiloxane compound, a polyether modified polysiloxane compound is preferable in the viewpoint of the discharge stability improvement in an inkjet.
Examples of polyether modified polysiloxane compounds are, for example:
SILWET L-7604, SILWET L-7607N, SILWET FZ-2104, SILWET FZ-2161 (all manufactured by Nippon Unicar Co., Ltd.);
BYK306, BYK307, BYK331, BYK333, BYK347, BYK348 etc. (all by BYK Chemie);
KF-351A, KF-352A, KF-353L, KF-354A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-6191, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017 (above, Shin-Etsu Chemical Co., Ltd. product);
Can be mentioned.

When the clear ink contains a surfactant, the content of the surfactant is preferably 0.0001% by mass to 1% by mass with respect to the total amount of the clear ink.

(Resin other than vinyl chloride-vinyl acetate copolymer)
The clear ink may contain at least one resin other than vinyl chloride-vinyl acetate copolymer.
Examples of resins other than vinyl chloride-vinyl acetate copolymer include polyamide resin, polyurethane resin, cellulose resin, (meth) acrylic resin, polyolefin resin, polyester resin, and the like.

The weight average molecular weight of the resin is preferably 5,000 to 100,000, more preferably 10,000 to 100,000, and still more preferably 20,000 to 80,000.

However, in order to more effectively exhibit the effect of the vinyl chloride-vinyl acetate copolymer contained in the clear ink, the clear ink does not contain a resin other than the vinyl chloride-vinyl acetate copolymer, or The content of the resin other than vinyl chloride-vinyl acetate copolymer is 5% by mass or less (more preferably 3% by mass or less, still more preferably 2% by mass or less, further preferably 1% by mass, based on the total amount of the clear ink % Or less) is particularly preferred.

(Other ingredients)
The clear ink may contain other components in addition to the components described above.
Examples of other components include the same components (for example, polymerizable compounds and the like) as the components that may be contained in the colored ink described later.
However, as described above, the content of the colorant in the clear ink is less than 0.5% by mass (more preferably less than 0.1% by mass, particularly preferably 0% by mass).

The clear ink may contain a small amount of water.
The clear ink is preferably a non-aqueous ink substantially free of water.
Specifically, the content of water relative to the total amount of the clear ink is preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less. The content of water relative to the total amount of the clear ink may be 0% by mass.

The preferred physical properties (viscosity and surface tension) of the clear ink are the same as the preferred physical properties of the colored ink described later.

<Colored ink>
The colored ink contains at least one colorant.
The colored ink is not particularly limited except this point.
A combination of the recording medium containing at least one of a urethane resin and a vinyl chloride resin and the clear ink containing a vinyl chloride-vinyl acetate copolymer regardless of the type of the colored ink. The effect of the effect exerted by (i.e., the improvement of the peel strength between the laminate base and the recording medium) is exerted.
The liquid component in the colored ink is preferably at least one of an organic solvent described later and a polymerizable monomer described later.

(Colorant)
There is no restriction | limiting in particular as a coloring agent, A pigment may be sufficient and a dye may be sufficient.
The colorant is preferably a pigment or an oil-soluble dye from the viewpoint of excellent weatherability and color reproducibility, and a pigment is particularly preferable.

The pigment is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include known organic pigments and inorganic pigments, and resin particles dyed with dyes, commercially available pigment dispersions and surface treatments For example, pigments obtained by dispersing the pigment (for example, pigments dispersed in an insoluble resin as a dispersion medium, or polymers grafted with a resin on the pigment surface) may also be mentioned.
In addition, as a pigment, for example, Ito Seishiro ed., "Dictionary of pigment" (2000 annual publication), W. Herbst, K. Examples thereof include those described in Hunger “Industrial Organic Pigments”, JP-A-2002-12607, JP-A-2002-188025, JP-A-2003-26978, and JP-A-2003-342503.

Examples of organic pigments and inorganic pigments include yellow pigments, magenta pigments, cyan pigments, green pigments, orange pigments, brown pigments, violet pigments, black pigments, white pigments, and the like.
With regard to these pigments, for example, the description in paragraphs 0029 to 0042 of JP-A-2011-94112 can be referred to as appropriate.

The colored ink may contain only one type of colorant or may contain two or more types.
The content (total content in the case of two or more types) of the coloring agent in the colored ink is preferably 0.5% by mass to 20% by mass, and more preferably 1% by mass to 20% by mass with respect to the total amount of the colored ink. The content is more preferably in the range of 1% by mass to 10% by mass.

The colored ink preferably further contains at least one of a vinyl chloride-vinyl acetate copolymer and a polymerizable compound.
When the colored ink contains a vinyl chloride-vinyl acetate copolymer, the cohesive failure of the colored image, the interfacial peeling between the colored image and the clear ink layer, and the colored image when the heat-fused body is formed. It is possible to further suppress interfacial peeling between the toner and the recording medium. Therefore, when the colored ink contains a vinyl chloride-vinyl acetate copolymer, the peel strength between the laminate substrate and the recording medium can be further improved when the heat-fused product is formed.
When the colored ink contains a polymerizable compound, the colored ink can be cured to form a colored image by polymerization of the polymerizable compound. For this reason, cohesive failure of the colored image and interfacial peeling between the recording medium and the colored image can be further suppressed. Therefore, in the case where the colored ink contains a polymerizable compound, the laminated base material and the recording base are formed when the heat-sealed body having a laminated structure of laminate base / clear ink layer / colored image / recording medium is formed. Peeling strength with the medium can be further improved.

(Vinyl chloride-vinyl acetate copolymer)
As mentioned above, the colored ink may contain at least one vinyl chloride-vinyl acetate copolymer.
Preferred embodiments (such as Mw) of the vinyl chloride-vinyl acetate copolymer that can be contained in the colored ink are the same as the preferred embodiments of the vinyl chloride-vinyl acetate copolymer that can be contained in the clear ink.

When the colored ink contains a vinyl chloride-vinyl acetate copolymer, the content of the vinyl chloride-vinyl acetate copolymer contained in the colored ink is preferably 0.1% by mass to the total amount of the colored ink. It is 5.0% by mass, more preferably 0.2% by mass to 4.0% by mass, and still more preferably 0.5% by mass to 2.0% by mass.
When the content of vinyl chloride-vinyl acetate copolymer is 0.1% by mass or more, a laminate substrate in a heat-sealed body having a laminate structure of laminate substrate / clear ink layer / colored image / recording medium The peel strength with the recording medium is further improved.
When the content of the vinyl chloride-vinyl acetate copolymer is 5.0% by mass or less, the dischargeability of the colored ink is further improved.

In the case where the colored ink contains a vinyl chloride-vinyl acetate copolymer,
The total content of non-volatile components contained in the clear ink is Mt1
Let the content mass of the vinyl chloride-vinyl acetate copolymer contained in the clear ink be Mt2.
The total content mass of the non-volatile components contained in the colored ink is Mc1
When the content mass of the vinyl chloride-vinyl acetate copolymer contained in the colored ink is Mc2,
It is preferable that Mt1, Mt2, Mc1, and Mc2 satisfy the following formula (1).
Mc2 / Mc1 ≦ Mt2 / Mt1 ... Formula (1)

When Mt1, Mt2, Mc1, and Mc2 satisfy the above-mentioned formula (1), a laminate substrate in a heat-sealed body having a laminate structure of laminate substrate / clear ink layer / colored image / recording medium The peel strength with the recording medium is further improved.

It goes without saying that the formula (1) means that Mt2 / Mt1 is 1 or more times that of Mc2 / Mc1.
The Mt2 / Mt1 is preferably 1.5 times or more, more preferably 5 times or more the Mc2 / Mc1.
Further, Mt2 / Mt1 is preferably 15 times or less of Mc2 / Mc1.

The meanings of the non-volatile components Mc1 and Mc2 contained in the colored ink are respectively the same as the meanings of the non-volatile components Mt1 and Mt2 contained in the clear ink described above.
The total content mass (Mc1) with the non-volatile component contained in the colored ink corresponds to the total mass excluding the organic solvent from the colored ink when the colored ink contains the organic solvent.

When forming a multicolor colored image using two or more types of colored inks in the colored image forming step, at least one of the two or more types of colored inks and the clear ink have the above formula (1 It is preferable to satisfy the above, and it is particularly preferable that all types of two or more kinds of colored inks and clear ink satisfy the above-mentioned formula (1).

(Polymerizable compound)
As mentioned above, the colored ink may contain at least one polymerizable compound.
In the present specification, the polymerizable compound means a compound having a polymerizable group.
The polymerizable group in the polymerizable compound is preferably a group containing an ethylenically unsaturated bond, and more preferably a group containing at least one of a vinyl group and a 1-methylvinyl group.
As the polymerizable group, a (meth) acryloyl group is particularly preferable from the viewpoint of the polymerization reactivity and the hardness of the formed colored image.

The weight average molecular weight (Mw) of the polymerizable compound is preferably 30000 or less, more preferably 20000 or less, and still more preferably 15000 or less from the viewpoint of the dischargeability of the colored ink.

When the colored ink contains a polymerizable compound, the preferred range of the content of the polymerizable compound is Mw of the polymerizable compound, Mw of the polymerizable compound, and other components (vinyl chloride-vinyl acetate copolymer, organic solvent, etc.) in the colored ink. It is selected appropriately in consideration of the presence or absence.
The content of the polymerizable compound can be, for example, in the range of 0.3% by mass to 90% by mass with respect to the total amount of the colored ink.

-Polymerizable oligomer-
The colored ink may contain at least one of polymerizable oligomers.
Here, the polymerizable oligomer refers to a polymerizable compound having a weight average molecular weight (Mw) of 1,000 to 30,000.
The Mw of the polymerizable oligomer is more preferably 1000 to 20000, still more preferably 1000 to 15000, and still more preferably 2000 to 15000.

The polymerizable oligomer is preferably a urethane (meth) acrylate oligomer from the viewpoint of further improving the peel strength between the laminate substrate and the recording medium in the heat-fused material, and a bifunctional or higher urethane (meth) acrylate oligomer is preferable. More preferably, a bifunctional urethane (meth) acrylate oligomer is more preferable.

When the colored ink contains a bifunctional urethane (meth) acrylate oligomer, the colored ink is a urethane (meth) acrylate oligomer other than the bifunctional urethane (meth) acrylate oligomer (preferably, a trifunctional or higher functional urethane (meth) Acrylate oligomers) may be contained. In this case, the content of the urethane (meth) acrylate oligomer other than the bifunctional urethane (meth) acrylate oligomer is preferably smaller than the content of the bifunctional urethane (meth) acrylate oligomer.

A commercial item may be used as a urethane (meth) acrylate oligomer more than bifunctional.
Commercially available products include CN 9001 (made by Sartmar), violet light UV-3200B, violet light UV-3300B, violet light UV-3310B, violet light UV-6630B, violet light UV-7600B (all manufactured by Japan Synthetic Chemical Industry Co., Ltd.), etc. Can be mentioned.

When the colored ink contains a polymerizable oligomer, the content of the polymerizable oligomer is preferably 0.3% by mass to 50% by mass, and more preferably 3% by mass to 30% by mass, with respect to the total amount of the colored ink. Is more preferable, and 5 to 20% by mass is even more preferable.
When the colored ink contains a polymerizable oligomer, the colored ink preferably contains an organic solvent.

When the colored ink contains a bifunctional urethane (meth) acrylate oligomer, the content of the bifunctional urethane (meth) acrylate oligomer is 0.3% by mass to 50% by mass with respect to the total amount of the colored ink Is preferable, 3 to 30% by mass is more preferable, and 5 to 20% by mass is more preferable.

-Polymerizable monomer-
The colored ink may contain at least one of polymerizable monomers.
Here, the polymerizable monomer refers to a polymerizable compound having a molecular weight of less than 1000.
The molecular weight of the polymerizable monomer is preferably 100 or more and less than 1000, more preferably 100 or more and 800 or less, and still more preferably 150 or more and 700 or less.

As the polymerizable monomer, at least one of a monofunctional radically polymerizable monomer (hereinafter, also referred to as "monofunctional monomer") and a difunctional radically polymerizable monomer (hereinafter, also referred to as "bifunctional monomer") is preferable.

As a monofunctional monomer,
N-vinyl compounds such as N-vinylcaprolactam, N-vinylpyrrolidone and the like;
2-phenoxyethyl acrylate (PEA), benzyl acrylate, cyclic trimethylol propane formal acrylate (CTFA), isobornyl acrylate (IBOA), tetrahydrofurfuryl acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, octyl acrylate, Decyl acrylate, tridecyl acrylate, isodecyl acrylate, lauryl acrylate, 3,3,5-trimethylcyclohexyl acrylate (TMCHA), dicyclopentenyl acrylate (DCPA), 4-t-butylcyclohexyl acrylate, cyclohexyl acrylate, caprolactone modified acrylate, Hydroxyethyl acrylate, hydroxybutyl acrylate, polyethylene glycol acrylate Polypropylene glycol acrylate, nonylphenoxy polyethylene glycol acrylate, monofunctional acrylate compounds such as nonylphenoxy polypropylene glycol acrylate;
2-phenoxyethyl methacrylate, benzyl methacrylate, isobornyl methacrylate, tetrahydrofurfuryl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, octyl methacrylate, decyl methacrylate, tridecyl methacrylate, isodecyl methacrylate, lauryl methacrylate, 3,3 , 5-trimethylcyclohexyl methacrylate, dicyclopentenyl methacrylate, 4-t-butylcyclohexyl methacrylate, cyclohexyl methacrylate, caprolactone modified methacrylate, hydroxyethyl methacrylate, hydroxybutyl methacrylate, polyethylene glycol methacrylate, polypropylene glycol methacrylate, nonylphenoxypolyethylene glycol Lumpur methacrylate, a monofunctional methacrylate compound such as nonylphenoxy polypropylene glycol methacrylate;
Monofunctional vinyl ether compounds such as normal propyl vinyl ether, isopropyl vinyl ether, normal butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexane dimethanol monovinyl ether;
Acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide,
Acryloyl morpholine, N-isopropyl acrylamide, N-hydroxyethyl acrylamide, N-butyl acrylamide, N-tert-butyl acrylamide, N- (1,1-dimethyl-3-oxobutyl) acrylamide, N-dodecyl acrylamide, N- (butoxy Monofunctional acrylamide compounds such as methyl) acrylamide, etc .;
Monofunctional methacrylamide compounds such as methacrylamide, N-phenyl methacrylamide, N- (methoxymethyl) methacrylamide, N, N-dimethyl methacrylamide, N-tert-butyl methacrylamide, etc.
Etc.

As a bifunctional monomer,
Hexanediol diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), polyethylene glycol diacrylate, polypropylene glycol diacrylate, nonane diol diacrylate, decanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol modified bisphenol A diacrylate , Difunctional acrylate compounds such as dioxane glycol diacrylate, cyclohexane dimethanol diacrylate and tricyclodecane dimethanol diacrylate;
2- (2-vinyloxyethoxy) ethyl acrylate (VEEA);
Difunctional vinyl compounds such as 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether (DVE3);
Difunctional methacrylate compounds such as hexanediol dimethacrylate, dipropylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, noneopentyl glycol dimethacrylate, and polyethylene glycol modified bisphenol A dimethacrylate;
Etc.

The polymerizable monomer may contain a trifunctional or higher radically polymerizable monomer (hereinafter also referred to as a “trifunctional or higher monomer”).
As a trifunctional or higher monomer, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate (DPHA), trimethylolpropane triacrylate (TMPTA), ditrimethylolpropane tetraacrylate, pentaerythritol Examples thereof include trifunctional or higher trifunctional (meth) acrylate compounds such as trimethacrylate and pentaerythritol tetramethacrylate.

When the colored ink contains a polymerizable monomer, the total content of the polymerizable monomer is preferably 50% by mass or more, more preferably 60% by mass or more, based on the total amount of the colored ink. More preferably, it is at least%.
The upper limit of the total content of the polymerizable monomers is not particularly limited, but the upper limit is, for example, 95% by mass, preferably 90% by mass.

When the colored ink contains at least one of a monofunctional monomer and a difunctional monomer, the total content of the monofunctional monomer and the difunctional monomer is preferably 50% by mass or more based on the total amount of the colored ink, 60 mass % Or more is more preferable, and 65% by mass or more is even more preferable.
The upper limit of the total content of the monofunctional monomer and the difunctional monomer is not particularly limited, but the upper limit is, for example, 95% by mass, preferably 90% by mass.

(Photopolymerization initiator)
When the colored ink contains a polymerizable compound, the colored ink preferably contains at least one photopolymerization initiator.
A photopolymerization initiator is a compound that causes a chemical change when irradiated with actinic radiation (also referred to herein as "light") and generates a polymerization initiation species.
As the photopolymerization initiator, actinic radiation to be irradiated, for example, ultraviolet light of 200 nm to 400 nm, far ultraviolet light, g-ray, h-ray, i-ray, KrF excimer laser light, ArF excimer laser light, electron beam, X-ray, molecule Those having sensitivity to a line or an ion beam can be appropriately selected and used.
As a photoinitiator, a radical polymerization initiator is preferable from a viewpoint which is excellent in curability and fixability of colored ink.

As preferable photopolymerization initiators, (a) aromatic ketones, (b) aromatic onium salts, (c) organic peroxides, (d) hexaarylbiimidazole compounds, (e) ketoxime ester compounds, ((e) f) borate compounds, (g) azinium compounds, (h) metallocene compounds, (i) active ester compounds, (j) compounds having a carbon halogen bond, and the like.

From the viewpoint of curability, aromatic ketones are preferable as the radical polymerization initiator.
Moreover, as a radical polymerization initiator, an acyl phosphine oxide compound is preferable.
As an acyl phosphine oxide compound, a monoacyl phosphine oxide compound, a bisacyl phosphine oxide compound, etc. can be used, and as a monoacyl phosphine oxide compound, a well-known monoacyl phosphine oxide compound can be used. For example, monoacyl phosphine oxide compounds described in JP-B 60-8047 and JP-B 63-40799 can be mentioned.

Specific examples of monoacyl phosphine oxide compounds include isobutyryl methyl phosphinic acid methyl ester, iso butyryl phenyl phosphinic acid methyl ester, pivaloyl phenyl phosphinic acid methyl ester, 2-ethylhexanoyl phenyl phosphinic acid methyl ester, pi Baroyl phenylphosphinic acid isopropyl ester, p-toluylphenyl phosphinic acid methyl ester, o-toluylphenyl phosphinic acid methyl ester, 2,4-dimethyl benzoyl phenyl phosphinic acid methyl ester, pt-butyl benzoyl phenyl phosphinic acid isopropyl ester, Acryloyl phenyl phosphinic acid methyl ester, isobutyryl diphenyl phosphine oxide, 2-ethylhexanoyl diphenyl phosphine oxy O-toluyldiphenyl phosphine oxide, p-t-butyl benzoyl diphenyl phosphine oxide, 3-pyridylcarbonyl diphenyl phosphine oxide, acryloyl diphenyl phosphine oxide, benzoyl diphenyl phosphine oxide, pivaloyl phenyl phosphinic acid vinyl ester, adipoyl bis diphenyl phosphine Oxide, pivaloyldiphenylphosphine oxide, p-toluyldiphenylphosphine oxide, 4- (t-butyl) benzoyldiphenylphosphine oxide, 2-methylbenzoyldiphenylphosphine oxide, 2-methyl-2-ethylhexanoyldiphenylphosphine oxide, 1 -Methylcyclohexanoyl diphenyl phosphine oxide, pivaloyl phenyl phosphinic acid Chiruesuteru and pivaloyl phenyl phosphinic acid isopropyl ester.

Known bisacylphosphine oxide compounds can be used as the bisacylphosphine oxide compound.
Examples of the bisacylphosphine oxide compound include the bisacylphosphine oxide compounds described in JP-A-3-101686, JP-A-5-345790, and JP-A-6-298818.
Specific examples of the bisacyl phosphine oxide compound include bis (2,6-dichlorobenzoyl) phenyl phosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenyl phosphine oxide, bis (2,6-dichloro) Benzoyl) -4-ethoxyphenyl phosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenyl phosphine oxide, bis (2,6-dichlorobenzoyl) -2-naphthyl phosphine oxide, bis (2,6-dichloro phosphine) Benzoyl) -1-naphthyl phosphine oxide, bis (2,6-dichlorobenzoyl) -4-chlorophenyl phosphine oxide, bis (2,6-dichlorobenzoyl) -2,4-dimethoxyphenyl phosphine oxide, bis (2,6- Dichlorobenzo B) decyl phosphine oxide, bis (2,6-dichlorobenzoyl) -4-octylphenyl phosphine oxide, bis (2,4,6-trimethyl benzoyl) phenyl phosphine oxide, bis (2,4,6-trimethyl benzoyl)- 2,5-dimethylphenyl phosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -2,5-dimethylphenyl phosphine oxide, bis (2,6-dichloro-3,4,5 -Trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenyl phosphine oxide, bis (2-methyl-1-naphthoyl) -4-ethoxyphenyl phosphine oxide , Bis (2-methyl-1-naphthoyl) -2- Phythyl phosphine oxide, bis (2-methyl-1-naphthoyl) -4-propylphenyl phosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenyl phosphine oxide, bis (2-methoxy-1) -Naphthoyl) -4-ethoxyphenylphosphine oxide, bis (2-chloro-1-naphthoyl) -2,5-dimethylphenyl phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine And the like.

As the acyl phosphine oxide compound, bis (2,4,6-trimethyl benzoyl) phenyl phosphine oxide (IRGACURE 819: manufactured by BASF), bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phenyl phosphine Oxide, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide (DAROCUR TPO: manufactured by BASF, LUCIRIN TPO: manufactured by BASF), or 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2- Methyl-1-propan-1-one (IRGACURE 2959, manufactured by BASF) is preferred.

The colored ink contains, as a photopolymerization initiator, a compound that functions as a sensitizer (hereinafter, also simply referred to as a "sensitizer") in order to absorb specific actinic radiation and promote the decomposition of the polymerization initiator. You may
Examples of sensitizers include polynuclear aromatics (eg, pyrene, perylene, triphenylene, 2-ethyl-9, 10-dimethoxyanthracene, etc.), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, and the like). Rose Bengal etc., cyanines (eg thiacarbocyanine, oxacarbocyanine etc.), merocyanines (eg merocyanine, carbomerocyanine etc.), thiazines (eg thionine, methylene blue, toluidine blue etc.), acridines (eg , Acridine orange, chloroflavin, acriflavine etc.), anthraquinones (eg anthraquinone etc.), squaliums (eg squalium etc.), coumarins (eg 7-diethylamino-4-methylcoumarin etc.), etc.

Moreover, a sensitizer may be used individually by 1 type, and may use 2 or more types together.
When the colored ink contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1% by mass to 20% by mass with respect to the total amount of the colored ink, and 0.5% by mass It is more preferably ~ 18% by mass, still more preferably 1% by mass to 15% by mass, and still more preferably 1% by mass to 10% by mass.

(Polymerization inhibitor)
When the colored ink contains a polymerizable compound, the colored ink may further contain at least one polymerization inhibitor.
Examples of the polymerization inhibitor include nitroso type polymerization inhibitors, hindered amine type polymerization inhibitors, hindered phenol type polymerization inhibitors, hydroquinone, benzoquinone, p-methoxyphenol, TEMPO, TEMPOL, cuperone Al and the like.
When the colored ink contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.02% by mass to 2% by mass with respect to the total amount of the colored ink.

(Organic solvent)
The colored ink preferably contains at least one organic solvent.
Examples of the organic solvent that can be contained in the colored ink are the same as the examples of the organic solvent that can be contained in the clear ink.

When the colored ink contains an organic solvent, the content of the organic solvent is preferably 40% by mass to 95% by mass, more preferably 50% by mass to 90% by mass, and still more preferably 60% by mass to 85% by mass. % By mass is more preferred.

However, when the colored ink contains at least one of the above-mentioned monofunctional monomer and difunctional monomer at 50% by mass or more as the total content of the monofunctional monomer and the difunctional monomer, the content of the organic solvent is colored It may be, for example, 0% by mass to 10% by mass with respect to the total amount of the ink.

(Surfactant)
The colored ink may contain at least one surfactant.
Examples of surfactants that can be contained in the colored ink are the same as examples of surfactants that can be contained in the clear ink.
When the colored ink contains a surfactant, the content of the surfactant is preferably 0.0001% by mass to 1% by mass with respect to the total amount of the colored ink.

(Polysiloxane compound having an acrylic resin chain)
The colored ink may contain at least one kind of polysiloxane compound having an acrylic resin chain.
As a polysiloxane compound which has an acrylic resin chain, the compound which has a polysiloxane chain and an acrylic resin chain is more preferable, and it is especially preferable that it is a polysiloxane compound to which the acrylic resin chain was grafted.
Although there is no restriction | limiting in particular as a polysiloxane compound which has an acrylic resin chain | strand, The Nisshin Chemical Industry Co., Ltd. product sharine series, Toagosei Co., Ltd. product cymac series etc. are mentioned.
When the colored ink contains a polysiloxane compound having an acrylic resin chain, the content of the polysiloxane compound having an acrylic resin chain is 0.01% by mass to 8% by mass with respect to the total amount of the colored ink. The content is preferably 0.1% by mass to 4% by mass, and more preferably 0.25% by mass to 1.5% by mass.

(Dispersant)
The colored ink may contain at least one dispersant.
When the colored ink contains a pigment as a colorant, the colored ink preferably contains a dispersant.
As a dispersing agent, a polymeric dispersing agent is preferable.
Here, the “polymer dispersant” means a dispersant having a weight average molecular weight (Mw) of 1000 or more.

As polymer dispersants, DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-111, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-167 , DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-182 (BYK Chemie Co., Ltd.); EFKA7462, EFKA7500, EFKA7570, EFKA7575, EFKA7580, EFKA7701 (manufactured by Efka Additive); Dispers Aid 6, Dispers Aid 8, Dispers Aid 15, Dispers Aid 9100 (Sannopco Co., Ltd.); Sol Sparse (SOLSPERSE 3000, 5000, 9000, 12000, 13240, 13940, 17000, 22000, 24000, 26000, 28000, 32000, 36000, 39000, 41000, 71000, etc. Various sol spars dispersion agents (manufactured by Noveon); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, 108, L121, P-123 (manufactured by ADEKA Co., Ltd.), Ionet S-20 (manufactured by Sanyo Chemical Industries, Ltd.); Disparon KS-860, 873 SN, 874 (polymer dispersant), # 2150 (aliphatic polybasic) Valence carboxylic acid), # 7004 (polyether ester type) (manufactured by Kushimoto Chemical Co., Ltd.).

When the colored ink contains a dispersant, the colored ink may contain only one type of dispersant, or two or more types of dispersant.
When the colored ink contains a dispersant, the content (total content in the case of two or more types) of the dispersant is 0.05% by mass to 10% by mass with respect to the total amount of the colored ink. Preferably, 0.1% by mass to 5% by mass is more preferable.

(Other ingredients)
The colored ink may contain other components in addition to the components described above.
Other components include UV absorbers, antioxidants, antifading agents, surface conditioners, leveling agents, matting agents, waxes, antifoaming agents, pH adjusters, charge imparting agents, bactericides, preservatives, deodorizing agents Well-known additives such as agents, charge control agents, wetting agents, anti-skin agents, perfumes, pigment derivatives and the like can be mentioned.

The colored ink may contain a small amount of water.
The colored ink is preferably a non-aqueous ink substantially free of water.
Specifically, the content of water based on the total amount of the colored ink is preferably 3% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less. The content of water relative to the total amount of the colored ink may be 0% by mass.

(Preferred physical properties)
The viscosity at 25 ° C. of the colored ink is preferably 1 mPa · s to 40 mPa · s, and more preferably 3 mPa · s to 30 mPa · s, from the viewpoint of suppression of bleeding when the colored ink lands.
Further, from the viewpoint of suppression of bleeding when the colored ink lands, the colored ink has a viscosity of 1 mPa at a discharge temperature (preferably 25 ° C. to 80 ° C., more preferably 25 ° C. to 50 ° C.) when discharged from the inkjet head. S to 30 mPa · s is preferable, and 3 mPa · s to 25 mPa · s is more preferable.

The method of measuring the viscosity of the colored ink is not particularly limited, but preferred is a method using a conical rotor / plate viscometer (for example, RE 80 viscometer manufactured by Toki Sangyo Co., Ltd.) corresponding to E-type.
In this method, rotor code no. It is preferable to measure the viscosity of the colored ink at a rotation number of 10 rpm (round per minute) using a No. 1 rotor. However, it is preferable to change the rotational speed to 5 rpm, 2.5 rpm, 1 rpm, 0.5 rpm, etc. if necessary for the colored ink having a viscosity higher than 60 mPa · s.

The surface tension of the colored ink at 25 ° C. is preferably 18 mN / m to 50 mN / m, and more preferably 20 mN / m to 40 mN / m, from the viewpoint of appropriate droplet deposition by the inkjet method.
In addition, the surface tension of the colored ink is measured at a liquid temperature of 25 ° C. by the Wilhelmy method using a generally used surface tension meter (for example, surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd.). Value.

(Preferred embodiment of colored ink)
Preferred embodiments of the colored ink include the first to third embodiments described below.

-First aspect-
The colored ink according to the first aspect contains a colorant, an organic solvent, and a polymerizable oligomer. As the colored ink according to the first aspect, a UV curable solvent ink (sometimes referred to as "SUV ink" in this specification) is preferable.
The colored ink of the first aspect contains a polymerizable oligomer as a polymerizable compound. For this reason, in the case of using the colored ink of the first aspect, as described above, in the case of forming a heat-fused body having a laminated structure of laminate base material / clear ink layer / colored image / recording medium, The peel strength between the substrate and the recording medium is further improved.
The colored ink according to the first aspect preferably further contains a vinyl chloride-vinyl acetate copolymer. Thereby, when the above-mentioned heat-fusion body is formed, the peel strength between the laminate base and the recording medium is further improved.

-Second aspect-
The colored ink according to the second aspect contains a colorant, an organic solvent, and a vinyl chloride-vinyl acetate copolymer.
As the colored ink according to the second aspect, a solvent ink (sometimes referred to as "S ink" in this specification) is preferable.
The colored ink of the second aspect contains a vinyl chloride-vinyl acetate copolymer.
Therefore, also when the colored ink of the second aspect is used, as described above, the peel strength between the laminate base and the recording medium is further improved when the heat-fused body is formed.

-Third aspect-
The colored ink according to the third aspect contains a colorant and a polymerizable monomer.
The colored ink according to the third aspect is preferably a UV curable ink (sometimes referred to herein as "UV ink").

[Laminate]
The laminate of the present disclosure is
A recording medium containing at least one of a urethane resin and a vinyl chloride resin;
A colored image (i.e., a colored image formed by an inkjet method) which is disposed on a recording medium and is an inkjet recording material;
A clear ink layer disposed on at least a colored image on a recording medium and containing a vinyl chloride-vinyl acetate copolymer;
Equipped with

The recording medium, the colored image, and the clear ink layer in the laminate of the present disclosure are the same as the recording medium, the colored image, and the clear ink layer in the recording method of the present disclosure described above.

The laminate of the present disclosure comprises a combination of a recording medium containing at least one of a urethane resin and a vinyl chloride resin, and a clear ink layer containing a vinyl chloride-vinyl acetate copolymer. For this reason, when a heat-sealed body having a laminated structure of laminate base / clear ink layer / colored image / recording medium is formed for the reason described above, the peel strength between the lamination base and the recording medium is excellent. .
The laminate of the present disclosure is preferably produced by the recording method of the present disclosure described above.

In the clear ink layer, the ratio of the content weight of the vinyl chloride-vinyl acetate copolymer to the total mass of the clear ink layer (ie, the ratio [content weight of the vinyl chloride-vinyl acetate copolymer contained in the clear ink layer / clear The preferred range of the total mass of the ink layer] is the same as the preferred range of Mt2 / Mt1 described above.

Also, from the viewpoint of more effectively exhibiting the effect of the vinyl chloride-vinyl acetate copolymer contained in the clear ink layer, the clear ink layer does not contain any resin other than the vinyl chloride-vinyl acetate copolymer Or the ratio of the content mass of the resin other than the vinyl chloride-vinyl acetate copolymer to the total mass of the clear ink layer (that is, the ratio [the resin other than the vinyl chloride-vinyl acetate copolymer contained in the clear ink layer It is preferable that the contained mass / the total mass of the clear ink layer] is 0.20 or less (more preferably 0.10 or less, still more preferably 0.05 or less, and still more preferably 0.01 or less).

The laminate of the present disclosure preferably further comprises a laminate substrate heat-sealed on the clear ink layer.
The laminate of this aspect is a heat-fused material having a laminate structure of laminate base / clear ink layer / colored image / recording medium. This heat-sealed body is more excellent in the peel strength between the laminate base and the recording medium.

The laminate substrate is the same as the preferred embodiment of the laminate substrate in the recording method of the present disclosure described above.
The laminate of the present disclosure of the aspect comprising the laminate substrate is preferably produced by the heat fusion step in the recording method of the present disclosure described above.

In the present specification, “a laminate includes a laminate base heat-fused on a clear ink layer” means a laminate having a laminate structure of clear ink layer / colored image / recording medium, and laminate. It means that the substrate is heat-sealed in the arrangement where the clear ink layer and the laminate substrate are in contact with each other.

The layered product (heat fusion body) of the present disclosure is particularly suitable as a floor material or wall material of transportation equipment (railway, bus, etc.), a floor material or wall material of a building, and the like.

Examples of the present disclosure will be shown below, but the present disclosure is not limited to the following examples.
In addition, unless there is particular notice, "part" and "%" are mass references.
Hereinafter, the detail of the various components used by the Example and the comparative example is shown.

<Colorant>
-PB 15: 4 ... CISFigment Blue 15: 4 (HELIOGEN BLUE D 7110 F) manufactured by BASF. Cyan pigment.
-Mixed quinacridone: CINQUASIA MAGENTA L 4540 manufactured by BASF. Magenta pigment.
PY 155: CIgent Yellow 155 (INK JET YELLOW 4 GC) manufactured by Clariant. Yellow pigment.
-Carbon black: Carbon black "MOGUL E" manufactured by CABOT. Black pigment.

<Dispersing agent>
・ SOL 32000 ... "SOLSPERSE 32000" manufactured by Luburizol
<Organic solvent>
Details of the organic solvents used in Examples and Comparative Examples are shown in Table 1.
Hereinafter, "BP" means boiling point.

<Polymerizable Oligomer (Polymerizable Compound)>
Details of the polymerizable oligomers (specifically, urethane (meth) acrylate oligomers) used in Examples and Comparative Examples are shown in Table 2.

<Vinyl chloride-vinyl acetate copolymer>
Details of the vinyl chloride-vinyl acetate copolymer used in the examples and comparative examples are shown in Table 3.

<Polymerizable Monomer (Polymerizable Compound)>
PEA: 2-phenoxyethyl acrylate, Sartmar "SR339C".
· CTFA ... cyclic trimethylolpropane formal acrylate · IBOA ... isobornyl acrylate · TMPTA ... trimethylolpropane triacrylate · VEEA ... 2- (2-vinyloxyethoxy) ethyl acrylate

<Polymerization inhibitor>
-UV22: BASF AG "IRGASTAB (registered trademark) UV22" (Poly [oxy (methyl-1,2-ethanediyl)]-α, α ', α "-1,2,3-propanetriyltris [-[(1 -oxo-2-propen-1-yl) oxy] -2,6-bis (1,1-dimethylethyl) -4- (phenylenemethylene) cyclohexa-2,5-dien-1-one]; hindered phenol polymerization Inhibitor)

<Photoinitiator>
· Irg 819 ... "IRGACURE (registered trademark) 819" (bis (2, 4, 6- trimethyl benzoyl) phenyl phosphine oxide) manufactured by BASF.
· Irg 2959 ··· BASF AG "IRGACURE ® 2959" (1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one)
TPO: "IRGACURE (registered trademark) TPO" (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by BASF.

<Surfactant>
-BYK 331 ... "BYK (registered trademark) 331" (polyether modified polysiloxane compound) manufactured by BYK Chemie

<Acrylic resin>
・ BR113 ... "DIANAL (registered trademark) BR113" manufactured by Mitsubishi Chemical Corporation

<Polyester resin>
・ LTH ... "TEGO (registered trademark) AddBond LTH" manufactured by Evonik

<Polyvinyl acetal resin>
・ BL-10 ... "S-LEC (registered trademark) BL-10" manufactured by Sekisui Chemical Co., Ltd.

Preparation of Pigment Mill Base (Pigment Dispersion)
The compositions other than the pigments listed in Table 4 were mixed, and stirred using a mixer manufactured by SILVERSON (10 to 15 minutes, 2000 to 3000 revolutions / minute) to obtain a dispersant dilution liquid. A pigment was added to the dispersant dilution liquid, and the mixture was further stirred by a mixer (10 to 20 minutes, 2000 to 3000 rpm) to obtain 500 parts of a preliminary dispersion.
Thereafter, dispersion treatment was carried out using a circulation type bead mill apparatus (SL-012C1) manufactured by Dispermat Co., Ltd. to obtain a pigment mill base (pigment dispersion). This dispersion treatment was carried out by filling 200 parts of zirconia beads with a diameter of 0.65 mm in SL-012C1, under the conditions of a circumferential velocity of 15 m / s and a dispersion time of 1 to 6 hours.

<Preparation of coloring ink set>
The colored inks (cyan inks C1 to C6, magenta inks M1 to M6, yellow inks Y1 to Y6, and black inks K1 to K6) shown in Tables 5 to 10 below were prepared.
Furthermore, colored ink sets (SUV1 to SUV4, UV1 and S1) comprising combinations of cyan ink, magenta ink, yellow ink and black ink shown in Tables 5 to 10 below were prepared.

Each colored ink was prepared by mixing each component shown in the following Tables 5 to 10 in respective amounts, and stirring (10 to 15 minutes, 2000 to 3000 rotations / minute) with a mixer made by SILVERSON.
In Tables 5 to 10 below, numerical values indicating the amounts of the respective components mean parts by mass.
Blanks in the following Tables 5 to 10 mean that the corresponding components are not contained.
Table 5 to Table 10 below show the ratio of the total content (Mc1) of the non-volatile components contained in the colored ink to the content (Mc2) of the vinyl chloride-vinyl acetate copolymer contained in the colored ink (Mc2 / Mc1) is also described.

<Preparation of clear ink>
The components shown in Tables 11 to 13 below were mixed in respective amounts, and a clear ink was prepared by stirring (10 to 15 minutes, 2000 to 3000 revolutions / minute) with a mixer made by SILVERSON.
In Tables 11 to 13 below, numerical values indicating the amount of each component mean parts by mass.
Blanks in Tables 11 to 13 below mean that the corresponding components are not contained.
The clear inks T2, T17, T18, and T19 are all clear inks for comparison.
Table 11 to Table 13 below show the ratio of the total content (Mt1) of non-volatile components contained in the clear ink to the content (Mt2) of vinyl chloride-vinyl acetate copolymer contained in the clear ink (Mt2 / Mt1) was also written.

[Examples 1 to 29, Comparative Examples 1 to 5]
<Preparation of inkjet printer remodeling machine>
A rubber heater (SR100 manufactured by Three High Co., Ltd.) and an ultraviolet (UV) irradiation apparatus (Vzero manufactured by Integration Technology) were attached to an inkjet printer (KEGON) manufactured by AFFIT Co., Ltd. to prepare an inkjet printer modified machine. The output of the rubber heater was set so that the recording medium to which the ink (colored ink or colored ink and clear ink) was applied could be heated to about 60.degree. The drying time of the ink when UV irradiation was performed (that is, the time from when the ink ejected from the ink jet head lands on the recording medium to when irradiating UV) was adjusted to be 10 seconds. The adjustment of the drying time of the colored ink in this case was performed by adjusting the transport speed (5 m / min to 25 m / min) and the timing of opening and closing the UV shutter.

<Colored image formation process>
Each color ink (cyan ink, magenta ink, yellow ink, and black ink) in the color ink set described above was discharged from the ink jet head of the ink jet printer remodeling machine to form a color image on the recording medium. The image density was set to 1200 dpi (dot per inch) × 600 dpi.

As a recording medium, any one of the following white PVC and white PU was used (see Table 14).
・ White PVC: Polyvinyl chloride base material “PVC 35 phr” manufactured by Okamoto
・ White PU ... Polyurethane leather "Elna (YP 528)" made by Yamaplus Co., Ltd.

As colored images, three types of images of the following images A to C were formed.

The image A is an image in which a cyan solid image, a magenta solid image, a yellow solid image, and a black solid image are arranged in an arrangement of vertical 2 rows × horizontal 2 rows. The areas of these solid images were the same, and the application amounts of cyan ink, magenta ink, yellow ink and black ink were all 5 g / m ² (that is, 20 g / m ² as the total application amount of colored ink). .

Image B, as shown in FIG.
A thin line group in which a black (K) thin line image, a cyan (C) thin line image, a magenta (M) thin line image, and a yellow (Y) thin line image extending in the vertical direction are arranged in the horizontal direction;
A thin line group in which a black thin line image, a cyan thin line image, a magenta thin line image, and a yellow thin line image extending in the horizontal direction are arranged in the vertical direction;
To create a grid-like image. Each line width of each thin line image was 1 mm. The distance between the center lines of the thin line image (that is, the distance between the center line in the line width direction of a specific thin line and the center line in the line width direction of the thin line adjacent to the specific thin line) is 3 mm And

The image C is an image in which the line width of each thin line image in the image B is changed to 2 mm.

When forming any of the images A to C, after the application of the four colored inks to the recording medium is completed, the applied four colored inks are heated by a rubber heater (hereinafter simply referred to as simply By applying at least one of “heating”) and UV irradiation (hereinafter, also simply referred to as “UV irradiation”) by a UV irradiation device, the applied four color ink is fixed on a recording medium to form an image. It formed.
Specifically, in an example using a colored ink containing an organic solvent and a polymerizable oligomer (that is, an example using colored ink sets SUV1 to SUV4), heating (heating temperature) is applied to the applied four colored inks. 60 ° C.) and UV irradiation (UV wavelength 385 nm, UV irradiation amount 300 mJ / m ² ) were applied in this order.
In an example using a colored ink containing an organic solvent but not a polymerizable oligomer (that is, an example using a colored ink set S1), heating (heating temperature 60 ° C.) is applied to the applied four color inks. ) Was performed but no UV irradiation was performed.
In an example using a colored ink containing a polymerizable monomer (that is, an example using a colored ink set UV1), the applied four colored inks are not heated, and UV irradiation (UV wavelength 385 nm, UV) The irradiation dose was 300 mJ / m ² ).

<Clear ink layer formation process>
In Examples 1 to 29 and Comparative Examples 2 to 5, the above-described clear ink (any one of the clear inks T1 to T21) is ejected from the inkjet head of the modified inkjet printer to form a colored image. A clear ink layer was formed covering the whole on the colored image (any one of the images A to C) and the non-image formation area of the recording medium. The image density of the clear ink layer was 1,200 dpi × 600 dpi, and the amount of clear ink applied was 10 g / m ² .
In Comparative Example 1, the clear ink layer was not formed.

The formation of the clear ink layer is carried out by applying heat (no UV irradiation) to the clear ink applied to the recording medium on which the colored image is formed, or by applying heating and UV irradiation in this order. The
Specifically, in the example using clear ink T2 to T5 containing a polymerizable oligomer, heating (heating temperature 60 ° C.) and UV irradiation (UV irradiation amount 300 mJ / m ² ) are applied to the applied clear ink. The clear ink layer was formed by applying in order.
In the example using clear ink T1 and T6 to T19 which do not contain a polymerizable oligomer, the applied clear ink is subjected to heating (heating temperature 60 ° C.) (that is, without UV irradiation) , A clear ink layer was formed.

<Heat fusion process>
In Examples 1 to 29 and Comparative Examples 2 to 5, the laminate base material is disposed on the clear ink layer of the recording medium on which the colored image and the clear ink layer are formed, and the desktop heat press (desktop automatic transfer press) Laminated base material / clear ink layer / coloring by thermally fusing the recording medium on which the colored image and the clear ink layer are formed and the laminating base material using AF-54 TEN (Asahi Textile Machinery Co., Ltd.) A thermally fused body sample having a laminated structure of an image / recording medium was obtained.
Here, the lamination pressure (heat fusion pressure) was 4.0 N / cm ² , the lamination temperature (heat fusion temperature) was a temperature shown in Table 14, and the lamination time (heat fusion time) was 10 seconds.

As a laminate substrate, any one of the following transparent PVC and transparent PU was used (see Table 14).
・ Transparent PVC: Polymeric vinyl chloride laminate film “SG800” (75 μm thick) manufactured by KN Trading Co., Ltd.
・ Transparent PU ... Urethane sheet "Higress HIGRESS (registered trademark)" manufactured by NAW Co., Ltd.

In Comparative Example 1, the laminate base is disposed on the colored image of the recording medium on which the colored image is formed, and the thermal fusion is performed under the same conditions as the thermal fusion in Example 1, and the laminate base / colored image / A heat-fused body sample having a laminated structure of the recording medium was obtained. As the recording medium and the laminate substrate in Comparative Example 1, the same ones as the recording medium and the laminate substrate in Example 1 were used, respectively.

<Evaluation of appearance of colored image>
Thermal fusion body sample including image B (ie, grid-like image consisting of thin line image with line width 1 mm) and thermal fusion containing image C (ie, grid-like image consisting of thin line image with line width 2 mm) The appearance of the colored image (image B and image C) was visually confirmed from the laminate base side using the adherend sample, and the appearance of the colored image was evaluated according to the following evaluation criteria.
The results are shown in Table 14.
In the following evaluation criteria, “5” is the most excellent in the appearance of the colored image.

-Evaluation criteria for appearance of colored image-
5: Visual observation from a position 30 cm apart does not confirm fine line image disturbance and lattice disturbance in both the image B and the image C.
4: By the visual observation from a position 30 cm apart, the disorder of the thin line image or the disorder of the lattice is confirmed in the image B, but in the image C, the disorder of the thin line image and the disorder of the lattice are not confirmed.
3: Visual observation from a position 30 cm apart confirms the thin line image disorder or lattice disorder in both Image B and Image C. In visual observation from a position 1 m away, in both the image B and the image C, distortion of the thin line image and lattice distortion are not confirmed.
2: Visual observation from a position 30 cm apart confirms distortion of the thin line image or lattice distortion in both the image B and the image C. In the visual observation from a position 1 m away, in the image B, the disturbance of the thin line image or the lattice is confirmed, but in the image C, the disturbance of the thin line image and the disturbance of the lattice are not confirmed.
1: Visual observation from a position 30 cm apart confirms distortion of the thin line image or lattice distortion in both the image B and the image C. Even in visual observation from a position 1 m away, in both the image B and the image C, distortion of the thin line image or lattice distortion is confirmed.

<Evaluation of Peeling Strength Between Laminated Substrate and Recording Medium>
The sample for evaluation of peel strength was produced by changing the heat-sealing step in producing the heat-fused body sample containing the image A as follows.
A 0.5 cm × 10 cm strip sample including a part of the image A from the recording medium on which the colored image and the clear ink layer are formed (in the comparative example 1, the recording medium on which the colored image is formed) A piece (hereinafter, referred to as a "recording medium sample piece") was collected.
Similarly, a strip-shaped sample piece of 0.5 cm × 10 cm (hereinafter, referred to as “laminated substrate sample piece”) was collected from the laminated substrate.
0.5 cm × on the clear ink layer of the recording medium sample piece (however, in Comparative Example 1, on the colored image of the recording medium sample piece; the same applies hereinafter), including one end of the recording medium sample piece in the longitudinal direction A PTFE (polytetrafluoroethylene) sheet was placed on a 3 cm area. Next, on the clear ink layer of the recording medium sample piece, 0 in the entire area (0.5 cm × 3 cm area) where the PTFE sheet is disposed and the remaining area (0.5 cm × 7 cm area). .5 cm x 10 cm laminate substrate sample pieces were stacked.
In this state, the recording medium sample piece and the laminate base material sample piece were thermally fused under the same conditions as the thermal fusion step in producing the thermally fused body sample containing the image A. By removing the PTFE sheet from the obtained laminate, a sample for evaluation of peel strength was obtained.

FIG. 2 is a schematic cross-sectional view conceptually showing a cross section parallel to the thickness direction and the longitudinal direction in the peel strength evaluation sample.
As shown in FIG. 2, in this peeling strength evaluation sample, in the region of 0.5 cm × 7 cm, the recording medium sample piece 14 (specifically, the recording medium in Examples 1 to 29 and Comparative Examples 2 to 7) The clear ink layer of the sample piece (the colored image of the recording medium sample piece in Comparative Example 1) and the laminate base material sample piece 12 are thermally fused, but the recording medium sample piece 14 and the laminate base material sample piece 12 The area (ie, the area of 0.5 cm × 3 cm) in which the PTFE sheet was interposed therebetween was not heat-sealed.

Next, in the peel strength evaluation sample, a portion (end) of the recording medium sample piece 14 not heat-sealed and a portion (end) of the laminate substrate sample piece 12 not heat-sealed are included. A pull test was carried out, pulling in the opposite direction (in the direction of the two block arrows in FIG. 2). This tensile test was performed using a tensile tester (Autograph AGS-X 5KN, manufactured by SHIMAZU).
The above tensile test was performed 10 times. That is, ten samples for evaluation of peel strength were prepared, and a tensile test was performed on each sample for evaluation of peel strength.
The peel strength between the laminate substrate and the recording medium was evaluated based on the results of the ten tensile tests according to the following evaluation criteria.
The results are shown in Table 14.
In the following evaluation criteria, the one with the highest peel strength between the laminate substrate and the recording medium is “10”.

-Evaluation criteria for peel strength-
10: The laminate substrate sample piece and the recording medium sample piece did not peel off in 10 out of 10 tests, and the laminate substrate sample piece or the recording medium sample piece was broken.
9: In 9 out of 10 tests, the laminate substrate sample piece and the recording medium sample piece did not peel off, and the laminate substrate sample piece or the recording medium sample piece was broken.
8: In 7 or 8 out of 10 tests, the laminate substrate sample piece and the recording medium sample piece did not peel off, and the laminate substrate sample piece or the recording medium sample piece was broken.
7: In 5 or 6 out of 10 tests, the laminate substrate sample piece and the recording medium sample piece did not peel off, and the laminate substrate sample piece or the recording medium sample piece was broken.
6: The laminate substrate sample piece and the recording medium sample piece did not peel off in three or four out of ten tests, and the laminate substrate sample piece or the recording medium sample piece was broken.
5: The laminate substrate sample piece and the recording medium sample piece did not peel off in one or two out of 10 tests, and the laminate substrate sample piece or the recording medium sample piece was broken.
4: The laminate substrate sample piece and the recording medium sample piece peeled off in 10 out of 10 tests, and the average value of the maximum point stress in 10 tests was 2 MPa or more.
3: The laminate substrate sample piece and the recording medium sample piece peel off in 10 times out of 10 tests, and the average value of the maximum point stress in 10 tests is 1.5 MPa or more and less than 2 MPa The
2: The laminate substrate sample piece and the recording medium sample piece peel off in 10 of 10 tests, and the average value of the maximum point stress in 10 tests is 1.0 MPa or more and less than 1.5 MPa Met.
1: The laminate substrate sample piece and the recording medium sample piece peeled off in 10 out of 10 tests, and the average value of the maximum point stress in 10 tests was less than 1.0 MPa.

<Evaluation of dischargeability of colored ink>
The dischargeability of the colored ink (hereinafter also referred to as “dischargeability C”) was evaluated as follows.
Using the A2 size recording paper (ink jet printing paper, painting, Fujifilm Co., Ltd.) as a recording medium, 40 sheets of the recording paper are produced under the same conditions as the formation of the image A in the colored image forming process described above. On the other hand, an image A (that is, an image A consisting of solid images of four colors) was formed continuously. Hereinafter, the recording sheet on which the image A is formed is referred to as a “discharge property C evaluation sample”.
The 40 samples for evaluation of dischargeability C were visually observed, and the number of dischargeability C evaluation samples for which nozzle missing (that is, an image defect caused by a discharge failure of the nozzle) was confirmed was examined. Based on this result, the dischargeability C was evaluated according to the following evaluation criteria.
The results are shown in Table 14.
In the following evaluation criteria, the one with the best dischargeability C is “10”.

-Evaluation criteria for dischargeability (dischargeability C) of colored ink-
10: No sample for which nozzle missing is confirmed 9: One sample for which nozzle missing is confirmed 8: Two samples for which nozzle missing is confirmed 7: Three samples where nozzle missing is confirmed 6: 4 samples 5 samples for which missing nozzles are confirmed: 5 samples for which missing nozzles are confirmed 4: 6 samples for which missing nozzles are confirmed 3: 3 samples for which missing nozzles are confirmed 2: 7 missing nozzles 8 samples for which 1 is confirmed: 9 or more samples for which nozzle missing is confirmed

<Evaluation of clear ink dischargeability>
The dischargeability of the clear ink (hereinafter, also referred to as “dischargeability T”) was evaluated as follows.
Using the A2 size recording paper (ink jet printing paper, painting, Fujifilm Co., Ltd.) as a recording medium, the above recording paper 40 under the same conditions as the formation of the clear ink layer in the above-mentioned clear ink layer forming step. Clear solid images were continuously formed on the sheet. Hereinafter, the recording sheet on which the clear solid image is formed is referred to as “discharge property T evaluation sample”.
Forty sheets of the ejection property T evaluation samples were visually observed, and the number of ejection property T evaluation samples in which nozzle missing (that is, an image defect caused by nozzle ejection failure) was confirmed was examined. Based on this result, the dischargeability T was evaluated according to the following evaluation criteria.
The results are shown in Table 14.
In the following evaluation criteria, the one with the best dischargeability T is “10”.
The evaluation of the dischargeability (dischargeability T) of the clear ink was performed in Examples 1 to 29 and Comparative Examples 2 to 7. In Comparative Example 1, the evaluation of the dischargeability of the clear ink was not performed.

-Evaluation criteria for clear ink dischargeability (dischargeability T)-
10: No sample for which nozzle missing is confirmed 9: One sample for which nozzle missing is confirmed 8: Two samples for which nozzle missing is confirmed 7: Three samples where nozzle missing is confirmed 6: 4 samples 5 samples for which missing nozzles are confirmed: 5 samples for which missing nozzles are confirmed 4: 6 samples for which missing nozzles are confirmed 3: 3 samples for which missing nozzles are confirmed 2: 7 missing nozzles 8 samples for which 1 is confirmed: 9 or more samples for which nozzle missing is confirmed

As shown in Table 14, a colored image forming step of forming a colored image by applying a coloring ink containing a coloring agent on a recording medium containing a urethane resin or a vinyl chloride resin by an inkjet method, and at least a coloring image A clear ink layer forming step of forming a clear ink layer by applying a clear ink containing a vinyl chloride-vinyl acetate copolymer thereon to form an ink jet recording method according to Examples 1 to 29, In the heat-fusion sample in which the laminate substrate was heat-fused on the clear ink layer, the peel strength between the recording medium and the laminate substrate was excellent.

With respect to these Examples, in Comparative Example 1 in which the clear ink layer was not formed, and in Comparative Examples 2 to 4 in which the clear ink did not contain a vinyl chloride-vinyl acetate copolymer, the recording medium was used. The peel strength with the laminate substrate was reduced.
In Comparative Example 5 in which the clear ink does not contain a vinyl chloride-vinyl acetate copolymer and contains a polyvinyl acetal resin, the discharge properties of the clear ink are poor and a clear ink layer can not be formed. It was not possible to make an evaluation.

From the results of Examples 1 and 12 to 15, when the heat sealing temperature in heat sealing the laminate substrate on the clear ink layer is 150 ° C. to 220 ° C. (Examples 1, 13 and 14) It can be seen that the peel strength and the appearance of the colored image are compatible at a higher level.

From the results of Examples 1 and 9, it is understood that when the colored ink further contains a vinyl chloride-vinyl acetate copolymer (Example 1), the peel strength is further improved.

From the comparison between Example 11 and Example 24, it is found that the peel strength is further improved when Mc2 / Mc1 ≦ Mt2 / Mt1 is satisfied (Example 11).

The disclosure of Japanese Patent Application No. 2017-213191, filed November 2, 2017, is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are as specific and distinct as when individual documents, patent applications, and technical standards are incorporated by reference. Hereby incorporated by reference.

Claims

Applying a coloring ink containing a coloring agent onto the recording medium containing at least one of a urethane resin and a vinyl chloride resin by an inkjet method to form a colored image;
Applying a clear ink containing a vinyl chloride-vinyl acetate copolymer on at least the colored image to form a clear ink layer;
An inkjet recording method comprising:
The ink jet recording method according to claim 1, further comprising the step of thermally fusing a laminate substrate containing at least one of a urethane resin and a vinyl chloride resin on the clear ink layer.
The ink jet recording method according to claim 2, wherein the heat fusion temperature in the heat fusion step is 150 ° C to 220 ° C.
The content of the vinyl chloride-vinyl acetate copolymer contained in the clear ink is 0.5% by mass to 10.0% by mass with respect to the total amount of the clear ink. The inkjet recording method according to any one of the items.
The total content mass of the non-volatile components contained in the clear ink is Mt1
When the content mass of the vinyl chloride-vinyl acetate copolymer contained in the clear ink is Mt2.
5. The ink jet recording method according to any one of claims 1 to 4, wherein Mt2 / Mt1 is 0.40 or more.
The ink jet recording method according to any one of claims 1 to 5, wherein the weight average molecular weight of the vinyl chloride-vinyl acetate copolymer contained in the clear ink is 13,000 to 30,000.
The ink jet recording method according to any one of claims 1 to 6, wherein the colored ink further contains at least one of a vinyl chloride-vinyl acetate copolymer and a polymerizable compound.
The colored ink contains the vinyl chloride-vinyl acetate copolymer,
The ink jet recording method according to claim 7, wherein the weight average molecular weight of the vinyl chloride-vinyl acetate copolymer contained in the colored ink is 13,000 to 30,000.
The colored ink contains the vinyl chloride-vinyl acetate copolymer,
The total content mass of the non-volatile components contained in the clear ink is Mt1
Let the content mass of the vinyl chloride-vinyl acetate copolymer contained in the clear ink be Mt2.
The total content of non-volatile components contained in the colored ink is Mc1
When the mass of the vinyl chloride-vinyl acetate copolymer contained in the colored ink is Mc2,
The ink jet recording method according to claim 7 or 8, wherein Mt1, Mt2, Mc1 and Mc2 satisfy the following formula (1).
Mc2 / Mc1 ≦ Mt2 / Mt1 ... Formula (1)
The ink jet recording method according to any one of claims 1 to 9, wherein the colored ink and the clear ink each contain an organic solvent.
A recording medium containing at least one of a urethane resin and a vinyl chloride resin;
A colored image which is disposed on the recording medium and is an inkjet recording material;
A clear ink layer disposed on at least the colored image on the recording medium and containing a vinyl chloride-vinyl acetate copolymer;
Stack comprising.
The laminate according to claim 11, further comprising a laminate substrate heat-sealed on the clear ink layer and containing at least one of a urethane resin and a vinyl chloride resin.
The laminate according to claim 11 or 12, wherein the ratio of the content weight of the vinyl chloride-vinyl acetate copolymer to the total weight of the clear ink layer is 0.40 or more.